arXiv daily: Materials Science

arXiv daily: Materials Science (cond-mat.mtrl-sci)

1.Microdroplet Approach for Measuring Aqueous Solubility and Nucleation Kinetics of a Metastable Polymorph: The case of KDP Phase IV

Authors:Ruel Cedeno CINaM, AMU, Romain Grossier CINaM, AMU, Nadine Candoni CINaM, AMU, Stéphane Veesler CINaM, AMU

Abstract: Solubility and interfacial energy are two fundamental parameters underlying the competitive nucleation of polymorphs. However, solubility measurement of metastable phases comes with a risk of solventmediated transformations which can render the results unreliable. In this work, we present a rapid microfluidic technique for measuring aqueous solubility of the metastable form using KDP Phase IV as a model system. This bracketing approach involves analyzing the dissolution behavior of crystals in contact with supersaturated microdroplets generated via evaporation. Then, with the help of our recently developed nucleation time measurement technique, together with Mersmann calculation of interfacial energies from solubilities, we were able to access the interfacial energies of both metastable and stable phases. To gain further insights into the observed nucleation behavior, we employed the Classical Nucleation Theory (CNT) to model the competition of polymorphs using our measured solubility and calculated interfacial energies. The results show that the stable form is favored at lower supersaturation while the metastable form is favored at higher supersaturation, in good agreement with our observations and experimental reports in the literature. Overall, our microfluidic approach allows access to unprecedentedly deep levels of supersaturation and reveals an interesting interplay between thermodynamics and kinetics in polymorphic nucleation. The experimental methods and insights presented herein can be of great interest, notably in the mineral processing and pharmaceutical industry.

2.Theoretical study on spintronic and optical property prediction of doped magnetic Borophene

Authors:S. Koley

Abstract: Two dimensional materials are attracting new research for optoelectronics and spintronics due to their unique physical properties. A wide range of emerging spintronic devices are achieved from parent and doped two dimensional materials. First-principles electronic structure calculations of a two-dimensional monolayer of borophene in its P6/mmm form is explored in this study. The electronic, magnetic, and optical properties of doped borophene are analyzed for doping with lithium, sodium, and magnesium. Density functional theory calculations advocate their good dynamical and thermal stability. Spin-polarized electronic properties of these materials are observed to be useful for predicting new spintronic materials. Additionally optical analysis exhibits the absorption peaks in monolayers along the in-plane direction. These properties of doped magnetic borophene suggest the material to be a suitable candidate for designing optoelectronic devices. The most competent spintronic material among three different doped borophenes is lithium doping that can imply a promising avenue for the fast-growing electronics industry.

3.Characterizing MRO in atomistic models of vitreous SiO$_2$ generated using ab-initio molecular dynamics

Authors:Sruti Sangeeta Jena, Shakti Singh, Sharat Chandra

Abstract: Vitreous silica is the most versatile material for scientific and commercial applications. Although large-scale atomistic models of vitreous-SiO$_2$ (v-SiO$_2$) having medium-range order (MRO) have been successfully developed by melt-quench through classical molecular dynamics, the MRO is not well studied for the smaller-scale models developed by melt-quench using ab-initio molecular dynamics (AIMD). In this study, we obtain atomistic models of v-SiO$_2$ by performing melt-quench simulation using AIMD. The final structure is compared with the experimental data and some recent atomistic models, on the basis of the structural properties. Since AIMD allows for the estimation of electronic structure, a detailed study of electronic properties is also done. It shows the presence of defect states mainly due to dangling bonds in the band-gap region of electronic density of states, whereas the edge-shared type of defective structures in the glassy models are found to contribute mainly in the valence band. In addition, Oxygen and Silicon vacancies as well as bridging Oxygen type of defects were created and their contributions to the band-gap were studied.

4.Stable Nanofacets in [111] Tilt Grain Boundaries of Face-Centered Cubic Metals

Authors:Tobias Brink, Lena Langenohl, Swetha Pemma, Christian H. Liebscher, Gerhard Dehm

Abstract: Grain boundaries can dissociate into facets if that reduces their excess energy. This, however, introduces line defects at the facet junctions, which present a driving force to grow the facets in order to reduce the total number of junctions and thus the system's energy. Often, micrometer-sized facet lengths are observed and facet growth only arrests for kinetic reasons. So far, energetically stable, finite-sized facets have not been observed, even though theoretical stability conditions have already been proposed. Here, we show a case where nanometer-sized facets are indeed stable compared to longer facets in [111] tilt grain boundaries in Cu by atomistic simulation and transmission electron microscopy. The facet junctions lack a Burgers vector component, which is unusual, but which leads to attractive interactions via line forces. Atomistic simulations predict that the same phenomenon also occurs in at least Al and Ag.

5.Interlayer-spin-interaction-driven Sliding Ferroelectricity in a van der Waals Magnetic Heterobilayer

Authors:Chengxi Huang, Erjun Kan

Abstract: Sliding ferroelectricity is widely existed in van der Waals (vdW) two-dimensional (2D) multilayers, exhibiting great potential on low-dissipation non-volatile memories. However, in a vdW heterostructure, interlayer sliding usually fails to reverse or distinctly change the electric polarization, which makes the electrical control difficult in practice. Here we propose that in a vdW magnetic system, the interlayer spin interaction could provide an extra degree-of-freedom to remarkably tune the electric polarization. Combining tight-binding model analysis and first-principles calculations, we show that in the CrI3/MnSe2 and other vdW magnetic heterobilayers, the switching of the interlayer magnetic order can greatly change, even reverse the off-plane electronic polarization. Furthermore, interlayer sliding causes a non-volatile switching of the magnetic order and, thus, reverses the electric polarization, suggesting a non-volatile magnetoelectric coupling effect. These findings will significantly advances the development of 2D ferroelectrics and multiferroics for spintronic applications.

6.Chemical Doping-Driven Giant Anomalous Hall and Nernst Conductivity in Magnetic Cubic Heusler Compounds

Authors:Guangzong Xing, Keisuke Masuda, Terumasa Tadano, Yoshio Miura

Abstract: Chemical doping efficiently optimizes the physical properties of Heusler compounds, especially their anomalous transport properties, including anomalous Hall conductivity (AHC) and anomalous Nernst conductivity (ANC). This study systematically investigates the effect of chemical doping on AHC and ANC in 1493 magnetic cubic Heusler compounds using high-throughput first-principles calculations. Notable trends emerge in Co- and Rh-based compounds, where chemical doping effectively enhances the AHC and ANC. Intriguingly, certain doped candidates exhibit outstanding enhancement in AHCs and ANCs, such as (Co$_{0.8}$Ni$_{0.2}$)$_2$FeSn with considerable AHC and ANC values of $-2567.78$~S\,cm$^{-1}$ and $8.27$~A\,m$^{-1}$K$^{-1}$, respectively, and (Rh$_{0.8}$Ru$_{0.2}$)$_2$MnIn with an AHC of $1950.49$~S\,cm$^{-1}$. In particular, an extraordinary ANC of $8.57$~A\,m$^{-1}$K$^{-1}$ is identified exclusively in Rh$_2$Co$_{0.7}$Fe$_{0.3}$In, nearly double the maximum value of $4.36$~A\,m$^{-1}$K$^{-1}$ observed in the stoichiometric Rh$_2$CoIn. A comprehensive band structure analysis underscores that the notable enhancement in ANC arises from the creation and modification of the energy-dependent nodal lines through chemical doping. This mechanism generates a robust Berry curvature, resulting in significant ANCs. These findings emphasize the pivotal role of chemical doping in engineering high-performance materials, thereby expanding the horizons of transport property optimization within Heusler compounds.

7.Facilitating the systematic nanoscale study of battery materials by atom probe tomography through in-situ metal coating

Authors:Mahander P Singh, Eric V Woods, Se Ho Kim, Chanwon Jung, Leonardo S. Aota, Baptiste Gault

Abstract: Through its capability for 3D mapping of Li at the nanoscale, atom probe tomography (APT) is poised to play a key role in understanding the microstructural degradation of lithium-ion batteries (LIB) during successive charge and discharge cycles. However, APT application to materials for LIB is plagued by the field induced delithiation (deintercalation) of Li-ions during the analysis itself that prevents the precise assessment of the Li distribution. Here, we showcase how a thin Cr-coating, in-situ formed on APT specimens of NMC811 in the focused-ion beam (FIB), preserves the sample's integrity and circumvent this deleterious delithiation. Cr-coated specimens demonstrated remarkable improvements in data quality and virtually eliminated premature specimen failures, allowing for more precise measurements via. improved statistics. Through improved data analysis, we reveal substantial cation fluctuations in commercial grade NMC811, including complete grains of LiMnO. The current methodology stands out for its simplicity and cost-effectiveness and is a viable approach to prepare battery cathodes and anodes for systematic APT studies.

1.Lattice Thermal Conductivity from First Principles and Active Learning with Gaussian Process Regression

Authors:Rasmus Tranås, Ole Martin Løvvik, Kristian Berland

Abstract: The lattice thermal conductivity ($\kappa_{\ell}$) is a key materials property in power electronics, thermal barriers, and thermoelectric devices. Identifying a wide pool of compounds with low $\kappa_{\ell}$ is particularly important in the development of materials with high thermoelectric efficiency. The present study contributed to this with a reliable machine learning (ML) model based on a training set consisting of 268 cubic compounds. For those, $\kappa_{\ell}$ was calculated from first principles using the temperature-dependent effective potential (TDEP) method based on forces and phonons calculated by density functional theory (DFT). 238 of these were preselected and used to train an initial ML model employing Gaussian process regression (GPR). The model was then improved with active learning (AL) by selecting the 30 compounds with the highest GPR uncertainty as new members of an expanded training set. This was used to predict $\kappa_{\ell}$ of the 1574 cubic compounds in the \textsc{Materials Project} (MP) database with a validation R2-score of 0.81 and Spearman correlation of 0.93. Out of these, 27 compounds were predicted to have very low values of $\kappa_{\ell}$ ($\leq 1.3$ at 300~K), which was verified by DFT calculations. Some of these have not previously been reported in the literature, suggesting further investigations of their electronic thermoelectric properties.

2.Computing solubility and thermodynamics properties of H2O2 in water

Authors:Tijin H. G. Saji, José Manuel Vicent-Luna, Thijs J. H. Vlugt, Sofía Calero, Behnaz Bagheri

Abstract: Hydrogen peroxide plays a key role in many environmental and industrial chemical processes. We performed classical Molecular Dynamics and Continuous Fractional Component Monte Carlo simulations to calculate thermodynamic properties of H2O2 in aqueous solutions. The quality of the available force fields for H2O2 developed by Orabi & English, and by Cordeiro was systematically evaluated. To assess which water force field is suitable for predicting properties of H2O2 in aqueous solutions, four water force fields were used, namely the TIP3P, TIP4P/2005, TIP5P-E, and a modified TIP3P force field. While the computed densities of pure H2O2 in the temperature range of 253-353 K using the force field by Orabi & English are in excellent agreement with experimental results, the densities using the force field by Cordeiro are underestimated by 3%. The TIP4P/2005 force field in combination with the H2O2 force field developed by Orabi & English can predict the densities of H2O2 aqueous solution for the whole range of H2O2 mole fractions in very good agreement with experimental results. The TIP4P/2005 force field in combination with either of the H2O2 force fields can predict the viscosities of H2O2 aqueous solutions for the whole range of H2O2 mole fractions in good agreement with experimental results. The diffusion coefficients for H2O2 and water molecules using the TIP4P/2005 force field with either of the H2O2 force fields are almost constant for the whole range of H2O2 mole fractions. The Cordeiro force field for H2O2 in combination with either of the water force fields can predict the Henry coefficients of H2O2 in water in better agreement with experimental values than the force field by Orabi & English.

3.Funneling and spin-orbit coupling in transition-metal dichalcogenide nanotubes and wrinkles

Authors:Mohammadreza Daqiqshirazi, Thomas Brumme

Abstract: Strain engineering provides a powerful means to tune the properties of two-dimensional materials. Accordingly, numerous studies have investigated the effect of bi- and uniaxial strain. Yet, the strain fields in many systems such as nanotubes and nanoscale wrinkles are intrinsically inhomogeneous and the consequences of this symmetry breaking are much less studied. Understanding how this affects the electronic properties is crucial especially since wrinkling is a powerful method to apply strain to two-dimensional materials in a controlled manner. In this paper, we employ density functional theory to understand the correlation between the atomic and the electronic structure in nanoscale wrinkles and nanotubes of the prototypical transition metal dichalcogenide $\mathrm{WSe}_2$. Our research shows that the symmetry breaking in these structures leads to strong Rashba-like splitting of the bands at the $\Gamma$ point and they thus may be utilized in future tunable spintronic devices. The inhomogeneous strain reduces the band gap and leads to a localization of the band edges in the highest-curvature region, thus funneling excitons there. Moreover, we show how wrinkles can be modeled as nanotubes with the same curvature and when this comparison breaks down and further inhomogenities have to be taken into account.

4.Magnon gap excitations in van der Waals antiferromagnet MnPSe$_3$

Authors:Dipankar Jana, D. Vaclavkova, I. Mohelsky, P. Kapuscinski, C. W. Cho, I. Breslavetz, M. Białek, J. -Ph. Ansermet, B. A. Piot, M. Orlita, C. Faugeras, M. Potemski

Abstract: Magneto-spectroscopy methods have been employed to study the zero-wavevector magnon excitations in MnPSe$_3$. Experiments carried out as a function of temperature and the applied magnetic field show that two low-energy magnon branches of MnPSe$_3$ in its antiferromagnetic phase are gapped. The observation of two low-energy magnon gaps (at 14 and 0.7 cm$^{-1}$) implies that MnPSe$_3$ is a biaxial antiferromagnet. A relatively strong out-of-plane anisotropy imposes the spin alignment to be in-plane whereas the spin directionality within the plane is governed by a factor of 2.5 $\times$ 10$^{-3}$ weaker in-plane anisotropy.

5.Calculating the Stability of Different Surfaces of GaAsxP1-x Mixed-Crystals using the Virtual Crystal Approximation

Authors:Marsel Karmo, Hartmut Grille, Isaac Azahel Ruiz Alvarado

Abstract: The theoretical treatment of mixed-crystals is very demanding. A straight-forward approach to attack this problem is using a super cell method (SCM). Another one is the Virtual Crystal Approximation (VCA), which is an undocumented feature of the Vienna Ab initio Simulation Package (VASP). For comparison we use both methods to calculate the total energy (Etot) and the density of states (DOS) of bulk GaAsxP1-x. We then apply VCA to compute the stability of different surfaces using an extended version of the surface formation energy Omega. Our calculations show, on one hand, a working VCA implementation with its flaws (overestimation of Etot) and strengths (well modelling of DOS). On other hand, a further result is that bulk of the slab of a mixed-crystal has a minor influence on the configuration of the surface.

6.Modeling Dislocation Dynamics Data Using Semantic Web Technologies

Authors:Ahmad Zainul Ihsan, Said Fathalla, Stefan Sandfeld

Abstract: Research in the field of Materials Science and Engineering focuses on the design, synthesis, properties, and performance of materials. An important class of materials that is widely investigated are crystalline materials, including metals and semiconductors. Crystalline material typically contains a distinct type of defect called "dislocation". This defect significantly affects various material properties, including strength, fracture toughness, and ductility. Researchers have devoted a significant effort in recent years to understanding dislocation behavior through experimental characterization techniques and simulations, e.g., dislocation dynamics simulations. This paper presents how data from dislocation dynamics simulations can be modeled using semantic web technologies through annotating data with ontologies. We extend the already existing Dislocation Ontology by adding missing concepts and aligning it with two other domain-related ontologies (i.e., the Elementary Multi-perspective Material Ontology and the Materials Design Ontology) allowing for representing the dislocation simulation data efficiently. Moreover, we show a real-world use case by representing the discrete dislocation dynamics data as a knowledge graph (DisLocKG) that illustrates the relationship between them. We also developed a SPARQL endpoint that brings extensive flexibility to query DisLocKG.

7.Anomalous Hall effect and magnetoresistance in micro-ribbons of the magnetic Weyl semimetal candidate PrRhC2

Authors:Mickey Martini, Helena Reichlova, Laura T. Corredor, Dominik Kriegner, Yejin Lee, Luca Tomarchio, Kornelius Nielsch, Ali G. Moghaddam, Jeroen van den Brink, Bernd Büchner, Sabine Wurmehl, Vitaliy Romaka, Andy Thomas

Abstract: PrRhC2 belongs to the rare-earth carbides family whose properties are of special interest among topological semimetals due to the simultaneous breaking of both inversion and time-reversal symmetry. The concomitant absence of both symmetries grants the possibility to tune the Weyl nodes chirality and to enhance topological effects like the chiral anomaly. In this work, we report on the synthesis and compare the magnetotransport measurements of a poly- and single crystalline PrRhC2 sample. Using a remarkable and sophisticated technique, the PrRhC2 single crystal is prepared via focused ion beam cutting from the polycrystalline material. Our magnetometric and specific heat analyses reveal a non-collinear antiferromagnetic state below 20K, as well as short-range magnetic correlations and/or magnetic fluctuations well above the onset of the magnetic transition. The transport measurements on the PrRhC2 single crystal display an electrical resistivity peak at 3K and an anomalous Hall effect below 6K indicative of a net magnetization component in the ordered state. Furthermore, we study the angular variation of magnetoresistivities as a function of the angle between the in-plane magnetic field and the injected electrical current. We find that both the transverse and the longitudinal resistivities exhibit fourfold angular dependencies due to higher-order terms in the resistivity tensor, consistent with the orthorhombic crystal symmetry of PrRhC2. Our experimental results may be interpreted as features of topological Weyl semimetallic behavior in the magnetotransport properties.

8.Amorphous VO$_x$ films with high temperature coefficient of the resistivity grown by reactive e-beam evaporation of V metal

Authors:E. V. Tarkaeva, V. A. Ievleva, A. I. Duleba, A. V. Muratov, A. Yu. Kuntsevich

Abstract: Amorphous VO$_x$ films without a hysteretic phase transition are stable with respect to thermal cycling and highly demanded as sensitive elements of the resistive thermometers and microbolometers. In this paper we present simple and low-temperature growth of amorphous vanadium oxide films by reactive electron beam evaporation of vanadium metal in $\sim 10^{-4}$ mBar oxygen atmosphere. The temperature coefficient of the resistivity (TCR) of the films is weakly sensitive to substrate material and temperature and could be tuned by oxygen pressure in the growth chamber up to -2.2\% /K. The resistivity value is stable for months. It depends on the substrate material and substrate temperature during the evaporation. Simplicity and controllability of the method should lead to various laboratory and industrial applications.

9.Prediction of Van Hove singularity systems in ternary borides

Authors:Yang Sun, Zhen Zhang, Andrew P Porter, Kirill Kovnir, Kai-Ming Ho, Vladimir Antropov

Abstract: A computational search for stable structures among both $\alpha$ and $\beta$ phases of ternary ATB4 borides (A= Mg, Ca, Sr, Ba, Al, Ga, and Zn, T is 3d or 4d transition elements) has been performed. We found that $\alpha$-ATB4 compounds with A=Mg, Ca, Al, and T=V, Cr, Mn, Fe, Ni, and Co form a family of structurally stable or almost stable materials. These systems are metallic in non-magnetic states and characterized by the formation of the localized molecular-like state of 3d transition metal atom dimers, which leads to the appearance of numerous Van Hove singularities (VHS) in the electronic spectrum. The closeness of these VHS to the Fermi level can be easily tuned by electron doping. For the atoms in the middle of the 3d row (Cr, Mn, and Fe), these VHS led to magnetic instabilities and new magnetic ground states with a weakly metallic or semiconducting nature. The magnetic ground states in these systems appear as an analog of the spin glass state. Experimental attempts to produce MgFeB4 and associated challenges are discussed, and promising directions for further synthetic studies are formulated.

1.Electronic structure and optoelectronic properties of halide double perovskites: Fundamental insights and design of a theoretical workflow

Authors:Mayank Gupta, Susmita Jana, B. R. K. Nanda

Abstract: Like single perovskites, halide double perovskites (HDP) have truly emerged as efficient optoelectronic materials since they display superior stability and are free of toxicity. However, challenges still exist due to either wide and indirect bandgaps or parity-forbidden transitions in many of them. The lack of understanding in chemical bonding and the formation of parity-driven valence and conduction band edge states have hindered the design of optoelectronically efficient HDPs. In this study, we have developed a theoretical workflow using a multi-integrated approach involving ab-initio density functional theory (DFT) calculations, model Hamiltonian studies, and molecular orbital picture leading to momentum matrix element (MME) estimation. This workflow gives us detailed insight into chemical bonding and parity-driven optical transition between edge states. In the process, we have developed a band-projected molecular orbital picture (B-MOP) connecting free atomic orbital states obtained at the Hartree-Fock level and orbital-resolved DFT bands. From the B-MOP, we show that the nearest neighbor cation-anion interaction determines the position of atom-resolved band states, while the second neighbor cation-cation interactions determine the shape and width of band dispersion and, thereby, MME. The latter is critical to quantify the optical absorption coefficient. Considering both B-MOP and MME, we demonstrate a mechanism of tailoring bandgap and optical absorptions through chemical doping at the cation sites. Furthermore, the cause of bandgap bowing, a common occurrence in doped HDPs, is explained by ascribing it to chemical effect and structural distortion.

2.A robust synthetic data generation framework for machine learning in High-Resolution Transmission Electron Microscopy (HRTEM)

Authors:Luis Rangel DaCosta, Katherine Sytwu, Catherine Groschner, Mary Scott

Abstract: Machine learning techniques are attractive options for developing highly-accurate automated analysis tools for nanomaterials characterization, including high-resolution transmission electron microscopy (HRTEM). However, successfully implementing such machine learning tools can be difficult due to the challenges in procuring sufficiently large, high-quality training datasets from experiments. In this work, we introduce Construction Zone, a Python package for rapidly generating complex nanoscale atomic structures, and develop an end-to-end workflow for creating large simulated databases for training neural networks. Construction Zone enables fast, systematic sampling of realistic nanomaterial structures, and can be used as a random structure generator for simulated databases, which is important for generating large, diverse synthetic datasets. Using HRTEM imaging as an example, we train a series of neural networks on various subsets of our simulated databases to segment nanoparticles and holistically study the data curation process to understand how various aspects of the curated simulated data -- including simulation fidelity, the distribution of atomic structures, and the distribution of imaging conditions -- affect model performance across several experimental benchmarks. Using our results, we are able to achieve state-of-the-art segmentation performance on experimental HRTEM images of nanoparticles from several experimental benchmarks and, further, we discuss robust strategies for consistently achieving high performance with machine learning in experimental settings using purely synthetic data.

3.High-pressure hydrothermal growth and characterization of Sr3Os4O14 single crystals

Authors:N. D. Zhigadlo

Abstract: Single crystals of the novel strontium osmate Sr3Os4O14 have been grown by the hydrothermal method using opposed anvil high-pressure and high-temperature technique. The reaction took place in sealed gold capsules at 3 GPa and a temperature of 1100 C, with water acting as a solvent. The employed method yields up to 1 mm crystals with quite uncommon double-terminated morphologies. The crystal structure was identified as tetragonal by single-crystal X-ray diffraction, with lattice parameters a = 12.2909(8) A and c = 7.2478(5) A. The structural analysis suggests P42nm or P42/mnm as a possible space group. In general, the structure belongs to the pyrochlore type and is composed of a network of symmetrically arranged OsO6 octahedra. Resistivity measurements evidence a metallic behavior, accompanied by a temperature-independent paramagnetism. Heat capacity measurements reveal a slightly enhanced value of the Sommerfeld coefficient 34 mJ/mol K2. Superconductivity has not been observed down to 2 K.

4.Developing correlation-consistent numeric atom-centered orbital basis sets for Krypton: Applications in RPA-based correlated calculations

Authors:Sixian Yang, Igor Ying Zhang, Xinguo Ren

Abstract: Localized atomic orbitals are the preferred basis-set choice for large-scale explicit correlated calculations, and high-quality hierarchical correlation-consistent basis sets are a prerequisite for correlated methods to deliver numerically reliable results. At present, Numeric Atom-centered Orbital (NAO) basis sets with valence correlation consistency (VCC), designated as NAO-VCC-$n$Z, are only available for light elements from hydrogen (H) to argon (Ar) (\textit{New J. Phys.} \textbf{15}, 123033, (2013) ). In this work, we extend this series by developing NAO-VCC-$n$Z basis sets for krypton (Kr), a prototypical element in the fourth row of periodic table. We demonstrate that NAO-VCC-$n$Z basis sets facilitate the convergence of electronic total-energy calculations using the Random Phase Approximation (RPA), which can be used together with a two-point extrapolation scheme to approach the complete-basis-set (CBS) limit. Notably, the Basis Set Superposition Error (BSSE) associated with the newly generated NAO basis sets is minimal, making them suitable for applications where BSSE correction is either cumbersome or impractical to do. After confirming the reliability of NAO basis sets for Kr, we proceed to calculate the Helmholtz free energy for Kr crystal at the theoretical level of RPA plus renormalized single excitation (rSE) correction. From this, we derive the pressure-volume ($P$-$V$) diagram, which shows excellent agreement with the latest experimental data. Our work demonstrates the capability of correlation-consistent NAO basis sets for heavy elements, paving the way toward numerically reliable correlated calculations for bulk materials.

5.Distinguishing the importance of different charge trapping centers in CaF2-based 2D material MOSFETs

Authors:Zhe Zhao, Tao Xiong, Jian Gong, Yue-Yang Liu

Abstract: Crystalline CaF2 is drawing huge attentions due to its great potential of being the gate dielectric of two-dimensional (2D) material MOSFETs. It is deemed to be much superior than boron nitride and traditional SiO2 because of its larger dielectric constant, wider band gap, and lower defect density. Nevertheless, the CaF2-based MOSFETs fabricated in experiment still present notable reliability issues, and the underlying reason remains unclear. Here we studied the various intrinsic defects and adsorbates in CaF2/MoS2 and CaF2/MoSi2N4 interface systems to reveal the most active charge trapping centers in CaF2-based 2D material MOSFETs. An elaborate Table that comparing the importance of different defects in both n-type and p-type device is provided. Most impressively, the oxygen molecules adsorbed at the interface or surface, which are inevitable in experiments, are as active as the intrinsic defects in channel materials, and they can even change the MoSi2N4 to p-type spontaneously. These results mean that it is necessary to develop high vacuum packaging process as well as preparing high-quality 2D materials for better device performance.

6.Optoelectronic and Transport Properties of Vacancy Ordered Double Perovskite Halides: A First-principles Study

Authors:Supriti Ghorui, Jiban Kangsabanik, M. Aslam, Aftab Alam

Abstract: In the search for stable lead (Pb) free perovskites, Vacancy ordered double perovskite (VODP), A$_2$BX$_6$ has emerged as a promising class of materials for solar harvesting owing to their nontoxicity, better stability, and unique optoelectronic properties. Here, we present the stability and the key physical attributes of few selected compounds in a systematic manner using state-of-the-art first-principle calculations. A careful structural and stability analysis via simulating convex hull and compositional phase diagrams for different structural prototypes discloses 14 stable and 1 metastable compounds in this class. The electronic structure calculations using hybrid functional reveals six compounds to acquire band gap in the ideal visible region. These six compounds, namely Cs$_2$SnI$_6$, Cs$_2$PdI$_6$, Cs$_2$TeI$_6$, Cs$_2$TiI$_6$, Cs$_2$PtI$_6$, and Cs$_2$PdBr$_6$, show high optical absorption ($\approx$ 10$^{5}$ cm $^{-1}$) giving rise to high spectroscopic limited maximum efficiency, SLME (15-23\%) in the thin-film thickness range. Close inspection of transport properties reveals polar optical phonon scattering to be the dominant mechanism limiting the overall mobility. Further analysis of the polaron excitations discloses the possibility of large polaron formation at low to moderate defect concentrations. At high defect concentrations, ionized impurity scattering takes over. This suggests that, a simulation based guided control of defect concentrations during synthesis can yield a desired candidate for promissing device application. Additionally, few selected compounds show moderate to high electron mobility values ($\sim$13-63 cm$^2$V$^{-1}$ s$^{-1}$) at room temperature. Overall, the present study paves an important path to help design VODP as Pb-free potential candidates for future optoelectronic applications.

7.Design monolayer iodinenes based on halogen bond and tiling theory

Authors:Kejun Yu, Botao Fu, Runwu Zhang, Da-shuai Ma, Xiao-ping Li, Zhi-Ming Yu, Cheng-Cheng Liu, Yugui Yao

Abstract: Xenes, two-dimensional (2D) monolayers composed of a single element, with graphene as a typical representative, have attracted widespread attention. Most of the previous Xenes, X from group-IIIA to group-VIA elements have bonding characteristics of covalent bonds. In this work, we for the first time unveil the pivotal role of a halogen bond, which is a distinctive type of bonding with interaction strength between that of a covalent bond and a van der Waals interaction, in 2D group-VIIA monolayers. Combing the ingenious non-edge-to-edge tiling theory and state-of-art ab initio method with refined local density functional M06-L, we provide a precise and effective bottom-up construction of 2D iodine monolayer sheets, iodinenes, primarily governed by halogen bonds, and successfully design a category of stable iodinenes, encompassing herringbone, Pythagorean, gyrated truncated hexagonal, i.e. diatomic-kagome, and gyrated hexagonal tiling pattern. These iodinene structures exhibit a wealth of properties, such as flat bands, nontrivial topology, and fascinating optical characteristics, offering valuable insights and guidance for future experimental investigations. Our work not only unveils the unexplored halogen bonding mechanism in 2D materials but also opens a new avenue for designing other non-covalent bonding 2D materials.

8.Proximity-induced interfacial room-temperature ferromagnetism in semiconducting Fe3GeTe2

Authors:Qianwen Zhao, Yingmei Zhu, Hanying Zhang, Baiqing Jiang, Yuan Wang, Tunan Xie, Kaihua Lou, ChaoChao Xia, Hongxin Yang, C. Bi

Abstract: The discoveries of two-dimensional ferromagnetism and magnetic semiconductors highly enrich the magnetic material family for constructing spin-based electronic devices but with an acknowledged challenge that the Curie temperature (Tc) is usually far below room temperature. Many efforts such as voltage control and magnetic ion doping are currently underway to enhance the functional temperature, in which the involvement of additional electrodes or extra magnetic ions limits their plenty of applications in practical devices. Here we demonstrate that the magnetic proximity, a robust effect but with elusive mechanisms, can induce room-temperature ferromagnetism at the interface between sputtered Pt and semiconducting Fe3GeTe2, both of which do not show ferromagnetism at 300 K. The independent electrical and magnetization measurements, structure analysis, and control samples with Ta highlighting the role of Pt confirm that the ferromagnetism with the Tc of above 400 K arises from the Fe3GeTe2/Pt interfaces, rather than Fe aggregation or other artificial effects. Moreover, contrary to conventional ferromagnet/Pt structures, the spin current generated by the Pt layer is enhanced more than two times at the Fe3GeTe2/Pt interfaces, indicating the potential applications of the unique proximity effect in building high-efficient spintronic devices. These results may pave a new avenue to create room-temperature functional spin devices based on low-Tc materials and provide clear evidences of magnetic proximity effects by using non-ferromagnetic materials.

9.Probing spatial variation of magnetic order in strained SrMnO$_3$ thin films using Spin Hall Magnetoresistance

Authors:J. J. L. van Rijn, T. Banerjee

Abstract: SrMnO$_{3}$ (SMO) is a magnetic insulator and predicted to exhibit a multiferroic phase upon straining. Strained films of SMO display a wide range of magnetic orders, ranging from G-type to C-and A-type, indicative of competing magnetic interactions. The potential of spin Hall magnetoresistance (SMR) is exploited as an electrical probe for detecting surface magnetic order, to read surface magnetic moments in SMO and its spatial variation, by designing and positioning electrodes of different sizes on the film. The findings demonstrate antiferromagnetic domains with different magnetocrystalline anisotropies along with a ferromagnetic order, where the magnetization arises from double exchange mediated ferromagnetic order and canted antiferromagnetic moments. Further, from a complete analysis of the SMR, a predominance of antiferromagnetic domain sizes of 3.5 $\mu$m$^2$ is extracted. This work enhances the applicability of SMR in unraveling the richness of correlation effects in complex oxides, as manifested by the detection of coexisting and competing ground states and lays the foundation for the study of magnon transport for different magnetoelectric based computing applications.

10.Investigating the Cocoon Effect in Niobium-Copper Alloy: Metallic Nano-Precipitate Distribution and Niobium Migration

Authors:Rogério L. de Almeida, José-Albino O. Aguiar, Carlos A. C. Passos

Abstract: We report the observation of the metallic niobium migration within the molten Cu-Nb alloy mass on the synthesis of nano-granular Cuxwt\%Nb evolution, we prepared a series of granular samples by rapidly cooling a molten mixture of Cuxwt\%Nb, where the niobium concentration varied (x=3,5,15,20). Our main goal in this work was not only to establish a systematic, innovative and robust method to obtaining good quality samples, but also provide a clear recipe for obtaining similar systems to the investigations of their interesting physical properties. Beyond the understanding of the Cocoon Effect in Niobium-Copper alloys, we include a wide complementary elsewhere investigation into the very interesting and rich superconducting properties exhibited by the Niobium-Copper alloy. By employing a robust synthesis method, we successfully obtained samples characterized by well-defined spherical nano-precipitates of niobium, featuring regular sizes and grain spacing. Our study contributes not only to our understanding of the Niobium-Copper molten phase separation, micro-structure and the Cocoon Effect in these metallic alloys, but also sheds light on the intricate and important implications for the development and optimization of good quality granular metallic alloys for various applications. From our work, we obtained very impressive micro structural results, such as: $ d_{m} $ = 1.2 \mu, $ D_{m} $\le 2.2 \mu$m$ \ and \ \rho =1.785 \mu$m^{2}$, where $ d_{m} $ is the distance between Niobium grains, $D_{m}$ is the mean diameter of Niobium grains and \rho$ is the Niobium grain mean density in the Copper matrix.

11.A universal interatomic potential for perovskite oxides

Authors:Jing Wu, Jiyuan Yang, Yuan-Jinsheng Liu, Duo Zhang, Yudi Yang, Yuzhi Zhang, Linfeng Zhang, Shi Liu

Abstract: With their celebrated structural and chemical flexibility, perovskite oxides have served as a highly adaptable material platform for exploring emergent phenomena arising from the interplay between different degrees of freedom. Molecular dynamics (MD) simulations leveraging classical force fields, commonly depicted as parameterized analytical functions, have made significant contributions in elucidating the atomistic dynamics and structural properties of crystalline solids including perovskite oxides. However, the force fields currently available for solids are rather specific and offer limited transferability, making it time-consuming to use MD to study new materials systems since a new force field must be parameterized and tested first. The lack of a generalized force field applicable to a broad spectrum of solid materials hinders the facile deployment of MD in computer-aided materials discovery (CAMD). Here, by utilizing a deep-neural network with a self-attention scheme, we have developed a unified force field that enables MD simulations of perovskite oxides involving 14 metal elements and conceivably their solid solutions with arbitrary compositions. Notably, isobaric-isothermal ensemble MD simulations with this model potential accurately predict the experimental phase transition sequences for several markedly different ferroelectric oxides, including a 6-element ternary solid solution, Pb(In$_{1/2}$Nb$_{1/2}$)O$_3$--Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_3$--PbTiO$_3$. We believe the universal interatomic potential along with the training database, proposed regression tests, and the auto-testing workflow, all released publicly, will pave the way for a systematic improvement and extension of a unified force field for solids, potentially heralding a new era in CAMD.

12.In operando cryo-STEM of pulse-induced charge density wave switching in TaS$_2$

Authors:James L Hart, Saif Siddique, Noah Schnitzer, Stephen D. Funni, Lena F. Kourkoutis, Judy J. Cha

Abstract: The charge density wave (CDW) material 1T-TaS$_2$ exhibits a pulse-induced insulator-to-metal transition, which shows promise for next-generation electronics such as memristive memory and neuromorphic hardware. However, the rational design of TaS$_2$ devices is hindered by a poor understanding of the switching mechanism, the pulse-induced phase, and the influence of material defects. Here, we operate a 2-terminal TaS$_2$ device within a scanning transmission electron microscope (STEM) at cryogenic temperature, and directly visualize the changing CDW structure with nanoscale spatial resolution and down to 300 {\mu}s temporal resolution. We show that the pulse-induced transition is driven by Joule heating, and that the pulse-induced state corresponds to nearly commensurate and incommensurate CDW phases, depending on the applied voltage amplitude. With our in operando cryo-STEM experiments, we directly correlate the CDW structure with the device resistance, and show that dislocations significantly impact device performance. This work resolves fundamental questions of resistive switching in TaS$_2$ devices critical for engineering reliable and scalable TaS$_2$ electronics.

13.Wurtzite vs rock-salt MnSe epitaxy: electronic and altermagnetic properties

Authors:Michał J. Grzybowski, Carmine Autieri, Jarosław Domagała, Cezary Krasucki, Anna Kaleta, Sławomir Kret, Katarzyna Gas, Maciej Sawicki, Rafał Bożek, Jan Suffczyński, Wojciech Pacuski

Abstract: Newly discovered altermagnets are magnetic materials exhibiting both compensated magnetic order, similar to antiferromagnets, and simultaneous non-relativistic spin-splitting of the bands, akin to ferromagnets. This characteristic arises from the specific symmetry operations that connect the spin sublattices. In this report, we show with ab initio calculations that the semiconductive MnSe exhibits altermagnetic spin-splitting in the wurtzite phase as well as a critical temperature well above room temperature. It is the first material from such space group identified to possess altermagnetic properties. Furthermore, we demonstrate experimentally through structural characterization techniques that it is possible to obtain thin films of both the intriguing wurtzite phase of MnSe and the more common rock-salt MnSe using molecular beam epitaxy on GaAs substrates. The choice of buffer layers plays a crucial role in determining the resulting phase and consequently extends the array of materials available for the physics of altermagnetism.

14.Accelerating Defect Predictions in Semiconductors Using Graph Neural Networks

Authors:Md Habibur Rahman, Prince Gollapalli, Panayotis Manganaris, Satyesh Kumar Yadav, Ghanshyam Pilania, Brian DeCost, Kamal Choudhary, Arun Mannodi-Kanakkithodi

Abstract: Here, we develop a framework for the prediction and screening of native defects and functional impurities in a chemical space of Group IV, III-V, and II-VI zinc blende (ZB) semiconductors, powered by crystal Graph-based Neural Networks (GNNs) trained on high-throughput density functional theory (DFT) data. Using an innovative approach of sampling partially optimized defect configurations from DFT calculations, we generate one of the largest computational defect datasets to date, containing many types of vacancies, self-interstitials, anti-site substitutions, impurity interstitials and substitutions, as well as some defect complexes. We applied three types of established GNN techniques, namely Crystal Graph Convolutional Neural Network (CGCNN), Materials Graph Network (MEGNET), and Atomistic Line Graph Neural Network (ALIGNN), to rigorously train models for predicting defect formation energy (DFE) in multiple charge states and chemical potential conditions. We find that ALIGNN yields the best DFE predictions with root mean square errors around 0.3 eV, which represents a prediction accuracy of 98 % given the range of values within the dataset, improving significantly on the state-of-the-art. Models are tested for different defect types as well as for defect charge transition levels. We further show that GNN-based defective structure optimization can take us close to DFT-optimized geometries at a fraction of the cost of full DFT. DFT-GNN models enable prediction and screening across thousands of hypothetical defects based on both unoptimized and partially-optimized defective structures, helping identify electronically active defects in technologically-important semiconductors.

1.Iterative Phase Retrieval Algorithms for Scanning Transmission Electron Microscopy

Authors:Georgios Varnavides, Stephanie M. Ribet, Steven E. Zeltmann, Yue Yu, Benjamin H. Savitzky, Vinayak P. Dravid, Mary C. Scott, Colin Ophus

Abstract: Scanning transmission electron microscopy (STEM) has been extensively used for imaging complex materials down to atomic resolution. The most commonly employed STEM imaging modality of annular dark field produces easily-interpretable contrast, but is dose-inefficient and produces little to no contrast for light elements and weakly-scattering samples. An alternative is to use phase contrast STEM imaging, enabled by high speed detectors able to record full images of a diffracted STEM probe over a grid of scan positions. Phase contrast imaging in STEM is highly dose-efficient, able to measure the structure of beam-sensitive materials and even biological samples. Here, we comprehensively describe the theoretical background, algorithmic implementation details, and perform both simulated and experimental tests for three iterative phase retrieval STEM methods: focused-probe differential phase contrast, defocused-probe parallax imaging, and a generalized ptychographic gradient descent method implemented in two and three dimensions. We discuss the strengths and weaknesses of each of these approaches using a consistent framework to allow for easier comparison. This presentation of STEM phase retrieval methods will make these methods more approachable, reproducible and more readily adoptable for many classes of samples.

2.Highly strain-tunable charge valley transport in bismuth

Authors:Suguru Hosoi, Fumu Tachibana, Mai Sakaguchi, Kentaro Ishida, Masaaki Shimozawa, Koichi Izawa, Yuki Fuseya, Yuto Kinoshita, Masashi Tokunaga

Abstract: The manipulation of the valley degree of freedom can boost the technological development of novel functional devices based on valleytronics. Here, we demonstrate the valley-dependent charge transport controlled by the external strain for bismuth with three equivalent electron valleys. The strain response of resistance, namely elastoresistance, exhibits the evolutions in both antisymmetric and symmetric channels with decreasing temperature. Our developed semiclassical transport model that captures the essence of elastoresistance behaviors pinpoints the primary role of changes in valley density depending on the symmetry of the induced strain, which is consistent with the results of strain-dependent quantum oscillation measurements. These facts suggest the successful tune and evaluation of the valley populations through strain-dependent charge valley transport.

3.Janus-graphene: a two-dimensional half-auxetic carbon allotropes with non-chemical Janus configuration

Authors:Linfeng Yu, Jianhua Xu, Chen Shen, Hongbin Zhang, Xiong Zheng, Huiming Wang, Zhenzhen Qin, Guangzhao Qin

Abstract: The asymmetric properties of Janus two-dimensional materials commonly depend on chemical effects, such as different atoms, elements, material types, etc. Herein, based on carbon gene recombination strategy, we identify an intrinsic non-chemical Janus configuration in a novel purely sp$^2$ hybridized carbon monolayer, named as Janus-graphene. With the carbon gene of tetragonal, hexagonal, and octagonal rings, the spontaneous unilateral growth of carbon atoms drives the non-chemical Janus configuration in Janus-graphene, which is totally different from the chemical effect in common Janus materials such as MoSSe. A structure-independent half-auxetic behavior is mapped in Janus-graphene that the structure maintains expansion whether stretched or compressed, which lies in the key role of $p_z$ orbital. The unprecedented half-auxeticity in Janus-graphene extends intrinsic auxeticity into pure sp$^2$ hybrid carbon configurations. With the unique half-auxeticity emerged in the non-chemical Janus configuration, Janus-graphene enriches the functional carbon family as a promising candidate for micro/nanoelectronic device applications.

4.Superfolded configuration induced low thermal conductivity in two-dimensional carbon allotropes revealed via machine learning force constant potential

Authors:Linfeng Yu, Kexin Dong, Qi Yang, Yi Zhang, Xiong Zheng, Huimin Wang, Zhenzhen Qin, Guangzhao Qin

Abstract: Understanding the fundamental link between structure and functionalization is crucial for the design and optimization of functional materials, since different structural configurations could trigger materials to demonstrate diverse physical, chemical, and electronic properties. However, the correlation between crystal structure and thermal conductivity (\k{appa}) remains enigmatic. In this study, taking two-dimensional (2D) carbon allotropes as study cases, we utilize phonon Boltzmann transport equation (BTE) along with machine learning force constant potential to thoroughly explore the complex folding structure of pure sp2 hybridized carbon materials from the perspective of crystal structure, mode-level phonon resolved thermal transport, and atomic interactions, with the goal of identifying the underlying relationship between 2D geometry and \k{appa}. We propose two potential structure evolution mechanisms for targeted thermal transport properties: in-plane and out-of-plane folding evolutions, which are generally applicable to 2D carbon allotropes. It is revealed that the folded structure produces strong symmetry breaking, and simultaneously produces exceptionally strongly suppressed phonon group velocities, strong phonon-phonon scattering, and weak phonon hydrodynamics, which ultimately lead to low \k{appa}. The insight into the folded effect of atomic structures on thermal transport deepens our understanding of the relationship between structure and functionalization, which offers straightforward guidance for designing novel nanomaterials with targeted \k{appa}, as well as propel developments in materials science and engineering.

5.Chemisorption Induced Formation of Biphenylene Dimer on Surfaces

Authors:Zhiwen Zeng, Dezhou Guo, Tao Wang, Qifan Chen, Adam Matěj, Jianmin Huang, Dong Han, Qian Xu, Aidi Zhao, Pavel Jelínek, Dimas G. de Oteyza, Jean-Sabin McEwen, Junfa Zhu

Abstract: We report an example that demonstrates the clear interdependence between surface-supported reactions and molecular adsorption configurations. Two biphenyl-based molecules with two and four bromine substituents, i.e. 2,2-dibromo-biphenyl (DBBP) and 2,2,6,6-tetrabromo-1,1-biphenyl (TBBP), show completely different reaction pathways on a Ag(111) surface, leading to the selective formation of dibenzo[e,l]pyrene and biphenylene dimer, respectively. By combining low-temperature scanning tunneling microscopy, synchrotron radiation photoemission spectroscopy, and density functional theory calculations, we unravel the underlying reaction mechanism. After debromination, a bi-radical biphenyl can be stabilized by surface Ag adatoms, while a four-radical biphenyl undergoes spontaneous intramolecular annulation due to its extreme instability on Ag(111). Such different chemisorption-induced precursor states between DBBP and TBBP consequently lead to different reaction pathways after further annealing. In addition, using bond-resolving scanning tunneling microscopy and scanning tunneling spectroscopy, we determine the bond length alternation of biphenylene dimer product with atomic precision, which contains four-, six-, and eight-membered rings. The four-membered ring units turn out to be radialene structures.

6.Thermal Raman study of Li4Ti5O12 and discussion about the number of its characteristic bands

Authors:Aleksey A. Nikiforov, Alexander S. Krylov, Svetlana N. Krylova, Vadim S. Gorshkov, Dmitry V. Pelegov

Abstract: Lithium battery industry is booming, and this fast growth should be supported by developing industry friendly tools to control the quality of positive and negative electrode materials. Raman spectroscopy was shown to be a cost effective and sensitive instrument to study defects and heterogeneities in lithium titanate, popular negative electrode material for high power applications, but there are still some points to be clarified. This work presents a detailed thermal Raman study for lithium titanate and discusses the difference of the number of predicted and experimentally observed Raman-active bands. The low temperature study and the analysis of thermal shifts of bands positions during heating let us to conclude about advantages of the proposed approach with surplus bands and recommend using shifts of major band to estimate the sample heating.

7.Topological nonsymmorphic insulator versus Dirac semimetal in KZnBi

Authors:Rahul Verma, Bikash Patra, Bahadur Singh

Abstract: KZnBi was discovered recently as a new three-dimensional (3D) Dirac semimetal with a pair of bulk Dirac fermions in contrast to the $\mathbb{Z}_2$ trivial insulator reported earlier. In order to address this discrepancy, we have performed electronic structure and topological state analysis of KZnBi using the local, semilocal, and hybrid exchange-correlation (XC) functionals within the density functional theory framework. We find that various XC functionals, including the SCAN meta-GGA and hybrid functionals with 25$\%$ Hartree-Fock (HF) exchange, resolve a topological nonsymmorphic insulator state with the glide-mirror protected hourglass surface Dirac fermions. By carefully tuning the modified Becke-Jhonson (mBJ) potential parameters, we recover the correct orbital ordering and Dirac semimetal state of KZnBi. We further show that increasing the default HF exchange in hybrid functionals ($> 40\%$) can also capture the desired Dirac semimetal state with the correct orbital ordering of KZnBi. The calculated energy dispersion and carrier velocities of Dirac states are found to be in excellent agreement with the available experimental results. Our results demonstrate that KZnBi is a unique topological material where large electron correlations are crucial to realize the Dirac semimetal state.

8.Photovoltaic potential of tin perovskites revealed through layer-by-layer investigation of optoelectronic and charge transport properties

Authors:Mahmoud H. Aldamasy, Artem Musiienko, Marin Rusu, Shengnan Zho, Hannes Hampel, Chiara Frasca, Zafar Iqbal, Thomas W. gries, Guixiang Li, Ece Aktas, Giuseppe Nasti, Meng Li, Jorge Pascual, Noor Titan Putri Hartono, Qiong Wang, Thomas Unold, Antonio Abate

Abstract: Tin perovskites are the most promising environmentally friendly alternative to lead perovskites. Among tin perovskites, FASnI3 (CH4N2SnI3) shows optimum band gap, and easy processability. However, the performance of FASnI3 based solar cells is incomparable to lead perovskites for several reasons, including energy band mismatch between the perovskite absorber film and the charge transporting layers (CTLs) for both types of carriers, i.e., for electrons (ETLs) and holes (HTLs). However, the band diagrams in the literature are inconsistent, and the charge extraction dynamics are poorly understood. In this paper, we study the energy band positions of FASnI3 based perovskites using Kelvin probe (KP) and photoelectron yield spectroscopy (PYS) to provide a precise band diagram of the most used device stack. In addition, we analyze the defects within the current energetic landscape of tin perovskites. We uncover the role of bathocuproine (BCP) in enhancing the electron extraction at the fullerene C60/BCP interface. Furthermore, we used transient surface photovoltage (tr-SPV) for the first time for tin perovskites to understand the charge extraction dynamics of the most reported HTLs such as NiOx and PEDOT, and ETLs such as C60, ICBA, and PCBM. Finally, we used Hall effect, KP, and time-resolved photoluminescence (TRPL) to estimate an accurate value of the p-doping concentration in FASnI3 and showed a consistent result of 1.5 * 1017 cm-3. Our findings prove that the energetic system of tin halide perovskites is deformed and should be redesigned independently from lead perovskites to unlock the full potential of tin perovskites.

9.Experimental realization of a high Curie temperature CoFeRuSn quaternary Heusler alloy for spintronic applications

Authors:Ravinder Kumar, Sachin Gupta

Abstract: We synthesize CoFeRuSn equiatomic quaternary Heusler alloy using arc-melt technique and investigate its structural, magnetic and transport properties. The room temperature powder X-ray diffraction analysis reveals that CoFeRuSn crystallizes in cubic crystal structure with small amount of DO3 - disorder. The field dependence of magnetization shows non-zero but small hysteresis and saturation behavior up to room temperature, indicating soft ferromagnetic nature of CoFeRuSn. The magnetic moment estimated from the magnetization data is found to be 4.15 {\mu}B / f.u., which is slightly less than the expected Slater-Pauling rule. The deviation in the value of experimentally observed moment from the theoretical value might be due to small disorder in the crystal. The low temperature fit to electrical resistivity data show absence of quadratic temperature dependence of resistivity, suggesting half-metallic behavior of CoFeRuSn. The high Curie temperature and possible half-metallic behavior of CoFeRuSn make it a highly promising candidate for room temperature spintronic applications.

10.Topological phase transition and tunable surface states in YBi

Authors:Ramesh Kumar, Mukhtiyar Singh

Abstract: A unique co-existence of extremely large magnetoresistance (XMR) and topological characteristics in non-magnetic rare-earth monopnictides stimulating intensive research on these materials. Yttrium monobismuthide (YBi) has been reported to exhibit XMR up to 105% but its Topological properties still need clarification. Here we use the hybrid density functional theory to probe the structural, electronic and topological properties of YBi in detail. We observe that YBi is topologically trivial semimetal at ambient pressure which is in accordance with reported experimental results. The topological phase transitions i.e., trivial to non-trivial are obtained with volumetric pressure of 6.5 GPa and 3% of epitaxial strain. This topological phase transitions are well within the structural phase transition of YBi (24.5 GPa). The topological non-trivial state is characterized by band inversions among Y-d band and Bi-p band near {\Gamma}- and X-point in the Brillouin zone. This is further verified with the help of surface band structure along (001) plane. The Z2 topological invariants are calculated with the help of product of parities and evolution of Wannier charge centers. The occurrence of non-trivial phase in YBi with a relatively small epitaxial strain, which a thin film geometry can naturally has, might make it an ideal candidate to probe inter-relationship between XMR and non-trivial topology.

11.Connection between inelastic x-ray scattering and complementary x-ray spectroscopies: probing excitons at Al K and L1 edges of $α$-Al$_2$O$_3$

Authors:M. Laura Urquiza, Matteo Gatti, Francesco Sottile

Abstract: We present an ab initio study of core excitations at the aluminum K and L1 edges in ${\alpha}$-Al2O3 within an all-electron many-body perturbation theory (MBPT) framework. Calculated XAS reveals excellent agreement with experiments, highlighting the dipole-forbidden nature of the pre-peak, which in experiments is enabled by sp mixing due to atomic vibrations. Non-resonant inelastic X-ray scattering (NRIXS) is employed to go beyond the dipole approximation and probe transition channels with s, p, and d character, enhancing multipole transitions that contribute to the pre-peak. The RIXS spectra at K and L1 edges are remarkably similar, opening the way to soft X-ray RIXS experiments to probe semi-core s states. The RIXS calculations reveal two distinct regimes based on the behavior with incoming photon energy ($\omega_1$). For $\omega_1$ in resonance with the XAS threshold, we observe Raman-like behavior, where the RIXS spectra show significant dependence on $\omega_1$ , reflecting the coupling between absorption and emission processes. For higher $\omega_1$ , above the XAS threshold, the study reveals fluorescence features that appear at constant emission energy, and can be explained via X-ray emission spectroscopy (XES).

12.Atomistic Control in Molecular Beam Epitaxy Growth of Intrinsic Magnetic Topological Insulator MnBi2Te4

Authors:Hyunsue Kim, Mengke Liu, Lisa Frammolino, Yanxing Li, Fan Zhang, Woojoo Lee, Chengye Dong, Yi-Fan Zhao, Guan-Yu Chen, Pin-Jui Hsu, Cui-Zu Chang, Joshua Robinson, Jiaqiang Yan, Xiaoqin Li, Allan H. MacDonald, Chih-Kang Shih

Abstract: Intrinsic magnetic topological insulators have emerged as a promising platform to study the interplay between topological surface states and ferromagnetism. This unique interplay can give rise to a variety of exotic quantum phenomena, including the quantum anomalous Hall effect and axion insulating states. Here, utilizing molecular beam epitaxy (MBE), we present a comprehensive study of the growth of high-quality MnBi2Te4 thin films on Si (111), epitaxial graphene, and highly ordered pyrolytic graphite substrates. By combining a suite of in-situ characterization techniques, we obtain critical insights into the atomic-level control of MnBi2Te4 epitaxial growth. First, we extract the free energy landscape for the epitaxial relationship as a function of the in-plane angular distribution. Then, by employing an optimized layer-by-layer growth, we determine the chemical potential and Dirac point of the thin film at different thicknesses. Overall, these results establish a foundation for understanding the growth dynamics of MnBi2Te4 and pave the way for the future applications of MBE in emerging topological quantum materials.

1.How close are the classical two-body potentials to ab initio calculations? Insights from linear machine learning based force matching

Authors:Zheng Yu, Ajay Annamareddy, Dane Morgan, Bu Wang

Abstract: In this work, we propose a linear machine learning force matching approach that can directly extract pair atomic interactions from ab initio calculations in amorphous structures. The local feature representation is specifically chosen to make the linear weights a force field as a force/potential function of the atom pair distance. Consequently, this set of functions is the closest representation of the ab initio forces given the two-body approximation and finite scanning in the configurational space. We validate this approach in amorphous silica. Potentials in the new force field (consisting of tabulated Si-Si, Si-O, and O-O potentials) are significantly softer than existing potentials that are commonly used for silica, even though all of them produce the tetrahedral network structure and roughly similar glass properties. This suggests that those commonly used classical force fields do not offer fundamentally accurate representations of the atomic interaction in silica. The new force field furthermore produces a lower glass transition temperature ($T_g\sim$1800 K) and a positive liquid thermal expansion coefficient, suggesting the extraordinarily high $T_g$ and negative liquid thermal expansion of simulated silica could be artifacts of previously developed classical potentials. Overall, the proposed approach provides a fundamental yet intuitive way to evaluate two-body potentials against ab initio calculations, thereby offering an efficient way to guide the development of classical force fields.

2.Bayesian optimization with active learning of Ta-Nb-Hf-Zr-Ti system for spin transport properties

Authors:Ruiwen Xie, Yixuan Zhang, Fu Li, Zhiyuan Li, Hongbin Zhang

Abstract: Designing materials with enhanced spin charge conversion, i.e., with high spin Hall conductivity (SHC) and low longitudinal electric conductivity (hence large spin Hall angle (SHA)), is a challenging task, especially in the presence of a vast chemical space for compositionally complex alloys (CCAs). In this work, focusing on the Ta-Nb-Hf-Zr-Ti system, we confirm that CCAs exhibit significant spin Hall conductivities and propose a multi-objective Bayesian optimization approach (MOBO) incorporated with active learning (AL) in order to screen for the optimal compositions with significant SHC and SHA. As a result, within less than 5 iterations we are able to target the TaZr-dominated systems displaying both high magnitudes of SHC (~-2.0 (10$^{-3}$ $\Omega$ cm)$^{-1}$) and SHA (~0.03). The SHC is mainly ascribed to the extrinsic skew scattering mechanism. Our work provides an efficient route for identifying new materials with significant SHE, which can be straightforwardly generalized to optimize other properties in a vast chemical space.

3.Emergence of Chaos in Magnetic-Field-Driven Skyrmions

Authors:Gyuyoung Park, Sang-Koog Kim

Abstract: We explore magnetic-field-driven chaos in magnetic skyrmions. Oscillating magnetic fields induce nonlinear dynamics in skyrmions, arising from the coupling of the secondary gyrotropic mode with a non-uniform, breathing-like mode. Through micromagnetic simulations, we observe complex patterns of hypotrochoidal motion in the orbital trajectories of the skyrmions, which are interpreted using bifurcation diagrams and local Lyapunov exponents. Our findings demonstrate that different nonlinear behaviors of skyrmions emerge at distinct temporal stages, depending on the nonlinear dynamic parameters. Investigating the abundant dynamic patterns of skyrmions during the emergence of chaos not only enhances device reliability but also provides useful guidelines for establishing chaos computing based on skyrmion dynamics.

4.The Effects of Ligand Substituents on the Character of Zn-Coordination in Zeolitic Imidazolate Frameworks

Authors:Joshua Edzards, Holger-Dietrich Saßnick, Ana Guilherme Buzanich, Ana M. Valencia, Franziska Emmerling, Sebastian Beyer, Caterina Cocchi

Abstract: Due to their favorable properties and high porosity, zeolitic imidazolate frameworks (ZIFs) have recently received much limelight for key technologies such as energy storage, optoelectronics, sensorics, and catalysis. Despite the widespread interest in these materials, fundamental questions regarding the zinc coordination environment remain poorly understood. By focusing on zinc(II)2-methylimidazolate (ZIF-8) and its tetrahedrally coordinated analogs with Br-, Cl-, and H-substitution in the 2-ring position, we aim to clarify how variations in the local environment of Zn impact the charge distribution and the electronic properties of these materials. Our results from density-functional theory confirm the presence of a Zn coordinative bond with a large polarization that is quantitatively affected by different substituents on the organic ligand. Moreover, our findings suggest that the variations induced by the functionalization in the Zn coordination have a negligible effect on the electronic structure of the considered compounds. On the other hand, halogen terminations of the ligands lead to distinct electronic contributions in the vicinity of the frontier region which ultimately reduce the band-gap size by a few hundred meV. Experimental results obtained from X-ray absorption spectroscopy (Zn $K$-edge) confirm the trends predicted by theory and, together with them, contribute to a better understanding of the structure-property relationships that are needed to tailor ZIFs for target applications.

5.Theoretical issues in the accurate computation of the electron-phonon interaction contribution to the total energy

Authors:Shilpa Paul, M. P. Gururajan, Amrita Bhattacharya, T. R. S. Prasanna

Abstract: The total energy is the most fundamental quantity in ab initio studies. To include electron-phonon interaction (EPI) contribution to the total energy, we have recast Allen's equation, for the case of semiconductors and insulators. This equivalent expression can be computed using available software, leading to more accurate total energy. We calculate the total energies and their differences for carbon-diamond and carbon-hexagonal polytypes. For ab initio investigations on crystalline materials, the accepted norm is to compute important quantities only for the primitive unit cell because per-atom quantities are independent of unit cell size. Our results, unexpectedly, show that the per-atom total energy (EPI included) depends on the unit cell size and violates the unit cell independence. For example, it differs for carbon-diamond by 1 eV/atom between the primitive cell and supercells. We observe that reliable energy differences between polytypes are obtained when, instead of primitive cells, supercells with identical number of atoms are used. A crucial inference of general validity is that any equation which contains a partial Fan-Migdal self-energy term violates the unit cell independence. Further theoretical studies are needed to establish if the total energy (EPI included) is an exception or can be reconciled with the unit cell independence.

6.Exciton-carrier coupling in a metal halide perovskite nanocrystal assembly probed by two-dimensional coherent spectroscopy

Authors:Esteban Rojas-Gatjens, David Otto Tiede, Katherine A. Koch, Carlos Romero-Perez, Juan F. Galisteo-Lopez, Mauricio E. Calvo, Hernan Miguez, Ajay Ram Srimath Kandada

Abstract: The surface chemistry and inter-connectivity within perovskite nanocrystals play a critical role in determining the electronic interactions. They manifest in the Coulomb screening of electron-hole correlations and the carrier relaxation dynamics, among other many-body processes. Here, we characterize the coupling between the exciton and free carrier states close to the band-edge in a ligand-free formamidinium lead bromide nanocrystal assembly via two-dimensional coherent spectroscopy. The optical signatures observed in this work show: (i) a nonlinear spectral lineshape reminiscent of Fano-like interference that evidences the coupling between discrete electronic states and a continuum, (ii) symmetric excited state absorption cross-peaks that suggest the existence of a coupled exciton-carrier excited state, and (iii) ultrafast carrier thermalization and exciton formation. Our results highlight the presence of coherent coupling between exciton and free carriers, particularly in the sub-100 femtosecond timescales.

7.Understanding the role of Hubbard corrections in the rhombohedral phase of BaTiO$_3$

Authors:G. Gebreyesus, Lorenzo Bastonero, Michele Kotiuga, Nicola Marzari, Iurii Timrov

Abstract: We present a first-principles study of the low-temperature rhombohedral phase of BaTiO$_3$ using Hubbard-corrected density-functional theory. By employing density-functional perturbation theory, we compute the onsite Hubbard $U$ for Ti($3d$) states and the intersite Hubbard $V$ between Ti($3d$) and O($2p$) states. We show that applying the onsite Hubbard $U$ correction alone to Ti($3d$) states proves detrimental, as it suppresses the Ti($3d$)-O($2p$) hybridization and drives the system towards a cubic phase. Conversely, when both onsite $U$ and intersite $V$ are considered, the localized character of the Ti($3d$) states is maintained, while also preserving the Ti($3d$)-O($2p$) hybridization, restoring the rhombohedral phase of BaTiO$_3$. The generalized PBEsol+$U$+$V$ functional yields remarkable agreement with experimental results for the band gap and dielectric constant, while the optimized geometry is slightly less accurate compared to PBEsol. Zone-center phonon frequencies and Raman spectra, being significantly influenced by the underlying geometry, demonstrate better agreement with experiments in the case of PBEsol, while PBEsol+$U$+$V$ exhibits reduced accuracy, and the PBEsol+$U$ Raman spectrum diverges remarkably from experimental data, highlighting the adverse impact of the $U$ correction alone in BaTiO$_3$. Our findings underscore the promise of the extended Hubbard PBEsol+$U$+$V$ functional with first-principles $U$ and $V$ for the investigation of other ferroelectric perovskites with mixed ionic-covalent interactions.

8.Theoretical investigation of the lattice thermal conductivities of II-IV-V2 pnictide semiconductors

Authors:Victor Posligua, Jose J. Plata, Antonio M. Márquez, Javier Fdez Sanz, Ricardo Grau-Crespo

Abstract: Ternary pnictides semiconductors with II-IV-V2 stoichiometry hold potential as cost effective thermoelectric materials with suitable electronic transport properties, but their lattice thermal conductivities ($\kappa$) are typically too high. Gaining insight into their vibrational properties is therefore crucial to finding strategies to reduce $\kappa$ and achieve improved thermoelectric performance. We present a theoretical exploration of the lattice thermal conductivities for a set of pnictide semiconductors with ABX2 composition (A = Zn, Cd; B = Si, Ge, Sn; and X = P, As), using machine-learning based regression algorithms to extract force constants from a reduced number of density functional theory simulations, and then solving the Boltzmann transport equation for phonons. Our results align well available experimental data, decreasing the mean absolute error by ~3 Wm-1K-1 with respect to the best previous set of theoretical predictions. Zn-based ternary pnictides have, on average, more than double the thermal conductivity of the Cd-based compounds. Anisotropic behaviour increases with the mass difference between A and B cations, but while the nature of the anion does not affect the structural anisotropy, the thermal conductivity anisotropy is typically higher for arsenides than for phosphides. We identify compounds, like CdGeAs2, for which nanostructuring to an affordable range of particle sizes could lead to values low enough for thermoelectric applications.

9.Symmetry constraints on the orbital transport in solids

Authors:S. Urazhdin

Abstract: We show that electron interaction with the crystal lattice imposes stringent symmetry constrains on the orbital moment propagation. We present examples that elucidate the underlying mechanisms and reveal an additional effect of ultrafast orbital moment oscillations not captured by the semiclassical models. The constraints revealed by our analysis warrant re-interpretation of prior observations, and suggest routes for efficient orbitronic device implementation.

1.Strong and nearly 100$\%$ spin-polarized second-harmonic generation from ferrimagnet Mn$_{2}$RuGa

Authors:Y. Q. Liu, M. S. Si, G. P. Zhang

Abstract: Second-harmonic generation (SHG) has emerged as a promising tool for detecting electronic and magnetic structures in noncentrosymmetric materials, but 100$\%$ spin-polarized SHG has not been reported. In this work, we demonstrate nearly 100$\%$ spin-polarized SHG from half-metallic ferrimagnet Mn$_{2}$RuGa. A band gap in the spin-down channel suppresses SHG, so the spin-up channel contributes nearly all the signal, as large as 3614 pm/V about 10 times larger than that of GaAs. In the spin-up channel, $\chi_{xyz}^{(2)}$ is dominated by the large intraband current in three highly dispersed bands near the Fermi level. With the spin-orbit coupling (SOC), the reduced magnetic point group allows additional SHG components, where the interband contribution is enhanced. Our finding is important as it predicts a large and complete spin-polarized SHG in a all-optical spin switching ferrimagnet. This opens the door for future applications.

2.Energy and morphology of martensite-twinned martensite interface in CuAlNi shape memory alloy: a phase-field study

Authors:Seyedshoja Amini, Mohsen Rezaee-Hajidehi, Stanislaw Stupkiewicz

Abstract: Needle-like twins are observed experimentally within the transition layer at the martensite-twinned martensite interface. We utilize a phase-field approach to investigate this microstructure. Our goal is to simulate the morphology of the transition layer and to perform a detailed analysis to characterize its interfacial and elastic micro-strain energy. To illustrate the micromechanical framework developed for that purpose, sample computations are carried out for a CuAlNi shape memory alloy undergoing the cubic-to-orthorhombic martensitic transformation. A particular focus of the study is on size-dependent morphology through examining the impact of twin spacing. Additionally, our results reveal that certain twin volume fractions lead to the emergence of twin branching, as a way to minimize the total free energy stored in the microstructure.

3.Observation of Antiferroelectric Domain Walls in a Uniaxial Hyperferroelectric

Authors:Michele Conroy, Didrik René Småbråten, Colin Ophus, Konstantin Shapovalov, Quentin M. Ramasse, Kasper Aas Hunnestad, Sverre M. Selbach, Ulrich Aschauer, Kalani Moore, J. Marty Gregg, Ursel Bangert, Massimiliano Stengel, Alexei Gruverman, Dennis Meier

Abstract: Ferroelectric domain walls are a rich source of emergent electronic properties and unusual polar order. Recent studies showed that the configuration of ferroelectric walls can go well beyond the conventional Ising-type structure. N\'eel-, Bloch-, and vortex-like polar patterns have been observed, displaying strong similarities with the spin textures at magnetic domain walls. Here, we report the discovery of antiferroelectric domain walls in the uniaxial ferroelectric Pb$_{5}$Ge$_{3}$O$_{11}$. We resolve highly mobile domain walls with an alternating displacement of Pb atoms, resulting in a cyclic 180$^{\circ}$ flip of dipole direction within the wall. Density functional theory calculations reveal that Pb$_{5}$Ge$_{3}$O$_{11}$ is hyperferroelectric, allowing the system to overcome the depolarization fields that usually suppress antiparallel ordering of dipoles along the longitudinal direction. Interestingly, the antiferroelectric walls observed under the electron beam are energetically more costly than basic head-to-head or tail-to-tail walls. The results suggest a new type of excited domain-wall state, expanding previous studies on ferroelectric domain walls into the realm of antiferroic phenomena.

4.Calculated iron $L_{2,3}$ x-ray absorption and XMCD of spin-crossover Fe(phen)$_{2}$(NCS)$_{2}$ molecule adsorbed on Cu(001) surface

Authors:R. Pasquier, M. Alouani

Abstract: The PAW method has been used to compute the iron L$_{2,3}$ edges of x-ray absorption spectra (XAS) and x-ray magnetic circular dichroism (XMCD) of the spin-crossover Fe(phen)$_{2}$(NCS)$_{2}$ molecule when adsorbed on Cu(001) surface and in the gas phase, for both the high spin (HS) and low spin (LS) states. It is found that the calculated XAS and XMCD with the static core hole or the Slater transition state half hole are in less good agreement with experiment than those using the so called initial state. This disagreement is due to the reduction of the iron spin magnetic moment caused by the static screening of the core hole by the photo-electron. The L$_{2,3}$ XAS formula is found to be directly related to the unoccupied $3d$ density of states (DOS), and hence the symmetry broken $e_g$ and the $t_{2g}$ iron DOS are used to explain the XAS and XMCD results. It is demonstrated that the dependence of the HS XMCD on the direction of incident x-ray circularly polarized light with respect to the magnetization direction can be used to determine the iron octahedron deformation, while the XMCD for various magnetization directions is directly related to the anisotropy of the orbital magnetic moment and the magneto-crystalline energy. It is also shown that the magnetic dipole moment $T_z$ is very large due to the strong distortion of the iron octahedron and is necessary for an accurate determination of the sum rule computed spin magnetic moment.

5.On the sign of the linear magnetoelectric coefficient in Cr$_2$O$_3$

Authors:Eric Bousquet, Eddy Lelièvre-Berna, Navid Qureshi, Jian-Rui Soh, Nicola A. Spaldin, Andrea Urru, Xanthe H. Verbeek, Sophie F. Weber

Abstract: We establish the sign of the linear magnetoelectric (ME) coefficient, $\alpha$, in chromia, Cr$_2$O$_3$. Cr$_2$O$_3$ is the prototypical linear ME material, in which an electric (magnetic) field induces a linearly proportional magnetization (polarization), and a single magnetic domain can be selected by annealing in combined magnetic (H) and electric (E) fields. Opposite antiferromagnetic domains have opposite ME responses, and which antiferromagnetic domain corresponds to which sign of response has previously been unclear. We use density functional theory (DFT) to calculate the magnetic response of a single antiferromagnetic domain of Cr$_2$O$_3$ to an applied in-plane electric field at 0 K. We find that the domain with nearest neighbor magnetic moments oriented away from (towards) each other has a negative (positive) in-plane ME coefficient, $\alpha_{\perp}$, at 0 K. We show that this sign is consistent with all other DFT calculations in the literature that specified the domain orientation, independent of the choice of DFT code or functional, the method used to apply the field, and whether the direct (magnetic field) or inverse (electric field) ME response was calculated. Next, we reanalyze our previously published spherical neutron polarimetry data to determine the antiferromagnetic domain produced by annealing in combined E and H fields oriented along the crystallographic symmetry axis at room temperature. We find that the antiferromagnetic domain with nearest-neighbor magnetic moments oriented away from (towards) each other is produced by annealing in (anti-)parallel E and H fields, corresponding to a positive (negative) axial ME coefficient, $\alpha_{\parallel}$, at room temperature. Since $\alpha_{\perp}$ at 0 K and $\alpha_{\parallel}$ at room temperature are known to be of opposite sign, our computational and experimental results are consistent.

6.Deformation twins as a probe for tribologically induced stress states

Authors:Antje Dollmann, Christian Kuebel, Vahid Tavakolli, Stefan J. Eder, Michael Feuerbacher, Tim Liening, Alexander Kauffmann, Julia Rau, Christian Greiner

Abstract: Friction and wear of metals are critically influenced by the microstructures of the bodies constituting the tribological contact. Understanding the microstructural evolution taking place over the lifetime of a tribological system therefore is crucial for strategically designing tribological systems with tailored friction and wear properties. Here, we focus on single-crystalline CoCrFeMnNi that is prone to form twins at room temperature. Deformation twins feature a pronounced orientation dependence with a tension-compression anisotropy, a distinct strain release in an extended volume and robust onset stresses. This makes deformation twinning an ideal probe to experimentally investigate the complex stress fields occurring in a tribological contact. Our results clearly show a grain orientation dependence of twinning under tribological load. Unexpectedly, neither the crystal direction parallel to the sliding nor the normal direction are solely decisive for twinning. This experimental approach is ideal to experimentally validate tribological stress field models, as is demonstrates here.

7.Optical absorption spectra of metal oxides from time-dependent density functional theory and many-body perturbation theory based on optimally-tuned hybrid functionals

Authors:Guy Ohad Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, Rehovoth, Israel, Weizmann Institute of Science, Stephen E. Gant Department of Physics, University of California Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, Dahvyd Wing Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, Rehovoth, Israel, Weizmann Institute of Science, Jonah B. Haber Department of Physics, University of California Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, María Camarasa-Gómez Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, Rehovoth, Israel, Weizmann Institute of Science, Francisca Sagredo Department of Physics, University of California Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, Marina R. Filip Department of Physics, University of Oxford, Oxford, United Kingdom, Jeffrey B. Neaton Department of Physics, University of California Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA Kavli Energy NanoSciences Institute at Berkeley, University of California, Berkeley, CA, Leeor Kronik Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, Rehovoth, Israel, Weizmann Institute of Science

Abstract: Using both time-dependent density functional theory (TDDFT) and the ``single-shot" $GW$ plus Bethe-Salpeter equation ($GW$-BSE) approach, we compute optical band gaps and optical absorption spectra from first principles for eight common binary and ternary closed-shell metal oxides (MgO, Al$_2$O$_3$, CaO, TiO$_2$, Cu$_2$O, ZnO, BaSnO$_3$, and BiVO$_4$), based on the non-empirical Wannier-localized optimally-tuned screened range-separated hybrid functional. Overall, we find excellent agreement between our TDDFT and $GW$-BSE results and experiment, with a mean absolute error less than 0.4 eV, including for Cu$_2$O and ZnO, traditionally considered to be challenging for both methods.

8.On the origin of circular dichroism in angular resolved photoemission from graphene, graphite, and WSe$_2$ family of materials

Authors:Lukasz Plucinski

Abstract: Circular dichroism in angle-resolved photoemission (CD-ARPES) is one of the promising techniques for obtaining experimental insight into topological properties of novel materials, in particular to the orbital angular momentum (OAM) in dispersive bands, which might be related, albeit certainly in a non-trivial way, to the momentum resolved Berry curvature of the bands. Therefore, it is important to understand how non-vanishing CD-ARPES signal arises in graphene, a material where Dirac bands are made from C $|2p_z\rangle$ orbitals that carry zero OAM, spin-orbit-coupling (SOC) can be neglected, and Berry curvature effectively vanishes. Dubs et al., Phys. Rev. B 32, 8389 (1985) have demonstrated non-vanishing cricular dichroism in angular distribution (CDAD) from an oriented $p_z$ orbital, and this process can be responsible for the experimentally observed CD-ARPES in graphene. In this paper, we derive the CD-ARPES from $p_z$ orbitals by elementary means, using only simple algebraic formulas and tabulated numerical values, and show that it leads to significant CD-ARPES signal over the entire vacuum ultraviolet and soft x-ray energy range, with an exception of the photon energy region near $h\nu \approx 40$ eV. We also demonstrate that another process, emerging from the finite electron inelastic mean free path, also leads to CD-ARPES of the potentially similar order of magnitude, as previously discussed by Moser, J. Electron Spectrosc. Relat. Phenom. 214, 29 (2017). We present calculated CDAD maps for selected orbitals and briefly discuss the consequences of the findings for CD-ARPES, focusing on graphene, graphite and WSe$_2$.

9.Unveiling the electronic properties of BiP$_3$ triphosphide from bulk to heterostructures by first principles calculations

Authors:Dominike P. de Andrade Deus, Igor S. S. de Oliveira, Roberto Hiroki Miwa, Erika L. Nascimento

Abstract: Triphosphides, with a chemical formula of XP$_3$ (X is a group IIIA, IVA, or VA element), have recently attracted much attention due to their great potential in several applications. Here, using density functional theory calculations, we describe for the first time the structural and electronic properties of the bulk bismuth triphosphide (BiP$_3$). Phonon spectra and molecular dynamics simulations confirm that the 3D crystal of BiP$_3$ is a metal thermodynamically stable with no bandgap. Unlike the bulk, the mono-, bi-, tri-, and tetra-layers of BiP$_3$ are semiconductors with a bandgap ranging from 1.4 to 0.06 eV. However, stackings with more than five layers exhibit metallic behavior equal to the bulk. The results show that quantum confinement is a powerful tool for tuning the electronic properties of BiP$_3$ triphosphide, making it suitable for technological applications. Building on this, the electronic properties of van der Waals heterostructure constructed by graphene (G) and the \bip~monolayer (m-\bip) were investigated. Our results show that the Dirac cone in graphene remains intact in this heterostructure. At the equilibrium interlayer distance, the G/m-BiP$_3$ forms an n-type contact with a Schottky barrier height of 0.5 eV. It is worth noting that the SHB in the G/m-BiP$_3$ heterostructure can be adjusted by changing the interlayer distance or applying a transverse electric field. Thus, we show that few-layers \bip~is an interesting material for realizing nanoelectronic and optoelectronic devices and is an excellent option for designing Schottky nanoelectronic devices.

10.Compressing and forecasting atomic material simulations with descriptors

Authors:Thomas D Swinburne

Abstract: Atomic simulations of material microstructure require significant resources to generate, store and analyze. Here, atomic descriptor functions are proposed as a general latent space to compress atomic microstructure, ideal for use in large-scale simulations. Descriptors can regress a broad range of properties, including character-dependent dislocation densities, stress states or radial distribution functions. A vector autoregressive model can generate trajectories over yield points, resample from new initial conditions and forecast trajectory futures. A forecast confidence, essential for practical application, is derived by propagating forecasts through the Mahalanobis outlier distance, providing a powerful tool to assess coarse-grained models. Application to nanoparticles and yielding of dislocation networks confirms low uncertainty forecasts are accurate and resampling allows for the propagation of smooth microstructure distributions. Yielding is associated with a collapse in the intrinsic dimension of the descriptor manifold, which is discussed in relation to the yield surface.

11.Controlling Spontaneous Orientation Polarization in Organic Semiconductors -- The Case of Phosphine Oxides

Authors:Albin Cakaj, Markus Schmid, Alexander Hofmann, Wolfgang Brütting

Abstract: Upon film growth by physical vapor deposition, the preferential orientation of polar organic molecules can result in a non-zero permanent dipole moment (PDM) alignment, causing a macroscopic film polarization. This effect, known as spontaneous orientation polarization (SOP), was studied in the case of different phosphine oxides. We investigate the control of SOP by molecular design and film-growth conditions. Our results show that using less polar phosphine oxides with just one phosphor-oxygen bond yields an exceptionally high degree of SOP with the so-called giant surface potential (slope) reaching more than 150mV/nm in a neat BCPO film grown at room temperature. Additionally, by altering the evaporation rate and the substrate temperature, we are able to control the SOP magnitude over a broad range from 0 to almost 300mV/nm. Diluting BCPO in a non-polar host enhances the PDM alignment only marginally, but combining temperature control together with dipolar doping can result in almost perfectly aligned molecules with more than 80% of their PDMs standing upright on the substrate on average.

12.Probing defect induced room temperature ferromagnetism in CVD grown MoO3 flakes: A correlation with electronic structure and first principle-based calculations

Authors:Sharmistha Dey, Vikash Mishra, Neetesh Dhakar, Sunil Kumar, Pankaj Srivastava, Santanu Ghosh

Abstract: In this paper, we report the growth of pure {\alpha}-MoO3 micro-flakes by CVD technique and their structural, electronic, optical, and magnetic properties. Samples are annealed at various temperatures in an H2 atmosphere to induce ferromagnetism. All the samples exhibit ferromagnetism at room temperature, and 250oC annealed sample shows the highest magnetic moment of 0.087 emu/g. It is evident from PL data that pristine as well as annealed samples contain different types of defects like oxygen vacancies, surface defects, interstitial oxygen, etc. It is deduced from the analysis of Mo3d and O1s core-level XPS spectra that oxygen vacancies increase up to an annealing temperature of 250oC that correlates with the magnetic moment. Significant changes in the total density of states and also in the magnetic moment for two and three oxygen vacancies are noticed through first-principle-based calculations. It is concluded that the magnetic moment is produced by oxygen vacancies or vacancy clusters, which is consistent with our experimental findings.

13.Electronic Structure and Scaling of Coulomb Defects in Carbon Nanotubes from Modified Hückel Calculations

Authors:Klaus H. Eckstein, Tobias Hertel

Abstract: Controlled doping and understanding its underlying microscopic mechanisms is crucial for advancement of nanoscale electronic technologies, especially in semiconducting single-wall carbon nanotubes (s-SWNTs), where adsorbed counterions are known to govern redox-doping levels. However, modeling the associated 'Coulomb defects' is challenging due to the need for large-scale simulations at low doping levels. Using modified H\"uckel calculations on 120 nm long s-SWNTs with adsorbed $\rm Cl^-$ ions, we study the scaling properties of shallow Coulomb defect states at the valence band edge and quantum well (QW) states in the conduction band. Interestingly, the QW states may underlie observed exciton band shifts of inhomogeneously doped semiconductors. Binding energies of Coulomb defects are found to scale with counterion distance, effective band mass, relative permittivity and counterion charge according to $d^{\alpha-2}m^{\alpha-1}\epsilon_r^{-\alpha}|z_j|^{\alpha}$, with $\alpha$ as an empirical parameter, deepening our understanding of s-SWNT doping.

14.Landau Theory of Barocaloric Plastic Crystals

Authors:Marín-Delgado R., Moya, X., Guzmán-Verri, G. G

Abstract: We present a simple Landau phenomenology for plastic-to-crystal phase transitions and use the resulting model to calculate barocaloric effects in plastic crystals that are driven by hydrostatic pressure. The essential ingredients of the model are (i) a multipole-moment order parameter that describes the orientational ordering of the constituent molecules, (ii) coupling between such order parameter and elastic strains, and (iii) the thermal expansion of the solid. The model captures main features of plastic-to-crystal phase transitions, namely large volume and entropy changes at the transition, and strong dependence of the transition temperature with pressure. Using solid C$_{60}$ under $0.60\,$GPa as case example, we show that calculated peak isothermal entropy changes of $\sim 58 \,{\rm J K^{-1} kg^{-1}}$ and peak adiabatic entropy changes of $\sim 23 \,{\rm K}$ agree well with experimental values.

15.Predictions and Uncertainty Estimates of Reactor Pressure Vessel Steel Embrittlement Using Machine Learning

Authors:Ryan Jacobs, Takuya Yamamoto, G. Robert Odette, Dane Morgan

Abstract: An essential aspect of extending safe operation of the active nuclear reactors is understanding and predicting the embrittlement that occurs in the steels that make up the Reactor pressure vessel (RPV). In this work we integrate state of the art machine learning methods using ensembles of neural networks with unprecedented data collection and integration to develop a new model for RPV steel embrittlement. The new model has multiple improvements over previous machine learning and hand-tuned efforts, including greater accuracy (e.g., at high-fluence relevant for extending the life of present reactors), wider domain of applicability (e.g., including a wide-range of compositions), uncertainty quantification, and online accessibility for easy use by the community. These improvements provide a model with significant new capabilities, including the ability to easily and accurately explore compositions, flux, and fluence effects on RPV steel embrittlement for the first time. Furthermore, our detailed comparisons show our approach improves on the leading American Society for Testing and Materials (ASTM) E900-15 standard model for RPV embrittlement on every metric we assessed, demonstrating the efficacy of machine learning approaches for this type of highly demanding materials property prediction.

16.Phononic drumhead surface state in distorted kagome compound RhPb

Authors:Andrzej Ptok, William R. Meier, Aksel Kobiałka, Surajit Basak, Małgorzata Sternik, Jan Łażewski, Paweł T. Jochym, Michael A. McGuire, Brian C. Sales, Hu Miao, Przemysław Piekarz, Andrzej M. Oleś

Abstract: RhPb was initially recognized as one of a CoSn-like compounds with $P6/mmm$ symmetry, containing an ideal kagome lattice of $d$-block atoms. However, theoretical calculations predict the realization of the phonon soft mode which leads to the kagome lattice distortion and stabilization of the structure with $P\bar{6}2m$ symmetry [A. Ptok et al., Phys. Rev. B 104, 054305 (2021)]. Here, we present the single crystal x-ray diffraction results supporting this prediction. Furthermore, we discuss the main dynamical properties of RhPb with $P\bar{6}2m$ symmetry. The bulk phononic dispersion curves contain several flattened bands, Dirac nodal lines, and triple degenerate Dirac points. As a consequence, the phononic drumhead surface state is realized for the (100) surface, terminated by the zigzag-like edge of Pb honeycomb sublattice.

17.Ruthenium dioxide RuO$_{2}$: effect of the altermagnetism on the physical properties

Authors:Andrzej Ptok

Abstract: Ruthenium oxide with the rutile structure is one of example of altermagnets. These systems are characterized by compensated magnetic moments (typical for antiferromagnets) and strong time reversal symmetry breaking (typical for ferromagnets). However, in such cases, the electronic band structure exhibit strong spin splitting along some directions in the momentum space. Occurrence of the compensated magnetic textures allows for realization of surfaces with specific magnetization, which dependent on the surface orientation and/or its termination. Here, we study interplay between the electronic surface states and the surface magnetization. We show that the spin-resolved spectra strongly depends on a direction in reciprocal space. Such properties can be used for the experimental confirmation of the altermagnetism in RuO$_{2}$ within the spectroscopic techniques. Additionally, we show that the most modified orbitals in the system are $d_{z^{2}}$ and $d_{xy}$ orbitals of Ru. Similarly, the Ru $e_{g}$ states are most sensitive on epitaxial strain, what can suggest some link between altermagnetism and strain.

1.Isostructural phase transition in Tb2Ti2O7 under pressure and temperature: Insights from synchrotron X-ray diffraction

Authors:Subrata Das, Sanjoy Kr Mahatha, Konstantin Glazyrin, R Ganesan, Suja Elizabeth, Tirthankar Chakraborty

Abstract: Tb2Ti2O7, a pyrochlore system, has garnered significant interest due to its intriguing structural and physical properties and their dependence on external physical parameters. In this study, utilizing high-brilliance synchrotron X-ray diffraction, we conducted a comprehensive investigation of structural evolution of Tb2Ti2O7 under external pressure and temperature. We have conclusively confirmed the occurrence of an isostructural phase transition beyond the pressure of 10 GPa. The transition exhibits a distinct signature in the variation of lattice parameters under pressure and leads to changes in mechanical properties. The underlying physics driving this transition can be understood in terms of localized rearrangement of atoms while retaining the overall cubic symmetry of the crystal. Notably, the observed transition remains almost independent of temperature. Our findings provide insights into the distinctive behaviour of the isostructural phase transition in Tb2Ti2O7.

2.Non-Einsteinian Viscosity Reduction in Boron Nitride Nanotube Nanofluids

Authors:André Guerra, Adam McElligott, Chong Yang Du, Milan Marić, Alejandro D. Rey, Phillip Servio

Abstract: (1) Introduction: Nanoparticles have multiple applications, including drug delivery systems, biosensing, and carbon capture. Non-Einstein-like viscosity reduction has been reported in nanoparticle-polymer blends at low nanoparticle concentrations. More recently, a similar non-Einsteinian viscosity reduction effect has been observed in aqueous ultra-low concentration carbon-based nanofluids. (2) Methods: We use a boron nitride nanotube functionalized with hydrophilic groups in rheological experiments to investigate the viscosity reduction in ultra-low concentration nanofluids (0.1-10 ppm). We measure the dynamic viscosity in an air atmosphere and methane (0-5 MPag) at low temperatures (0-10 C). (3) Results: A negligible effect on the temperature dependence of viscosity was found. Ultra-low concentrations of BNNT reduced the viscosity of the nanofluid by up to 29% at 10 ppm in the presence of methane. The results presented here were compared to similar studies on O-GNF and O-MWCNT nanofluids, which also reported significant viscosity reductions. (4) Conclusions: This work identified a non-Einsteinian viscosity reduction in BNNT nanofluids, which was exacerbated by methane dissolved in the nanofluid.

1.Extraordinary Thermoelectric Properties of Topological Surface States in Quantum-Confined Cd3As2 Thin Films

Authors:Wenkai Ouyang, Alexander C. Lygo, Yubi Chen, Huiyuan Zheng, Dung Vu, Brandi L. Wooten, Xichen Liang, Wang Yao, Joseph P. Heremans, Susanne Stemmer, Bolin Liao

Abstract: Topological insulators and semimetals have been shown to possess intriguing thermoelectric properties promising for energy harvesting and cooling applications. However, thermoelectric transport associated with the Fermi arc topological surface states on topological Dirac semimetals remains less explored. In this work, we systematically examine thermoelectric transport in a series of topological Dirac semimetal Cd3As2 thin films grown by molecular beam epitaxy. Surprisingly, we find significantly enhanced Seebeck effect and anomalous Nernst effect at cryogenic temperatures when the Cd3As2 layer is thin. Combining angle-dependent quantum oscillation analysis, magnetothermoelectric measurement, transport modelling and first-principles simulation, we isolate the contributions from bulk and surface conducting channels and attribute the unusual thermoeletric properties to the topological surface states. Our analysis showcases the rich thermoelectric transport physics in quantum-confined topological Dirac semimetal thin films and suggests new routes to achieving high thermoelectric performance at cryogenic temperatures.

2.Imaging the Electric Field with X-Ray Diffraction Microscopy

Authors:Trygve Magnus Ræder, Urko Petralanda, Thomas Olsen, Hugh Simons

Abstract: The properties of semiconductors and functional dielectrics are defined by their response in electric fields, which may be perturbed by defects and the strain they generate. In this work, we demonstrate how diffraction-based X-ray microscopy techniques may be utilized to image the electric field in insulating crystalline materials. By analysing a prototypical ferro- and piezoelectric material, BaTiO$_{3}$, we identify trends that can guide experimental design towards imaging the electric field using any diffraction-based X-ray microscopy technique. We explain these trends in the context of dark-field X-ray microscopy, but the framework is also valid for Bragg scanning probe X-ray microscopy, Bragg coherent diffraction imaging and Bragg X-ray ptychography. The ability to quantify electric field distributions alongside the defects and strain already accessible via these techniques offers a more comprehensive picture of the often complex structure-property relationships that exist in many insulating and semiconducting materials.

3.Persistence of structural distortion and bulk band Rashba splitting in SnTe above its ferroelectric critical temperature

Authors:Frédéric Chassot Department of Physics and Fribourg Center for Nanomaterials, Université de Fribourg, Fribourg, Switzerland, Aki Pulkkinen Department of Physics and Fribourg Center for Nanomaterials, Université de Fribourg, Fribourg, Switzerland New Technologies-Research Center, University of West Bohemia, Plzen, Czech Republic, Geoffroy Kremer Department of Physics and Fribourg Center for Nanomaterials, Université de Fribourg, Fribourg, Switzerland Institut Jean Lamour, UMR 7198, CNRS-Université de Lorraine, Campus ARTEM, 2 allée André Guinier, BP 50840, 54011 Nancy, France, Tetiana Zakusylo Institut für Halbleiter-und Festkörperphysik, Johannes Kepler Universität, Linz, Austria, Gauthier Krizman Institut für Halbleiter-und Festkörperphysik, Johannes Kepler Universität, Linz, Austria, Mahdi Hajlaoui Institut für Halbleiter-und Festkörperphysik, Johannes Kepler Universität, Linz, Austria, J. Hugo Dil Institute of Physics, Ecole Polytechnique Fédérale de Lausanne, Lausanne, Switzerland Photon Science Division, Paul Scherrer Institut, Villigen, Switzerland, Juraj Krempaský Photon Science Division, Paul Scherrer Institut, Villigen, Switzerland, Ján Minár New Technologies-Research Center, University of West Bohemia, Plzen, Czech Republic, Gunther Springholz Institut für Halbleiter-und Festkörperphysik, Johannes Kepler Universität, Linz, Austria, Claude Monney Department of Physics and Fribourg Center for Nanomaterials, Université de Fribourg, Fribourg, Switzerland

Abstract: The ferroelectric semiconductor $\alpha$-SnTe has been regarded as a topological crystalline insulator and the dispersion of its surface states has been intensively measured with angle-resolved photoemission spectroscopy (ARPES) over the last decade. However, much less attention has been given to the impact of the ferroelectric transition on its electronic structure, and in particular on its bulk states. Here, we investigate the low-energy electronic structure of $\alpha$-SnTe with ARPES and follow the evolution of the bulk-state Rashba splitting as a function of temperature, across its ferroelectric critical temperature of about $T_c\sim 110$ K. Unexpectedly, we observe a persistent band splitting up to room temperature, which is consistent with an order-disorder contribution to the phase transition that requires the presence of fluctuating local dipoles above $T_c$. We conclude that no topological surface state can occur at the (111) surface of SnTe, at odds with recent literature.

4.Reporting activities for the oxygen evolution reaction: Do we compare apples to apples?

Authors:Marcel Risch

Abstract: The oxygen evolution reaction (OER) is a key enabler of sustainable chemical energy storage. Here, the author assesses the current status of protocols for benchmarking the OER in materials- and device-centered investigations and makes suggestions for more comparable data.

5.Microscopic crystallographic analysis of dislocations in molecular crystals

Authors:Sang T. Pham, Natalia Koniuch, Emily Wynne, Andy Brown, Sean M. Collins

Abstract: Organic molecular crystals encompass a vast range of materials from pharmaceuticals to organic optoelectronics and proteins to waxes in biological and industrial settings. Crystal defects from grain boundaries to dislocations are known to play key roles in mechanisms of growth and also in the functional properties of molecular crystals. In contrast to the precise analysis of individual defects in metals, ceramics, and inorganic semiconductors enabled by electron microscopy, significantly greater ambiguity remains in the experimental determination of individual dislocation character and slip systems in molecular materials. In large part, nanoscale dislocation analysis in molecular crystals has been hindered by the severely constrained electron exposures required to avoid irreversibly degrading these crystals. Here, we present a low-dose, single-exposure approach enabling nanometre-resolved analysis of individual extended dislocations in molecular crystals. We demonstrate the approach for a range of crystal types to reveal dislocation character and operative slip systems unambiguously.

6.Meta-analysis of literature data in metal additive manufacturing: What can we (and the machine) learn from reported data?

Authors:Raymond Wong, Anh Tran, Bogdan Dovgyy, Claudia Santos Maldonado, Minh-Son Pham

Abstract: Obtaining in-depth understanding of the relationships between the additive manufacturing (AM) process, microstructure and mechanical properties is crucial to overcome barriers in AM. In this study, database of metal AM was created thanks to many literature studies. Subsequently meta-analyses on the data was undertaken to provide insights into whether such relationships are well reflected in the literature data. The analyses help reveal the bias and what the data tells us, and to what extent machine learning (ML) can learn from the data. The first major bias is associated with common practices in identifying the process based on optimizing the consolidation. Most reports were for consolidation while data on microstructure and mechanical properties was significantly less. In addition, only high consolidation values was provided, so ML was not able to learn the full spectrum of the process - consolidation relationship. The common identification of process maps based on only consolidation also poses another bias as mechanical properties that ultimately govern the quality of an AM build are controlled not only by the consolidation, but also microstructure. Meta-analysis of the literature data also shows weak correlation between process with consolidation and mechanical properties. This weak correlation is attributed to the stated biases and the non-monotonic and non-linear relationships between the process and quality variables. Fortunately, trained ML models capture well the influence and interactions between process parameters and quality variables, and predicts accurately the yield stress, suggesting that the correlation between process, microstructure and yield strength is well reflected in the data. Lastly, due to the current limitation in the process map identification, we propose to identify the process map based on not only the consolidation, but also mechanical properties.

7.Beyond domain alignment: Revealing the effect of intrinsic magnetic order on electrochemical water splitting

Authors:Emma van der Minne, Lucas Korol, Lidewij M. A. Krakers, Michael Verhage, Carlos M. M. Rosário, Thijs J. Roskamp, Raymond J. Spiteri, Chiara Biz, Mauro Fianchini, Guus Rijnders, Kees Flipse, Jose Gracia, Guido Mul, Hans Hilgenkamp, Robert J. Green, Gertjan Koster, Christoph Baeumer

Abstract: To reach a long term viable green hydrogen economy, rational design of active oxygen evolution reaction (OER) catalysts is critical. An important hurdle in this reaction originates from the fact that the reactants are singlet molecules, whereas the oxygen molecule has a triplet ground state with parallel spin alignment, implying that magnetic order in the catalyst is essential. Accordingly, multiple experimentalists reported a positive effect of external magnetic fields on OER activity of ferromagnetic catalysts. However, it remains a challenge to investigate the influence of the intrinsic magnetic order on catalytic activity. Here, we tuned the intrinsic magnetic order of epitaxial La$_{0.67}$Sr$_{0.33}$MnO$_{3}$ thin film model catalysts from ferro- to paramagnetic by changing the temperature in-situ during water electrolysis. Using this strategy, we show that ferromagnetic ordering below the Curie temperature enhances OER activity. Moreover, we show a slight current density enhancement upon application of an external magnetic field and find that the dependence of magnetic field direction correlates with the magnetic anisotropy in the catalyst film. Our work thus suggests that both the intrinsic magnetic order in La$_{0.67}$Sr$_{0.33}$MnO$_{3}$ films and magnetic domain alignment increase their catalytic activity. We observe no long-range magnetic order at the catalytic surface, implying that the OER enhancement is connected to the magnetic order of the bulk catalyst. Combining the effects found with existing literature, we propose a unifying picture for the spin-polarized enhancement in magnetic oxide catalysts.

8.Supercell Altermagnets

Authors:R. Jaeschke-Ubiergo, V. K. Bharadwaj, L. Šmejkal, Jairo Sinova

Abstract: Altermagnets are compensated magnets with unconvetional $d$, $g$ and $i$-wave spin-channel order in reciprocal space. So far the search for new altermagnetic candidates has been focused on materials in which the magnetic unit cell is identical to the non-magnetic one, i.e. magnetic structures with zero propagation vector. Here, we substantially broaden the family of altermagnetic candidates by predicting supercell altermagnets. Their magnetic unit cell is constructed by enlarging the paramagnetic primitive unit cell, resulting in a non-zero propagation vector for the magnetic structure. This connection of the magnetic configuration to the ordering of sublattices gives an extra degree of freedom to supercell altermagnets, which can allow for the control over the order parameter spatial orientation. We identify realistic candidates MnSe$_2$ with a $d$-wave order, and RbCoBr$_3$, CsCoCr$_3$, and BaMnO$_3$ with $g$-wave order. We demonstrate the reorientation of the order parameter in MnSe$_2$, which has two different magnetic configurations, whose energy difference is only 5 meV, opening the possibility of controlling the orientation of the altermagnetic order parameter by external perturbations.

9.Interlayer vibrational hybrid normal mode enabling molecular chiral phonons

Authors:Hanen Hamdi, Jannis Krumland, Ana M. Valencia, Carlos-Andres Palma, Caterina Cocchi

Abstract: Organic/inorganic interfaces formed by monolayer substrates and conjugated molecular adsorbates are attractive material platforms leveraging the modularity of organic compounds together with the long-range phenomena typical of condensed matter. New quantum states are known to be generated by electronic interactions in these systems as well as by their coupling with light. However, little is still known about hybrid vibrational modes. In this work, we discover from first principles the existence of an infrared-active chiral phonon mode in a pyrene-decorated MoSe$_{2}$ monolayer given by the combination of a frustrated rotation of the molecule around its central axis and an optical mode in the substrate. Our results suggest the possibility to enable phonon chirality in molecular superlattices.

10.Magnon Orbital Angular Momentum of Ferromagnetic Honeycomb and Zig-Zag Lattices

Authors:R. S. Fishman, T. Berlijn, J. Villanova, L. Lindsay

Abstract: By expanding the gauge $\lambda_n(k)$ for magnon band $n$ in harmonics of momentum ${\bf k} =(k,\phi )$, we demonstrate that the only observable component of the magnon orbital angular momentum $O_n({\bf k})$ is its angular average over all angles $\phi$, denoted by $F_n(k)$. For both the FM honeycomb and zig-zag lattices, we show that $F_n(k)$ is nonzero in the presence of a Dzyalloshinzkii-Moriya (DM) interaction. The FM zig-zag lattice model with exchange interactions $0<J_1< J_2$ provides a new system where the effects of orbital angular momentum are observable. For the zig-zag model with equal exchange interactions $J_{1x}$ and $J_{1y}$ along the $x$ and $y$ axis, the magnon bands are degenerate along the boundaries of the Brillouin zone with $k_x-k_y =\pm \pi/a$ and the Chern numbers $C_n$ are not well defined. However, a revised model with $J_{1y}\ne J_{1x}$ lifts those degeneracy and produces well-defined Chern numbers of $C_n=\pm 1$ for the two magnon bands. When $J_{1y}=J_{1x}$, the thermal conductivity $\kappa^{xy}(T)$ of the FM zig-zag lattice is largest for $J_2/J_1>6$ but is still about four times smaller than that of the FM honeycomb lattice at high temperatures. Due to the removal of band degeneracies, $\kappa^{xy}(T)$ is slightly enhanced when $J_{1y}\ne J_{1x}$.

11.Electronic band reconstruction across the insulator-metal transition in colossal magnetoresistive EuCd2P2

Authors:Huali Zhang, Feng Du, Xiaoying Zheng, Shuaishuai Luo, Yi Wu, Hao Zheng, Shengtao Cui, Zhe Sun, Zhengtai Liu, Dawei Shen, Michael Smidman, Yu Song, Ming Shi, Zhicheng Zhong, Chao Cao, Huiqiu Yuan, Yang Liu

Abstract: While colossal magnetoresistance (CMR) in Eu-based compounds is often associated with strong spin-carrier interactions, the underlying reconstruction of the electronic bands is much less understood from spectroscopic experiments. Here using angle-resolved photoemission, we directly observe an electronic band reconstruction across the insulator-metal (and magnetic) transition in the recently discovered CMR compound EuCd2P2. This transition is manifested by a large magnetic band splitting associated with the magnetic order, as well as unusual energy shifts of the valence bands: both the large ordered moment of Eu and carrier localization in the paramagnetic phase are crucial. Our results provide spectroscopic evidence for an electronic structure reconstruction underlying the enormous CMR observed in EuCd2P2, which could be important for understanding Eu-based CMR materials, as well as designing CMR materials based on large-moment rare-earth magnets.

12.Understanding defects in amorphous silicon with million-atom simulations and machine learning

Authors:Joe D. Morrow, Chinonso Ugwumadu, David A. Drabold, Stephen R. Elliott, Andrew L. Goodwin, Volker L. Deringer

Abstract: The structure of amorphous silicon is widely thought of as a fourfold-connected random network, and yet it is defective atoms, with fewer or more than four bonds, that make it particularly interesting. Despite many attempts to explain such "dangling-bond" and "floating-bond" defects, respectively, a unified understanding is still missing. Here, we show that atomistic machine-learning methods can reveal the complex structural and energetic landscape of defects in amorphous silicon. We study an ultra-large-scale, quantum-accurate structural model containing a million atoms, and more than ten thousand defects, allowing reliable defect-related statistics to be obtained. We combine structural descriptors and machine-learned local atomic energies to develop a universal classification of the different types of defects in amorphous silicon. The results suggest a revision of the established floating-bond model by showing that fivefold-coordinated atoms in amorphous silicon exhibit a wide range of local environments, and it is shown that fivefold (but not threefold) coordination defects tend to cluster together. Our study provides new insights into one of the most widely studied amorphous solids, and has general implications for modelling and understanding defects in disordered materials beyond silicon alone.

1.Exploring GaN crystallographic orientation disparity and its origin on bare and partly graphene-covered $m$-plane sapphire substrates

Authors:Hyunkyu Lee, Hyeonoh Jo, Jae Hun Kim, Jongwoo Ha, Su Young An, Jaewu Choi, Chinkyo Kim

Abstract: The crystallographic orientation of 3D materials grown over 2D material-covered substrates is one of the critical factors in discerning the true growth mechanism among competing possibilities, including remote epitaxy, van der Waals epitaxy, and pinhole-seeded lateral epitaxy also known as thru-hole epitaxy. However, definitive identification demands meticulous investigation to accurately interpret experimentally observed crystallographic orientations, as misinterpretation can lead to mistaken conclusions regarding the underlying growth mechanism. In this study, we demonstrate that GaN domains exhibit orientation disparities when grown on both bare and partly graphene-covered $m$-plane sapphire substrates. Comprehensive measurements of crystallographic orientation unambiguously reveal that GaN domains adopt (100) and (103) orientations even when grown under identical growth conditions on bare and partly graphene-covered $m$-plane sapphire substrates, respectively. Particularly, high-resolution transmission electron microscopy unequivocally establishes that GaN grown over partly graphene-covered $m$-plane sapphire substrates started to nucleate on the exposed sapphire surface. Our research elucidates that crystallographic orientation disparities can arise even from thru-hole epitaxy, challenging the commonly accepted notion that such disparities cannot be attributed to thru-hole epitaxy when grown under identical growth conditions.

2.Fermi level depinning via insertion of a graphene buffer layer at the gold-2D tin monoxide contact

Authors:Yujia Tian Nanyang Technological University Infineon Technologies Asia Pacific Pte. Ltd, Devesh R. Kripalani Nanyang Technological University, Ming Xue Infineon Technologies Asia Pacific Pte. Ltd, Kun Zhou Nanyang Technological University

Abstract: Two-dimensional (2D) tin monoxide (SnO) has attracted much attention owing to its distinctive electronic and optical properties, which render itself suitable as a channel material in field effect transistors (FETs). However, upon contact with metals for such applications, the Fermi level pinning effect may occur, where states are induced in its band gap by the metal, hindering its intrinsic semiconducting properties. We propose the insertion of graphene at the contact interface to alleviate the metal-induced gap states. By using gold (Au) as the electrode material and monolayer SnO (mSnO) as the channel material, the geometry, bonding strength, charge transfer and tunnel barriers of charges, and electronic properties including the work function, band structure, density of states, and Schottky barriers are thoroughly investigated using first-principles calculations for the structures with and without graphene to reveal the contact behaviours and Fermi level depinning mechanism. It has been demonstrated that strong covalent bonding is formed between gold and mSnO, while the graphene interlayer forms weak van der Waals interaction with both materials, which minimises the perturbance to the band structure of mSnO. The effects of out-of-plane compression are also analysed to assess the performance of the contact under mechanical deformation, and a feasible fabrication route for the heterostructure with graphene is proposed. This work systematically explores the properties of the Au-mSnO contact for applications in FETs and provides thorough guidance for future exploitation of 2D materials in various electronic applications and for selection of buffer layers to improve metal-semiconductor contact.

3.Machine-Learning-Assisted Construction of Ternary Convex Hull Diagrams

Authors:Hugo Rossignol, Michail Minotakis, Matteo Cobelli, Stefano Sanvito

Abstract: In the search for novel intermetallic ternary alloys, much of the effort goes into performing a large number of ab-initio calculations covering a wide range of compositions and structures. These are essential to build a reliable convex hull diagram. While density functional theory (DFT) provides accurate predictions for many systems, its computational overheads set a throughput limit on the number of hypothetical phases that can be probed. Here, we demonstrate how an ensemble of machine-learning spectral neighbor-analysis potentials (SNAPs) can be integrated into a workflow for the construction of accurate ternary convex hull diagrams, highlighting regions fertile for materials discovery. Our workflow relies on using available binary-alloy data both to train the SNAP models and to create prototypes for ternary phases. From the prototype structures, all unique ternary decorations are created and used to form a pool of candidate compounds. The SNAPs are then used to pre-relax the structures and screen the most favourable prototypes, before using DFT to build the final phase diagram. As constructed, the proposed workflow relies on no extra first-principles data to train the machine-learning surrogate model and yields a DFT-level accurate convex hull. We demonstrate its efficacy by investigating the Cu-Ag-Au and Mo-Ta-W ternary systems.

4.Mechanism of cathodic protection of iron and steel in porous media

Authors:Federico Martinelli-Orlando, Shishir Mundra, Ueli M. Angst

Abstract: Cathodic protection (CP) was introduced two centuries ago and since has found widespread application in protecting structures such as pipelines, offshore installations, and bridges from corrosion. Despite its extensive use, the fundamental working mechanism of CP remains debated, particularly for metals in porous media such as soil. Here, we offer resolution to the long-standing debate by employing in-situ and ex-situ characterisation techniques coupled with electrochemical measurements to characterise the spatio-temporal changes occurring at the steel-electrolyte interface. We show that upon CP, the interfacial electrolyte undergoes alkalinisation and deoxygenation, and that depending on polarisation conditions, an iron oxide film can simultaneously form on the steel surface. We further demonstrate that these changes in interfacial electrolyte chemistry and steel surface state result in altered anodic and cathodic reactions and their kinetics. We propose a mechanism of CP that integrates the long debated theories, based on both concentration and activation polarisation, complimentarily. Implications of this coherent scientific understanding for enhancing corrosion protection technologies and the safe, economic, and environmental-friendly operation of critical steel-based infrastructures are discussed.

5.Chemical heterogeneity enhances hydrogen resistance in high-strength steels

Authors:Binhan Sun, Wenjun Lu, Ran Ding, Surendra Kumar Makineni, Baptiste Gault, Chun-Hung Wu, Di Wan, Hao Chen, Dirk Ponge, Dierk Raabe

Abstract: When H, the lightest, smallest and most abundant atom in the universe, makes its way into a high-strength alloy (>650 MPa), the material's load-bearing capacity is abruptly lost. This phenomenon, known as H embrittlement, was responsible for the catastrophic and unpredictable failure of large engineering structures in service. The inherent antagonism between high strength requirements and H embrittlement susceptibility strongly hinders the design of lightweight yet reliable structural components needed for carbon-free hydrogen-propelled industries and reduced-emission transportation solutions. Inexpensive and scalable alloying and microstructural solutions that enable both, an intrinsically high resilience to H and high mechanical performance, must be found. Here we introduce a counterintuitive strategy to exploit typically undesired chemical heterogeneity within the material's microstructure that allows the local enhancement of crack resistance and local H trapping, thereby enhancing the resistance against H embrittlement. We deploy this approach to a lightweight, high-strength steel and produce a high-number density Mn-rich zones dispersed within the microstructure. These solute-rich buffer regions allow for local micro-tuning of the phase stability, arresting H-induced microcracks thus interrupting the H-assisted damage evolution chain, regardless of how and when H is introduced and also regardless of the underlying embrittling mechanisms. A superior H embrittlement resistance, increased by a factor of two compared to a reference material with a homogeneous solute distribution within each microstructure constituent, is achieved at no expense of the material's strength and ductility.

6.Unconventional band structure via combined molecular orbital and lattice symmetries in a surface-confined metallated graphdiyne sheet

Authors:Ignacio Piquero-Zulaica, Wenqi Hu, Ari Paavo Seitsonen, Felix Haag, Johannes Küchle, Francesco Allegretti, Yuanhao Lyu, Lan Chen, Kehui Wu, Zakaria M. Abd El-Fattah, Ethem Aktürk, Svetlana Klyatskaya, Mario Ruben, Matthias Muntwiler, Johannes V. Barth, Yi-Qi Zhang

Abstract: Graphyne (GY) and graphdiyne (GDY)-based materials represent an intriguing class of two-dimensional (2D) carbon-rich networks with tunable structures and properties surpassing those of graphene. However, the challenge of fabricating atomically well-defined crystalline GY/GDY-based systems largely hinders detailed electronic structure characterizations. Here, we report the emergence of an unconventional band structure in mesoscopically regular (~1 {\mu}m) metallated GDY sheets featuring a honeycomb lattice on Ag(111) substrates. Employing complementary scanning tunnelling and angle-resolved photoemission spectroscopies, electronic band formation with a gap of 2.5 eV is rigorously determined in agreement with real-space electronic characteristics. Extensive density functional theory calculations corroborate our observations as well as recent theoretical predictions that doubly degenerate frontier molecular orbitals on a honeycomb lattice give rise to flat, Dirac and Kagome bands close to Fermi level. These results illustrate the tremendous potential of engineering novel band structures via molecular orbital and lattice symmetries in atomically precise 2D carbon scaffolds.

7.Giant piezoelectricity driven by Thouless pump in conjugated polymers

Authors:Stefano Paolo Villani, Marco Campetella, Paolo Barone, Francesco Mauri

Abstract: Piezoelectricity of organic polymers has attracted increasing interest because of several advantages they exhibit over traditional inorganic ceramics. While most organic piezoelectrics rely on the presence of intrinsic local dipoles, a highly nonlocal electronic polarization can be foreseen in conjugated polymers, characterised by delocalized and highly responsive ${\pi}$-electrons. These 1D systems represent a physical realization of a Thouless pump, a mechanism of adiabatic charge transport of topological nature which results, as shown in this work, in anomalously large dynamical effective charges, inversely proportional to the band gap energy. A structural (ferroelectric) phase transition further contributes to an enhancement of the piezoelectric response reminiscent of that observed in piezoelectric perovskites close to morphotropic phase boundaries. First-principles Density Functional Theory (DFT) calculations performed in two representative conjugated polymers using hybrid functionals, show that state-of-the-art organic piezoelectric are outperformed by piezoelectric conjugated polymers, mostly thanks to strongly anomalous effective charges of carbon, larger than 5e - ordinary values being of the order of 1e - and reaching the giant value of 30e for band gaps of the order of 1 eV.

8.Computer Simulation of Carbonization and Graphitization of Coal

Authors:C. Ugwumadu, R. Olson III, N. L. Smith, K. Nepal, Y. Al-Majali, J. Trembly, D. A. Drabold

Abstract: This study describes computer simulations of carbonization and graphite formation, including the effects of hydrogen, nitrogen, oxygen, and sulfur. We introduce a novel technique to simulate carbonization, "Simulation of Thermal Emission of Atoms and Molecules (STEAM)," designed to elucidate the removal of volatiles and density variations in carbonization residue. The investigation extensively analyzes the functional groups that endure through high-temperature carbonization and examines the graphitization processes in carbon-rich materials containing non-carbon "impurity elements". The physical, vibrational, and electronic attributes of impure amorphous graphite are analyzed, and the impact of nitrogen on electronic conduction is investigated, revealing its substitutional integration into the sp$^2$ layered network.

9.Strengthening from dislocation restructuring and local climb at platelet linear complexions in Al-Cu alloys

Authors:Pulkit Garg, Daniel S. Gianola, Timothy J. Rupert

Abstract: Stress-driven segregation at dislocations can lead to structural transitions between different linear complexion states. In this work, we examine how platelet array linear complexions influence dislocation motion and quantify the associated strengthening effect in Al-Cu alloys using atomistic simulations. The presence of platelet complexions leads to faceting of the dislocations, with nanoscale segments climbing upwards along the platelet growth direction, resulting in a complex non-planar configuration that restricts subsequent dislocation motion. Upon deformation, the leading partial dislocation must climb down from the platelet complexions first, followed by a similar sequence at the trailing partial dislocation, in order to overcome the precipitates and commence plastic slip. The dislocation depinning mechanism of linear complexions is strikingly different from traditional precipitation-strengthened alloys, where dislocations overcome obstacles by either shearing through or looping around obstacles. The critical shear stress required to unpin dislocations from platelet complexions is found to be inversely proportional to precipitate spacing, which includes not just the open space (as observed in Orowan bowing) but also the region along the platelet particle where climb occurs. Thus, platelet linear complexions provide a new way to modify dislocation structure directly and improve the mechanical properties of metal alloys.

10.Evolution of highly anisotropic magnetism in the titanium-based kagome metals LnTi$_3$Bi$_4$ (Ln: La...Gd$^{3+}$, Eu$^{2+}$, Yb$^{2+}$)

Authors:Brenden R. Ortiz, Hu Miao, Fazhi Yang, Eleanor M. Clements, David S. Parker, Jiaqiang Yan, Andrew F. May, Michael A. McGuire

Abstract: Here we present the family of titanium-based kagome metals of the form LnTi$_3$Bi$_4$ (Ln: La...Gd$^{3+}$, Eu$^{2+}$, Yb$^{2+}$). Single crystal growth methods are presented alongside detailed magnetic and thermodynamic measurements. The orthorhombic (\textit{Fmmm}) LnTi$_3$Bi$_4$ family of compounds exhibit slightly distorted titanium-based kagome nets interwoven with zig-zag lanthanide-based (Ln) chains. Crystals are easily exfoliated parallel to the kagome sheets and angular resolved photoemission (ARPES) measurements highlight the intricacy of the electronic structure in these compounds, with Dirac points existing at the Fermi level. The magnetic properties and the associated anisotropy emerge from the quasi-1D zig-zag chains of Ln, and impart a wide array of magnetic ground states ranging from anisotropic ferromagnetism to complex antiferromagnetism with a cascade of metamagnetic transitions. Kagome metals continue to provide a rich direction for the exploration of magnetic, topologic, and highly correlated behavior. Our work here introduces the LnTi$_3$Bi$_4$ compounds to augment the continuously expanding suite of complex and interesting kagome materials.

11.Impurity atom configurations in diamond and their visibility via scanning transmission electron microscopy imaging

Authors:D. Propst, J. Kotakoski, E. H. Åhlgren

Abstract: Dispersed impurities in diamond present a flourishing platform for research in quantum informatics, spintronics and single phonon emitters. Based on the vast pool of experimental and theoretical work describing impurity atoms in diamond, we review the configurations by the chemical element discussing the relevant atomic configurations and most important properties. Dopant structures expand from single to co-doping configurations, also combined with carbon vacancies. Despite of their importance, not much is known about the exact atomic configurations associated with the dopant structures beyond computational models, partially due to difficulties in their microscopic observation. To assess the visibility of these structures, we carry out image simulations to show that the heavier dopants may be easily discernible in scanning transmission electron microscopy annular dark field images, with a window of visibility of up to over $\pm$ 10 nm in defocus. We further present the first atomic resolution images of an impurity atom configuration (substitutional Er atom) in the diamond lattice, confirmed by a comparison to the simulated images. Overall, our results demonstrate that there is a vast research field waiting for the microscopy community in resolving the exact atomic structure of various impurity atom configurations in diamond.

12.Understanding coupled mass-heat transport in fluids by approach-to-equilibrium molecular dynamics

Authors:Antonio Cappai, Luciano Colombo, Claudio Melis

Abstract: We present a generalization of AEMD approach, routinely applied to estimate thermal conductivity, to the more general case in which Soret and Dufour effects determine a coupled heat-mass transfer. We show that, by starting from microscopical definitions of heat and mass currents, conservation laws dictates the form of the differential equations governing the time evolution. In particular, we focus to the well specific case in which a closed-form solution of the system is possible and derive the analytical form of time-evolution of temperature and concentration scalar fields in the case in which step-like initial profiles are imposed across a rectangular simulation cell. The validity of this new generalized expression is finally validated using as benchamrk system a two-component Lennard-Jones liquid system, for which generalized diffusivities are estimated in different reduced temperature and density region of phase diagram.

13.High-throughput assessment of the microstructural stability of segregation-engineered nanocrystalline Al-Ni-Y alloys

Authors:W. Streit Cunningham, Jungho Shin, Tianjiao Lei, Timothy J Rupert, Daniel S. Gianola

Abstract: Segregation engineering has emerged as a promising pathway towards designing thermally stable nanocrystalline alloys with enhanced mechanical properties. However, the compositional and processing space for solute stabilized microstructures is vast, thus the application of high-throughput techniques to accelerate optimal material development is increasingly attractive. In this work, combinatorial synthesis is combined with high-throughput characterization techniques to explore microstructural transitions through annealing of a nanocrystalline ternary Al-base alloy containing a transition metal (TM=Ni) and rare earth dopant (RE=Y). A down-selected optimal composition with the highest thermal stability is annealed through in situ transmission electron microscopy, revealing that the removal of the RE species is correlated to a reduction in the microstructural stability at high temperatures as a result of variations in intermetallic phase formation. Results demonstrate the benefits of co-segregation for enhancing mechanical hardness and delaying the onset of microstructural instability.

1.Delocalisation enables efficient charge generation in organic photovoltaics, even with little to no energetic offset

Authors:Daniel Balzer, Ivan Kassal

Abstract: Organic photovoltaics (OPVs) are promising candidates for solar-energy conversion, with device efficiencies continuing to increase. However, the precise mechanism of how charges separate in OPVs is not well understood because low dielectric constants produce a strong attraction between the charges, which they must overcome to separate. Separation has been thought to require energetic offsets at donor-acceptor interfaces, but recent materials have enabled efficient charge generation with small offsets, or with none at all in neat materials. Here, we extend delocalised kinetic Monte Carlo (dKMC) to develop a three-dimensional model of charge generation that includes disorder, delocalisation, and polaron formation in every step from photoexcitation to charge separation. Our simulations show that delocalisation dramatically increases charge-generation efficiency, partly by enabling excitons to dissociate in the bulk. Therefore, charge generation can be efficient even in devices with little to no energetic offset, including neat materials. Our findings demonstrate that the underlying quantum-mechanical effect that improves the charge-separation kinetics is faster and longer-distance hops between delocalised states, mediated by hybridised states of exciton and charge-transfer character.

2.In-situ Plasma Studies using a Direct Current Microplasma in a Scanning Electron Microscope

Authors:Lukas Grünewald, Dmitry Chezganov, Robin De Meyer, Andrey Orekhov, Sandra Van Aert, Annemie Bogaerts, Sara Bals, Jo Verbeeck

Abstract: Microplasmas can be used for a wide range of technological applications and to improve our understanding of fundamental physics. Scanning electron microscopy, on the other hand, provides insights into the sample morphology and chemistry of materials from the mm-down to the nm-scale. Combining both would provide direct insight into plasma-sample interactions in real-time and at high spatial resolution. Up till now, very few attempts in this direction have been made, and significant challenges remain. This work presents a stable direct current glow discharge microplasma setup built inside a scanning electron microscope. The experimental setup is capable of real-time in-situ imaging of the sample evolution during plasma operation and it demonstrates localized sputtering and sample oxidation. Further, the experimental parameters such as varying gas mixtures, electrode polarity, and field strength are explored and experimental $V$-$I$ curves under various conditions are provided. These results demonstrate the capabilities of this setup in potential investigations of plasma physics, plasma-surface interactions, and materials science and its practical applications. The presented setup shows the potential to have several technological applications, e.g., to locally modify the sample surface (e.g., local oxidation and ion implantation for nanotechnology applications) on the $\mu$m-scale.

3.Unraveling the Complexity of Metal Ion Dissolution: Insights from Hybrid First-Principles/Continuum Calculations

Authors:Mingqing Liu, Tong-Yi Zhang, Sheng Sun

Abstract: The study of ion dissolution from metal surfaces has a long-standing history, wherein the gradual dissolution of solute atoms with increasing electrode potential, leading to their existence as ions in the electrolyte with integer charges, is well-known. However, our present work reveals a more intricate and nuanced physical perspective based on comprehensive first-principles/continuum calculations. We investigate the dissolution and deposition processes of 22 metal elements across a range of applied electrode potentials, unveiling diverse dissolution models. By analyzing the energy profiles and valence states of solute atoms as a function of the distance between the solute atom and metal surface, we identify three distinct dissolution models for different metals. Firstly, solute atoms exhibit an integer valence state following an integer-valence jump, aligning with classical understandings. Secondly, solute atoms attain an eventual integer valence, yet their valence state increases in a non-integer manner during dissolution. Lastly, we observe solute atoms exhibiting a non-integer valence state, challenging classical understandings. Furthermore, we propose a theoretical criterion for determining the selection of ion valence during electrode dissolution under applied potential. These findings not only contribute to a deeper understanding of the dissolution process but also offer valuable insights into the complex dynamics governing metal ion dissolution at the atomic level. Such knowledge has the potential to advance the design of more efficient electrochemical systems and open new avenues for controlling dissolution processes in various applications.

4.Unravelling H$_2$ chemisorption and physisorption on metal decorated graphene using quantum Monte Carlo

Authors:Yasmine S. Al-Hamdani, Andrea Zen, Dario Alfé

Abstract: Molecular hydrogen is at the core of hydrogen energy applications and has the potential to significantly reduce the use of carbon dioxide emitting energy processes. However, hydrogen gas storage is a major bottleneck for its large-scale use as current storage methods are energy intensive. Among different storage methods, physisorbing molecular hydrogen at ambient pressure and temperatures is a promising alternative - particularly thanks to tuneable lightweight nanomaterials and high throughput screening methods. Nonetheless, understanding hydrogen adsorption in well-defined nanomaterials remains experimentally challenging and reference information is scarce despite the proliferation of works predicting hydrogen adsorption. In this work, we focus on Li, Na, Ca, and K, decorated graphene sheets as substrates for hydrogen adsorption and compute the most accurate adsorption energies available to date using quantum diffusion Monte Carlo (DMC). Building on our previous insights at the density functional theory (DFT) level, we find that a weak covalent chemisorption of molecular hydrogen, known as Kubas binding, is feasible on Ca decorated graphene according to DMC, in agreement with DFT. This finding is in contrast to previous DMC predictions of the 4H$_2$/Ca$^+$ gas cluster where chemisorption is not favoured. However, we find that the adsorption energy of hydrogen on metal decorated graphene according to a widely-used DFT method is not fully consistent with DMC and the discrepancies are not systematic. The reference adsorption energies reported herein can be used to find better work-horse methods for application in large-scale modelling of hydrogen adsorption. Furthermore, the implications of this work affect strategies for finding suitable hydrogen storage materials and high-throughput methods.

5.A semiclassical model for charge transfer along ion chains in silicates

Authors:Juan F R Archilla, Jānis Bajārs, Yusuke Doi, Masayuki Kimura

Abstract: It has been observed in fossil tracks and experiments in the layered silicate mica muscovite the transport of charge through the cation layers sandwiched between the layers of tetrahedra-octahedra-tetrahedra. A classical model for the propagation of anharmonic vibrations along the cation chains has been proposed based on first principles and empirical functions. In that model, several propagating entities have been found as kinks or crowdions and breathers, both with or without wings, the latter for specific velocities and energies. Crowdions are equivalent to moving interstitials and transport electric charge if the moving particle is an ion, but they also imply the movement of mass, which was not observed in the experiments. Breathers, being just vibrational entities, do not transport charge. In this work, we present a semiclassical model obtained by adding a quantum particle, electron or hole to the previous model. We present the construction of the model based on the physics of the system. In particular, the strongly nonlinear vibronic interaction between the nuclei and the extra electron or hole is essential to explain the localized charge transport, which is not compatible with the adiabatic approximation. The formation of vibrational localized charge carriers breaks the lattice symmetry group in a similar fashion to the Jahn-Teller Effect, providing a new stable dynamical state. We study the properties and the coherence of the model through numerical simulations from initial conditions obtained by tail analysis and other means. We observe that although the charge spreads from an initial localization in a lattice at equilibrium, it can be confined basically to a single particle when coupled to a chaotic quasiperiodic breather. This is coherent with the observation that experiments imply that a population of charge is formed due to the decay of potassium unstable isotopes.

6.Insights into heterogeneous catalysis on surfaces with 3d transition metals: Spin-dependent chemisorption models and magnetic field effects

Authors:Satadeep Bhattacharjee, Swetarekha Ram, Seung-Cheol Lee

Abstract: This article provides a review of recent developments in the field of 3d transition metal (TM) catalysts for different reactions including oxygen-based reactions such as Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER). The spin moments of 3d TMs can be exploited to influence chemical reactions, and recent advances in this area, including the theory of chemisorption based on spin-dependent d-band centers and magnetic field effects, are discussed. The article also explores the use of scaling relationships and surface magnetic moments in catalyst design, as well as the effect of magnetism on chemisorption and vice versa. In addition, recent studies on the influence of a magnetic field on the ORR and OER are presented, demonstrating the potential of ferromagnetic catalysts to enhance these reactions through spin polarization.

7.Robust Zeeman-type band splitting in sliding ferroelectrics

Authors:Homayoun Jafari, Evgenii Barts, Przemysław Przybysz, Karma Tenzin, Paweł J. Kowalczyk, Paweł Dabrowski, Jagoda Sławińska

Abstract: Transition metal dichalcogenides exhibit giant spin-orbit coupling, and intriguing spin-valley effects, which can be harnessed through proximity in van der Waals (vdW) heterostructures. Remarkably, due to the prismatic crystal field, the Zeeman-type band splitting of valence bands reach values of several hundreds of meV. While this effect is suppressed in the commonly studied hexagonal (H)-stacked bilayers due to the presence of inversion symmetry, the recent discovery of sliding ferroelectricity in rhombohedral (R-)stacked MX$_2$ bilayers (M=Mo, W; X=S, Se) suggests that the Zeeman effect could be present in these non-centrosymmetric configurations, making it even more intriguing to investigate how the spin-resolved bands would evolve during the phase transition. Here, we perform density functional theory calculations complemented by symmetry analysis to unveil the evolution of ferroelectricity during sliding and the behavior of Zeeman splitting along the transition path. While the evolution of the out-of-plane component of the electric polarization vector resembles the conventional ferroelectric transition, we observe significant in-plane components parallel to the sliding direction, reaching their maximum at the intermediate state. Moreover, we demonstrate that the R-stacked bilayers exhibit persistent Zeeman-type band splitting throughout the transition path, allowed by the lack of inversion symmetry. Further analysis of different stacking configurations generated by sliding along various directions confirms that the Zeeman effect in MX$_2$, primarily arising from the polarity of prismatic ligand coordination of the metal atom, is remarkably robust and completely governs the spin polarization of bands, independently of the sliding direction. This resilience promises robust spin transport in vdW based MX$_2$ bilayers, opening new opportunities for ferroelectric spintronics.

8.ZundEig: The Structure of the Proton in Liquid Water From Unsupervised Learning

Authors:Solana Di Pino, Edward Danquah Donkor, Verónica M. Sánchez, Alex Rodriguez, Giuseppe Cassone, Damian Scherlis, Ali Hassanali

Abstract: The structure of the excess proton in liquid water has been the subject of lively debate from both experimental and theoretical fronts for the last century. Fluctuations of the proton are typically interpreted in terms of limiting states referred to as the Eigen and Zundel species. Here we put these ideas under the microscope taking advantage of recent advances in unsupervised learning that use local atomic descriptors to characterize environments of acidic water combined with advanced clustering techniques. Our agnostic approach leads to the observation of only a single charged cluster and two neutral ones. We demonstrate that the charged cluster involving the excess proton, is best seen as an ionic topological defect in water's hydrogen bond network forming a single local minimum on the global free-energy landscape. This charged defect is a highly fluxional moiety where the idealized Eigen and Zundel species are neither limiting configurations nor distinct thermodynamic states. Instead, the ionic defect enhances the presence of neutral water defects through strong interactions with the network. We dub the combination of the charged and neutral defect clusters as ZundEig demonstrating that the fluctuations between these local environments provide a general framework for rationalizing more descriptive notions of the proton in the existing literature.

9.Switchable in-plane anomalous Hall effect by magnetization orientation in monolayer $\mathrm{Mn}_{3}\mathrm{Si}_{2}\mathrm{Te}_{6}$

Authors:Ding Li, Maoyuan Wang, Dengfeng Li, Jianhui Zhou

Abstract: In-plane anomalous Hall effect (IPAHE) is a unconventional anomalous Hall effect (AHE) with the Hall current flows in the plane spanned by the magnetization or magnetic field and the electric field. Here, we predict a stable two-dimensional ferromagnetic monolayer $\mathrm{Mn}_{3}\mathrm{Si}_{2}\mathrm{Te}_{6}$ with collinear ordering of Mn moments in the basal plane. Moreover, we reveal that the monolayer $\mathrm{Mn}_{3}\mathrm{Si}_{2}\mathrm{Te}_{6}$ possesses a substantial periodic IPAHE due to the threefold rotational symmetry, which can be switched by changing the magnetization orientation by external magnetic fields. In addition, we briefly discuss the impacts of moderate strains on the electronic states and AHE, which lead to a near quantized Hall conductivity. Our work provides a potential platform for realizing a sizable and controllable IPAHE that greatly facilatates the application of energy-efficient spintronic devices.

10.Self-biased magnetoelectric Ni/LiNbO3/Ni for body embedded electronic energy harvesters

Authors:Tianwen Huang, Loïc Becerra, Aurélie Gensbittel, Yunlin Zheng, Hakeim Talleb, Ulises Acevedo Salas, Zhuoxiang Ren, Massimiliano Marangolo

Abstract: In this study, we present the fabrication and characterization of Ni/LiNbO3/Ni trilayers using RF sputtering. These trilayers exhibit thick Ni layers (10 microns) and excellent adherence to the substrate, enabling high magnetoelectric coefficients. By engineering the magnetic anisotropy of Nickel through anisotropic thermal residual stress induced during fabrication, and by selecting a carefully chosen cut angle for the LiNbO3 substrate, we achieved a self-biased behavior. We demonstrate that these trilayers can power medical implant devices remotely using a small AC magnetic field excitation, thereby eliminating the need for a DC magnetic field and bulky magnetic field sources. The results highlight the potential of these trilayers for the wireless and non-invasive powering of medical implants. This work contributes to the advancement of magnetoelectric materials and their applications in healthcare technology.

11.Comment on "First-Principles Calculation of the Optical Rotatory Power of Periodic Systems: Modern Theory with Modern Functionals''

Authors:Jacques K. Desmarais

Abstract: The article [Desmarais \textit{et al.} Phys Rev. B. \textbf{107} 224430 (2023)] provided a generalization of the ``\textit{modern theory of orbital magnetization}'' to include non-local Hamiltonians (e.g. hybrid functionals of the generalized Kohn-Sham theory) for magnetic response properties. The formulation was employed for the calculation of the optical rotatory power of periodic systems, where results indicated inequivalence between sampling of direct and reciprocal spaces for those calculations far from the complete basis set limit. We show that such results can be explained by the fact that the reported calculations correspond to an approximate treatment of the action of the $\boldsymbol{\nabla_k}$ operator on Bloch orbitals. In the article, calculations are missing a hidden ``response'' contribution to the reciprocal-space derivatives. The missing response term is shown to (generally) affect the results of calculations of not only magnetic, but also electric response properties, within the context of the ``\textit{modern theory of polarization}''. Necessary conditions are provided to permit avoiding the calculation of the hidden response term.

12.Three-dimensional imaging of embedded interfaces with multislice ptychography

Authors:Colum M. O'Leary, Jianhua Zhang, Cong Su, Salman Kahn, Huaidong Jiang, Alex Zettl, Jim Ciston, Jianwei Miao

Abstract: We demonstrate the application of multislice ptychography to a twisted hexagonal boron nitride (h-BN) heterointerface from a single-view data set. The propagation from the top flake, through the interface, to the bottom flake is visualized from separate slices of the reconstruction. The depth resolution of the reconstruction is determined to be 2.74 nm, which is a significant improvement over the aperture-limited depth resolution of 6.74 nm. This is attributed to the diffraction signal extending beyond the aperture edge with the depth resolution set by the curvature of the Ewald sphere. Future advances to this approach could improve the depth resolution to the sub-nanometer level and enable the identification of individual dopants, defects and color centers in twisted heterointerfaces and other materials.

1.Defects and Oxygen Impurities in Ferroelectric Wurtzite Al$_{1-x}$Sc$_x$N Alloys

Authors:Naseem Ud Din, Cheng-Wei Lee, Geoff L. Brennecka, Prashun Gorai

Abstract: III-nitrides and related alloys are widely used for optoelectronics and as acoustic resonators. Ferroelectric wurtzite nitrides are of particular interest because of their potential for direct integration with Si and wide bandgap semiconductors, and unique polarization switching characteristics; such interest has taken off since the first report of ferroelectric Al$_{1-x}$Sc$_x$N alloys. However, the coercive fields needed to switch polarization are on the order of MV/cm, which is 1-2 orders of magnitude larger than oxide perovskite ferroelectrics. Atomic-scale point defects are known to impact the dielectric properties, including breakdown fields and leakage currents, as well as ferroelectric switching. However, very little is known about the native defects and impurities in Al$_{1-x}$Sc$_x$N, and their effect on the dielectric properties. In this study, we use first-principles calculations to determine the formation energetics of native defects and unintentional oxygen incorporation in Al$_{1-x}$Sc$_x$N. We find that nitrogen vacancies are the dominant native defects, and that they introduce multiple mid-gap states that can lead to premature dielectric breakdown in ferroelectrics and carrier recombination in optoelectronics. Growth under N-rich conditions will reduce the concentration of these deep defects. We also investigate unintentional oxygen incorporation on the nitrogen site and find that the substitutional defect is present in high concentrations, which can contribute to increased temperature-activated leakage currents. Our findings provide fundamental understanding of the defect physics in Al$_{1-x}$Sc$_x$N alloys, which is critical for future deployment of ferroelectric devices.

2.Anisotropic and pressure tunable magnetism of titanium-based Kagome ferromagnet SmTi3Bi4

Authors:Long Chen, Ying Zhou, He Zhang, Zhongnan Guo, Xiaohui Yu, Gang Wang

Abstract: Kagome magnets showing diverse topological quantum responses are crucial for next-generation topological engineering. Here we report the physical properties of a newly discovered titanium-based Kagome ferromagnet SmTi3Bi4, mainly focusing on its anisotropy and high-pressure tunability of magnetism. The crystal structure of SmTi3Bi4 belongs to the RETi3Bi4 (RE = Rare earth element) prototype, featuring a distorted Ti Kagome lattice in TiBi layer and Sm-atomic zig-zag chain along the c axis. By the temperature-dependent resistivity, heat capacity, and magnetic susceptibility measurements, a ferromagnetic (FM) ordering temperature Tc is determined to be 23.2 K, above which a T-linear resistivity and quite large density of states near Fermi level are hinted to exist. A large magnetic anisotropy was observed by rotating the in-plane magnetic field, showing the b axis is the easy magnetizations axis. The resistance under high pressure shows a suppression from 23.2 K to 8.5 K up to 23.5 GPa first and a following little enhancement up to 44.8 GPa. Considering the large in-plane magnetization between stacked Kagome lattices and tunability of FM order, possible topological phase transitions can be anticipated in SmTi3Bi4, which should be a new promising platform to explore the complex electronic and magnetic phases based on Kagome lattice.

3.Exciton-exciton Interaction in Monolayer MoSe$_2$ from Mutual Screening of Coulomb Binding

Authors:Ke Xiao, Tengfei Yan, Chengxin Xiao, Feng-ren Fan, Ruihuan Duan, Zheng Liu, Kenji Watanabe, Takashi Taniguchi, Wang Yao, Xiaodong Cui

Abstract: The potential for low-threshold optical nonlinearity has received significant attention in the fields of photonics and conceptual optical neuron networks. Excitons in two-dimensional (2D) semiconductors are particularly promising in this regard as reduced screening and dimensional confinement foster their pronounced many-body interactions towards nonlinearity. However, experimental determination of the interactions remains ambiguous, as optical pumping in general creates a mixture of excitons and unbound carriers, where the impacts of band gap renormalization and carrier screening on exciton energy counteract each other. Here by comparing the influences on exciton ground and excited states energies in the photoluminescence spectroscopy of monolayer MoSe$_2$, we are able to identify separately the screening of Coulomb binding by the neutral excitons and by charge carriers. The energy difference between exciton ground state (A-1s) and excited state (A-2s) red-shifts by 5.5 meV when the neutral exciton density increases from 0 to $4\times 10^{11}$ cm$^{-2}$, in contrast to the blue shifts with the increase of either electron or hole density. This energy difference change is attributed to the mutual screening of Coulomb binding of neutral excitons, from which we extract an exciton polarizability of $\alpha_{2D}^{\rm exciton} = 2.55\times 10^{-17}$ eV(m/V)$^2$. Our finding uncovers a new mechanism that dominates the repulsive part of many-body interaction between neutral excitons.

4.Dense and single-phase KTaO$_{3}$ ceramics obtained by spark plasma sintering

Authors:L. Féger GREMAN UMR7347, CNRS, University of Tours, INSA Centre Val de Loire, Tours, F. Giovannelli GREMAN UMR7347, CNRS, University of Tours, INSA Centre Val de Loire, Tours, G. Vats Groningen Cognitive Systems and Materials Center Department of Physics and Astronomy, Katholieke Universiteit Leuven, J. Alves GREMAN UMR7347, CNRS, University of Tours, INSA Centre Val de Loire, Tours, B. Pignon GREMAN UMR7347, CNRS, University of Tours, INSA Centre Val de Loire, Tours, E. K. H. Salje Department of Earth Sciences, University of Cambridge, I. Monot-Laffez GREMAN UMR7347, CNRS, University of Tours, INSA Centre Val de Loire, Tours, G. F. Nataf GREMAN UMR7347, CNRS, University of Tours, INSA Centre Val de Loire, Tours

Abstract: Potassium tantalate (KTaO$_{3}$) is a promising material for dielectric applications at low temperature. However, dense and single-phase ceramics cannot be obtained by conventional sintering because of the evaporation of potassium that leads to secondary phases. Here, we demonstrate that spark plasma sintering is a suitable method to obtain dense and single-phase KTaO$_{3}$ ceramics, by optimizing three parameters: initial composition, temperature, and pressure. A 2 mol% K-excess in the precursors leads to a large grain growth and dense single-phase ceramics. Without K-excess, a small amount of secondary phase (K$_{6}$Ta$_{10.8}$O$_{30}$) is observed at the surface but can be removed by polishing. At 10 K, the dielectric permittivity is 4 times higher in the ceramic from the 2 mol% K-excess powder, because of the larger grain size. The thermal conductivity decreases with decreasing grain size and stays above the thermal conductivity of KNbO$_{3}$ ceramics.

5.Abnormal behavior of preferred formation of cationic vacancy from the interior in γ-GeSe monolayer with the stereo-chemical antibonding lone-pair state

Authors:Changmeng Huan, Yongqing Cai, Devesh R. Kripalani, Kun Zhou, Qingqing Ke

Abstract: Two-dimensional (2D) materials tend to have the preferably formation of vacancies at the outer surface. Here, contrary to the normal notion, we reveal a type of vacancy that thermodynamically initiates from the interior part of the 2D backbone of germanium selenide ({\gamma}-GeSe). Interestingly, the Ge-vacancy (VGe) in the interior part of {\gamma}-GeSe possesses the lowest formation energy amongst the various types of defects considered. We also find a low diffusion barrier (1.04 eV) of VGe which is a half of those of sulfur vacancy in MoS2. The facile formation of mobile VGe is rooted in the antibonding coupling of the lone-pair Ge 4s and Se 4p states near the valence band maximum, which also exists in other gamma-phase MX (M=Sn, Ge; X=S, Te). The VGe is accompanied by a shallow acceptor level in the band gap and induces strong infrared light absorption and p-type conductivity. The VGe located in the middle cationic Ge sublattice is well protected by the surface Se layers-a feature that is absent in other atomically thin materials. Our work suggests that the unique well-buried inner VGe, with the potential of forming structurally protected ultrathin conducting filaments, may render the GeSe layer an ideal platform for quantum emitting, memristive, and neuromorphic applications.

6.Thickness-dependent catalytic activity of hydrogen evolution based on single atomic catalyst of Pt above MXene

Authors:Zheng Shu, Yongqing Cai

Abstract: Hydrogen as the cleanest energy carrier is a promising alternative renewable resource to fossil fuels. There is an ever-increasing interest in exploring efficient and cost-effective approaches of hydrogen production. Recent experiments have shown that single platinum atom immobilized on the metal vacancies of MXenes allows a high-efficient hydrogen evolution reaction (HER). Here using ab initio calculations, we design a series of substitutional Pt-doped Tin+1CnTx (Tin+1CnTx-PtSA) with different thicknesses and terminations (n = 1, 2 and 3, Tx = O, F and OH), and investigate the quantum-confinement effect on the HER catalytic performance. Surprisingly, we reveal a strong thickness effect of the MXene layer on the HER performance. Amongst the various surface-terminated derivatives, Ti2CF2-PtSA and Ti2CH2O2-PtSA are found to be the best HER catalysts with the change of Gibbs free energy {\Delta}G*H ~ 0 eV, complying with the thermoneutral condition. The ab initio molecular dynamics simulations reveal that Ti2CF2-PtSA and Ti2CH2O2-PtSA possess a good thermodynamic stability. The present work shows that the HER catalytic activity of the MXene is not solely governed by the local environment of the surface such as Pt single atom. We point out the critical role of thickness control and surface decoration of substrate in achieving a high-performance HER catalytical activity.

7.High-throughput screening of heterogeneous transition metal dual-atom catalysts by synergistic effect for nitrate reduction to ammonia

Authors:Zheng Shu, Hongfei Chen, Xing Liu, Huaxian Jia, Hejin Yan, Yongqing Cai

Abstract: Nitrate reduction to ammonia has attracted much attention for nitrate (NO3-) removal and ammonia (NH3) production. Identifying promising catalyst for active nitrate electroreduction reaction (NO3RR) is critical to realize efficient upscaling synthesis of NH3 under low-temperature condition. For this purpose, by means of spin-polarized first-principles calculations, the NO3RR performance on a series of graphitic carbon nitride (g-CN) supported double-atom catalysts (denoted as M1M2@g-CN) are systematically investigated. The synergistic effect of heterogeneous dual-metal sites can bring out tunable activity and selectivity for NO3RR. Amongst 21 candidates examined, FeMo@g-CN and CrMo@g-CN possess a high performance with low limiting potentials of -0.34 and -0.39 V, respectively. The activities can be attributed to a synergistic effect of the M1M2 dimer d orbitals coupling with the anti-bonding orbital of NO3-. The dissociation of deposited FeMo and CrMo dimers into two separated monomers is proved to be difficult, ensuring the kinetic stability of M1M2@g-CN. Furthermore, the dual-metal decorated on g-CN significantly reduces the bandgap of g-CN and broadens the adsorption window of visible light, implying its great promise for photocatalysis. This work opens a new avenue for future theoretical and experimental design related to NO3RR photo-/electrocatalysts.

8.Magnetic kagome materials RETi3Bi4 family with weak interlayer interactions

Authors:Jingwen Guo, Liqin Zhou, Jianyang Ding, Gexing Qu, Zhengtai Liu, Yu Du, Heng Zhang, Jiajun Li, Yiying Zhang, Fuwei Zhou, Wuyi Qi, Fengyi Guo, Tianqi Wang, Fucong Fei, Yaobo Huang, Tian Qian, Dawei Shen, Hongming Weng, Fengqi Song

Abstract: Kagome materials have attracted a surge of research interest recently, especially for the ones combining with magnetism, and the ones with weak interlayer interactions which can fabricate thin devices. However, kagome materials combining both characters of magnetism and weak interlayer interactions are rare. Here we investigate a new family of titanium based kagome materials RETi3Bi4 (RE = Eu, Gd and Sm). The flakes of nanometer thickness of RETi3Bi4 can be obtained by exfoliation due to the weak interlayer interactions. According to magnetic measurements, out-of-plane ferromagnetism, out-of-plane anti-ferromagnetism, and in-plane ferromagnetism are formed for RE = Eu, Gd, and Sm respectively. The magnetic orders are simple and the saturation magnetizations can be relatively large since the rare earth elements solely provide the magnetic moments. Further by angle-resolved photoemission spectroscopy (ARPES) and first-principles calculations, the electronic structures of RETi3Bi4 are investigated. The ARPES results are consistent with the calculations, indicating the bands characteristic with kagome sublattice in RETi3Bi4. We expect these materials to be promising candidates for observation of the exotic magnetic topological phases and the related topological quantum transport studies.

9.Interaction of surface cations of cleaved mica with water in vapor and liquid forms

Authors:Giada Franceschi, Sebastian Brandstetter, Jan Balajka, Igor Sokolović, Jiri Paveleć, Martin Setvín, Michael Schmid, Ulrike Diebold

Abstract: Natural minerals contain ions that become hydrated when they come into contact with water in vapor and liquid forms. Muscovite mica -- a common phyllosilicate with perfect cleavage planes -- is an ideal system to investigate the details of ion hydration. The cleaved mica surface is decorated by an array of K$^+$ ions that can be easily exchanged with other ions or protons when immersed in an aqueous solution. Despite the vast interest in the atomic-scale hydration processes of these K$^+$ ions, experimental data under controlled conditions have remained elusive. Here, atomically resolved non-contact atomic force microscopy (nc-AFM) is combined with X-ray photoelectron spectroscopy (XPS) to investigate the cation hydration upon dosing water vapor at 100 K in ultra-high vacuum (UHV). The cleaved surface is further exposed to ultra-clean liquid water at room temperature, which promotes ion mobility and partial ion-to-proton substitution. The results offer the first direct experimental views of the interaction of water with muscovite mica in UHV. The findings are in line with previous theoretical predictions.

10.Anomalous Zeeman effect in SrTiO3 and its possible all-electric detection

Authors:Sergei Urazhdin

Abstract: We show that the interplay between spin-orbit coupling and cubic symmetry breaking in SrTiO3 results in a highly anisotropic Zeeman effect, which can be measured via electrically-driven, electrically-detected spin resonance enabled by the momentum dependence of spin-orbit coupling effects that become particularly effective if the inversion symmetry is broken. The proposed effects are expected to provide a unique insight into the roles of spin-orbit interaction and symmetry breaking in SrTiO3 and its heterostructures.

11.Ultrahigh Photoresponsivity of Gold Nanodisk Array/CVD MoS$_2$-based Hybrid Phototransistor

Authors:Shyam Narayan Singh Yadav, Po-Liang Chen, Yu-Chi Yao, Yen-Yu Wang, Der-Hsien Lien, Yu-Jung Lu, Ya-Ping Hsieh, Chang-Hua Liu, Ta-Jen Yen

Abstract: Owing to its atomically thin thickness, layer-dependent tunable band gap, flexibility, and CMOS compatibility, MoS$_2$ is a promising candidate for photodetection. However, mono-layer MoS2-based photodetectors typically show poor optoelectronic performances, mainly limited by their low optical absorption. In this work, we hybridized CVD-grown monolayer MoS$_2$ with a gold nanodisk (AuND) array to demonstrate a superior visible photodetector through a synergetic effect. It is evident from our experimental results that there is a strong light-matter interaction between AuNDs and monolayer MoS$_2$, which results in better photodetection due to a surface trap state passivation with a longer charge carrier lifetime compared to pristine MoS$_2$. In particular, the AuND/MoS$_2$ system demonstrated a photoresponsivity of $8.7 \times 10^{4}$ A/W, specific detectivity of $6.9 \times 10^{13}$ Jones, and gain $1.7 \times 10^{5}$ at $31.84 \mu W/cm^{2}$ illumination power density of 632 nm wavelength with an applied voltage of 4.0 V for an AuND/MoS$_2$-based photodetector. To our knowledge, these optoelectronic responses are one order higher than reported results for CVD MoS$_2$-based photodetector in the literature.

1.Electronic-grade epitaxial (111) KTaO3 heterostructures

Authors:Jieun Kim, Muqing Yu, Jung-Woo Lee, Shun-Li Shang, Gi-Yeop Kim, Pratap Pal, Jinsol Seo, Neil Campbell, Kitae Eom, Ranjani Ramachandran, Mark S. Rzchowski, Sang Ho Oh, Si-Young Choi, Zi-Kui Liu, Jeremy Levy, Chang-Beom Eom

Abstract: KTaO3 has recently attracted attention as a model system to study the interplay of quantum paraelectricity, spin-orbit coupling, and superconductivity. However, the high and low vapor pressures of potassium and tantalum present processing challenges to creating interfaces clean enough to reveal the intrinsic quantum properties. Here, we report superconducting heterostructures based on electronic-grade epitaxial (111) KTaO3 thin films. Electrical and structural characterizations reveal that two-dimensional electron gas at the heterointerface between amorphous LaAlO3 and KTaO3 thin film exhibits significantly higher electron mobility, superconducting transition temperature and critical current density than those in bulk single crystal KTaO3-based heterostructures owing to cleaner interface in KTaO3 thin films. Our hybrid approach may enable epitaxial growth of other alkali metal-based oxides that lie beyond the capabilities of conventional methods.

2.Ab initio based study on atomic ordering in {(Ba, Sr)}TiO$_3$

Authors:Aris Dimou, Ankita Biswas, Anna Gruenebohm

Abstract: \ We combine density functional theory and molecular dynamics simulations to investigate the impact of Sr concentration and atomic ordering on the structural and ferroelectric properties of (Ba, Sr)TiO$_3$. On one hand, the macroscopic structural properties are rather insensitive to atomic ordering. On the other hand, the Curie temperature and polarization differ by $9$\% and $17$\% for different symmetries of the Sr distribution, respectively. Local ordering of Sr induces preferential polarization directions and influences the relative stability of the three ferroelectric phases.

3.Is the topological surface state floating on top of a thick lead layer? The case of the Pb/Bi2Se3 interface

Authors:Oreste De Luca, Igor A. Shvets, Sergey V. Eremeev, Ziya S. Aliev, Marek Kopciuszynski, Alexey Barinov, Fabio Ronci, Stefano Colonna, Evgueni V. Chulkov, Raffaele G. Agostino, Marco Papagno, Roberto Flammini

Abstract: The puzzling question about the floating of the topological surface state on top of a thick Pb layer, has now possibly been answered. A study of the interface made by Pb on Bi2Se3 for different temperature and adsorbate coverage condition, allowed us to demonstrate that the evidence reported in the literature can be related to the surface diffusion phenomenon exhibited by the Pb atoms, which leaves the substrate partially uncovered. Comprehensive density functional theory calculations show that despite the specific arrangement of the atoms at the interface, the topological surface state cannot float on top of the adlayer but rather tends to move inward within the substrate.

4.Ionic liquid gating induced self-intercalation of transition metal chalcogenides

Authors:Fei Wang, Yang Zhang, Zhijie Wang, Haoxiong Zhang, Xi Wu, Changhua Bao, Jia Li, Pu Yu, Shuyun Zhou

Abstract: Ionic liquids provide versatile pathways for controlling the structures and properties of quantum materials. Previous studies have reported electrostatic gating of nanometre-thick flakes leading to emergent superconductivity, insertion or extraction of protons and oxygen ions in perovskite oxide films enabling the control of different phases and material properties, and intercalation of large-sized organic cations into layered crystals giving access to tailored superconductivity. Here, we report an ionic-liquid gating method to form three-dimensional transition metal monochalcogenides (TMMCs) by driving the metals dissolved from layered transition metal dichalcogenides (TMDCs) into the van der Waals gap. We demonstrate the successful self-intercalation of PdTe$_2$ and NiTe$_2$, turning them into high-quality PdTe and NiTe single crystals, respectively. Moreover, the monochalcogenides exhibit distinctive properties from dichalcogenides. For instance, the self-intercalation of PdTe$_2$ leads to the emergence of superconductivity in PdTe. Our work provides a synthesis pathway for TMMCs by means of ionic liquid gating driven self-intercalation.

5.Ptychographic nanoscale imaging of the magnetoelectric coupling in freestanding BiFeO$_3$

Authors:Tim A. Butcher, Nicholas W. Phillips, Chun-Chien Chiu, Chia-Chun Wei, Sheng-Zhu Ho, Yi-Chun Chen, Erik Fröjdh, Filippo Baruffaldi, Maria Carulla, Jiaguo Zhang, Anna Bergamaschi, Carlos A. F. Vaz, Armin Kleibert, Simone Finizio, Jan-Chi Yang, Shih-Wen Huang, Jörg Raabe

Abstract: Soft X-ray ptychography was employed to simultaneously image the ferroelectric and antiferromagnetic domains in an 80 nm thick freestanding multiferroic BiFeO$_3$. The antiferromagnetic spin cycloid was resolved by reconstructing the resonant elastic X-ray scattering and visualised together with mosaic-like ferroelectric domains in a linear dichroic contrast image at the Fe L$_3$ edge. The measurements reveal a near perfect coupling between the magnetic and ferroelectric ordering by which the propagation direction of the spin cycloid is locked orthogonally to the ferroelectric polarisation. The results provide a direct visualisation of the strong magnetoelectric coupling in BiFeO$_3$ and of its fine multiferroic domain structure, emphasising the potential of high resolution ptychographic imaging in opening new possibilities for the study of multiferroics and non-collinear magnetic materials with soft X-rays.

1.Coercivity Mechanisms of Single-Molecule Magnets

Authors:Lei Gu, Guoping Zhaov, Yan-Zhen Zheng, Ruqian Wu

Abstract: Magnetic hysteresis has become a crucial aspect for characterizing single-molecule magnets, but the comprehension of the coercivity mechanism is still a challenge. By using analytical derivation and quantum dynamical simulations, we reveal fundamental rules that govern magnetic relaxation of single molecule magnets under the influence of external magnetic fields, which in turn dictates the hysteresis behavior. Specifically, we find that energy level crossing induced by magnetic fields can drastically increase the relaxation rate and set a coercivity limit. The activation of optical-phonon-mediated quantum tunneling accelerates the relaxation and largely determines the coercivity. Intra-molecular exchange interaction in multi-ion compounds may enhance the coercivity by suppressing key relaxation processes. A single-occupant bond in mixed-valence complexes compromises coercivity, and pre-spin-flip of the bonding electron facilitates the overall magnetization reversal. Underlying these properties are magnetic relaxation processes modulated by the interplay of magnetic fields, phonon spectrum and spin state configuration, which also proposes a fresh perspective for the nearly centurial coercive paradox.

2.The effect of different In$_2$O$_3$(111) surface terminations on CO$_2$ adsorption

Authors:Sabrina M. Gericke Division of Combustion Physics, Lund University, 221 00 Lund, Sweden, Minttu M. Kauppinen Department of Physics and Competence Centre for Catalysis, Chalmers University of Technology, 412 96 Göteborg, Sweden, Margareta Wagner Institute of Applied Physics, TU Wien, 1040 Vienna, Austria, Michele Riva Institute of Applied Physics, TU Wien, 1040 Vienna, Austria, Giada Franceschi Institute of Applied Physics, TU Wien, 1040 Vienna, Austria, Alvaro Posada-Borbón Department of Physics and Competence Centre for Catalysis, Chalmers University of Technology, 412 96 Göteborg, Sweden, Lisa Rämisch Division of Combustion Physics, Lund University, 221 00 Lund, Sweden, Sebastian Pfaff Division of Combustion Physics, Lund University, 221 00 Lund, Sweden, Erik Rheinfrank Institute of Applied Physics, TU Wien, 1040 Vienna, Austria, Alexander M. Imre Institute of Applied Physics, TU Wien, 1040 Vienna, Austria, Alexei B. Preobrajenski MAX IV Laboratory, Lund University, 221 00 Lund, Sweden, Stephan Appelfeller MAX IV Laboratory, Lund University, 221 00 Lund, Sweden, Sara Blomberg Department of Chemical Engineering, Lund University, 221 00 Lund, Sweden, Lindsay R. Merte Department of Materials Science and Applied Mathematics, Malmö University, 205 06 Malmö, Sweden, Johan Zetterberg Division of Combustion Physics, Lund University, 221 00 Lund, Sweden, Ulrike Diebold Institute of Applied Physics, TU Wien, 1040 Vienna, Austria, Henrik Grönbeck Department of Physics and Competence Centre for Catalysis, Chalmers University of Technology, 412 96 Göteborg, Sweden, Edvin Lundgren Division of Synchrotron Radiation Research, Lund University, 221 00 Lund, Sweden

Abstract: In$_2$O$_3$-based catalysts have shown high activity and selectivity for CO$_2$ hydrogenation to methanol, however the origin of the high performance of In$_2$O$_3$ is still unclear. To elucidate the initial steps of CO$_2$ hydrogenation over In$_2$O$_3$, we have combined X-ray Photoelectron Spectroscopy (XPS) and Density Functional Theory (DFT) calculations to study the adsorption of CO$_2$ on the In$_2$O$_3$(111) crystalline surface with different terminations, namely the stoichiometric, the reduced, and the hydroxylated surface, respectively. The combined approach confirms that the reduction of the surface results in the formation of In ad-atoms and that water dissociates on the surface at room temperature. A comparison of the experimental spectra and the computed core-level-shifts (using methanol and formic acid as benchmark molecules) suggests that CO$_2$ adsorbs as a carbonate on all surface terminations. We find that CO$_2$ adsorption is hindered by hydroxyl groups on the hydroxylated surface.

3.Highly efficient room-temperature nonvolatile magnetic switching by current in Fe3GaTe2 thin flakes

Authors:Shaohua Yan, Shangjie Tian, Yang Fu, Fanyu Meng, Zhiteng Li, Shouguo Wang, Xiao Zhang, Hechang Lei

Abstract: Effectively tuning magnetic state by using current is essential for novel spintronic devices. Magnetic van der Waals (vdW) materials have shown superior properties for the applications of magnetic information storage based on the efficient spin torque effect. However, for most of known vdW ferromagnets, the ferromagnetic transition temperatures lower than room temperature strongly impede their applications and the room-temperature vdW spintronic device with low energy consumption is still a long-sought goal. Here, we realize the highly efficient room-temperature nonvolatile magnetic switching by current in a single-material device based on vdW ferromagnet Fe3GaTe2. Moreover, the switching current density and power dissipation are about 300 and 60000 times smaller than conventional spin-orbit-torque devices of magnet/heavymetal heterostructures. These findings make an important progress on the applications of magnetic vdW materials in the fields of spintronics and magnetic information storage.

4.Accelerated Neural Network Training through Dimensionality Reduction for High-Throughput Screening of Topological Materials

Authors:Ruman Moulik, Ankita Phutela, Sajjan Sheoran, Saswata Bhattacharya

Abstract: Machine Learning facilitates building a large variety of models, starting from elementary linear regression models to very complex neural networks. Neural networks are currently limited by the size of data provided and the huge computational cost of training a model. This is especially problematic when dealing with a large set of features without much prior knowledge of how good or bad each individual feature is. We try tackling the problem using dimensionality reduction algorithms to construct more meaningful features. We also compare the accuracy and training times of raw data and data transformed after dimensionality reduction to deduce a sufficient number of dimensions without sacrificing accuracy. The indicated estimation is done using a lighter decision tree-based algorithm, AdaBoost, as it trains faster than neural networks. We have chosen the data from an online database of topological materials, Materiae. Our final goal is to construct a model to predict the topological properties of new materials from elementary properties.

5.Nearly-room-temperature ferromagnetism and tunable anomalous Hall effect in atomically thin Fe4CoGeTe2

Authors:Shaohua Yan, Hui-Hui He, Yang Fu, Ning-Ning Zhao, Shangjie Tian, Qiangwei Yin, Fanyu Meng, Xinyu Cao, Le Wang, Shanshan Chen, Ki-Hoon Son, Jun Woo Choi, Hyejin Ryu, Shouguo Wang, Xiao Zhang, Kai Liu, Hechang Lei

Abstract: Itinerant ferromagnetism at room temperature is a key ingredient for spin transport and manipulation. Here, we report the realization of nearly-room-temperature itinerant ferromagnetism in Co doped Fe5GeTe2 thin flakes. The ferromagnetic transition temperature TC (323 K - 337 K) is almost unchanged when thickness is down to 12 nm and is still about 284 K at 2 nm (bilayer thickness). Theoretical calculations further indicate that the ferromagnetism persists in monolayer Fe4CoGeTe2. In addition to the robust ferromagnetism down to the ultrathin limit, Fe4CoGeTe2 exhibits an unusual temperature- and thickness-dependent intrinsic anomalous Hall effect. We propose that it could be ascribed to the dependence of band structure on thickness that changes the Berry curvature near the Fermi energy level subtly. The nearly-room-temperature ferromagnetism and tunable anomalous Hall effect in atomically thin Fe4CoGeTe2 provide opportunities to understand the exotic transport properties of two-dimensional van der Waals magnetic materials and explore their potential applications in spintronics.

6.Non-reciprocal coherent all-optical switching between magnetic multi-states

Authors:T. Zalewski, V. Ozerov, A. Maziewski, I. Razdolski, A. Stupakiewicz

Abstract: We present experimental and computational findings of the laser-induced non-reciprocal motion of magnetization during ultrafast photo-magnetic switching in garnets. We found distinct coherent magnetization precession trajectories and switching times between four magnetization states, depending on both directions of the light linear polarization and initial magnetic state. As a fingerprint of the topological symmetry, the choice of the switching trajectory is governed by an interplay of the photo-magnetic torque and magnetic anisotropy. Our results open a plethora of possibilities for designing energy-efficient magnetization switching routes at arbitrary energy landscapes.

7.Nanopore-patterned CuSe drives the realization of PbSe-CuSe lateral heterostructure

Authors:Bo Li, Jing Wang, Qilong Wu, Qiwei Tian, Ping Li, Li Zhang, Long-Jing Yin, Yuan Tian, Ping Kwan Johnny Wong, Zhihui Qin, Lijie Zhang

Abstract: Monolayer PbSe has been predicted to be a two-dimensional (2D) topological crystalline insulator (TCI) with crystalline symmetry-protected Dirac-cone-like edge states. Recently, few-layered epitaxial PbSe has been grown on the SrTiO3 substrate successfully, but the corresponding signature of the TCI was only observed for films not thinner than seven monolayers, largely due to interfacial strain. Here, we demonstrate a two-step method based on molecular beam epitaxy for the growth of the PbSe-CuSe lateral heterostructure on the Cu(111) substrate, in which we observe a nanopore patterned CuSe layer that acts as the template for lateral epitaxial growth of PbSe. This further results in a monolayer PbSe-CuSe lateral heterostructure with an atomically sharp interface. Scanning tunneling microscopy and spectroscopy measurements reveal a four-fold symmetric square lattice of such monolayer PbSe with a quasi-particle band gap of 1.8 eV, a value highly comparable with the theoretical value of freestanding PbSe. The weak monolayer-substrate interaction is further supported by both density functional theory (DFT) and projected crystal orbital Hamilton population, with the former predicting the monolayer's anti-bond state to reside below the Fermi level. Our work demonstrates a practical strategy to fabricate a high-quality in-plane heterostructure, involving a monolayer TCI, which is viable for further exploration of the topology-derived quantum physics and phenomena in the monolayer limit.

8.Two-dimensional germanium islands with Dirac signature on Ag2Ge surface alloy

Authors:Jiaqi Deng, Gulnigar Ablat, Yumu Yang, Xiaoshuai Fu, Qilong Wu, Ping Li, Li Zhang, Ali Safaei, Lijie Zhang, Zhihui Qin

Abstract: Two-dimensional (2D) Dirac materials have attracted intense research efforts due to their promise for applications ranging from field-effect transistors and low-power electronics to fault-tolerant quantum computation. One key challenge is to fabricate 2D Dirac materials hosting Dirac electrons. Here, monolayer germanene is successfully fabricated on a Ag2Ge surface alloy. Scanning tunneling spectroscopy measurements revealed a linear energy dispersion relation. The latter was supported by density functional theory calculations. These results demonstrate that monolayer germanene can be realistically fabricated on a Ag2Ge surface alloy. The finding opens the door to exploration and study of 2D Dirac material physics and device applications.

1.Native Pb vacancy defects induced p-type characteristic in epitaxial monolayer PbSe

Authors:Qiwei Tian, Ping Li, Li Zhang, Yuan Tian, Long-Jing Yin, Lijie Zhang, Zhihui Qin

Abstract: PbSe, a predicted two-dimensional (2D) topological crystalline insulator (TCI) in the monolayer limit, possess excellent thermoelectric and infrared optical properties. Native defects in PbSe take a crucial role for the applications. However, little attention has been paid to the defect induced doping characteristics. Here, we provide an experimental and theoretical investigation of defects induced p-type characteristic on epitaxial monolayer PbSe on Au(111). Scanning tunneling microscopy (STM) measurements demonstrate an epitaxial PbSe monolayer with a fourfold symmetric lattice. Combined scanning tunneling spectroscopy (STS) and density functional theory (DFT) calculations reveal a quasi-particle bandgap of 0.8eV of PbSe. STM results unveil that there are two types of defects on the surface, one is related the vacancies of Pb atoms and the other is the replacement of the absent Se atoms by Pb. Corresponding theoretical optimization confirms the structures of the defects. More importantly, both STS measurements and DFT calculations give evidence that the Pb vacancies move the Fermi energy inside the valence band and produce extra holes, leading to p-type characteristics of PbSe. Our work provides effective information for the future research of device performance based on PbSe films.

2.Magnetic-order-mediated carrier and phonon dynamics in MnBi2Te4

Authors:Liang Cheng, Tian Xiang, Jingbo Qi

Abstract: We investigate the quasiparticle dynamics in MnBi2Te4 single crystal using the ultrafast optical spectroscopy. Our results show that there exist anomalous dynamical optical responses below the antiferromagnetic (AFM) ordering temperature TN. In specific, we reveal that both the initial carrier decay and recombination processes can be modulated via introducing the AFM order in sub-picosecond and picosecond timescales, respectively. We also discover a long relaxation process emerging below TN with a timescale approaching to the nanosecond regime, and can be attributed to the T-dependent spin-lattice interaction. There also emerges an unusual phonon energy renormalization below TN , which is found to arise from its coupling the spin degree via the exchange interaction and magnetic anisotropy. Our findings provide key information for understanding the dynamical properties of non-equilibrium carrier, spin and lattice in MnBi2Te4.

3.A study of Pt, Rh, Ni and Ir dispersion on anatase TiO2(101) and the role of water

Authors:Lena Puntscher, Kevin Daninger, Michael Schmid, Ulrike Diebold, Gareth S. Parkinson

Abstract: Understanding how metal atoms are stabilized on metal oxide supports is important for predicting the stability of single-atom catalysts. In this study, we use scanning tunnelling microscopy (STM) and x-ray photoelectron spectroscopy (XPS) to investigate four catalytically active metals - Platinum, Rhodium, Nickel and Iridium - on the anatase TiO2(101) surface. The metals were vapor deposited at room temperature in ultrahigh vacuum (UHV) conditions, and also with a background water pressure of 2x10-8 mbar. Pt and Ni exist as a mixture of adatoms and nanoparticles in UHV at low coverage, with the adatoms immobilized at defect sites. Water has no discernible effect on the Pt dispersion, but significantly increases the amount of Ni single atoms. Ir is highly dispersed, but sinters to nanoparticles in the water vapor background leading to the formation of large clusters at step edges. Rh forms clusters on the terrace of anatase TiO2(101) irrespective of the environment. We conclude that introducing defect sites into metal oxide supports could be a strategy to aid the dispersion of single atoms on metal-oxide surfaces, and that the presence of water should be taken into account in the modelling of single-atom catalysts.

4.Room-Temperature Highly-Tunable Coercivity and Highly-Efficient Nonvolatile Multi-States Magnetization Switching by Small Current in Single 2D Ferromagnet Fe$_3$GaTe$_2$

Authors:Gaojie Zhang, Hao Wu, Li Yang, Wen Jin, Bichen Xiao, Wenfeng Zhang, Haixin Chang

Abstract: Room-temperature electrically-tuned coercivity and nonvolatile multi-states magnetization switching is crucial for next-generation low-power 2D spintronics. However, most methods have limited ability to adjust the coercivity of ferromagnetic systems, and room-temperature electrically-driven magnetization switching shows high critical current density and high power dissipation. Here, highly-tunable coercivity and highly-efficient nonvolatile multi-states magnetization switching are achieved at room temperature in single-material based devices by 2D van der Waals itinerant ferromagnet Fe$_3$GaTe$_2$. The coercivity can be readily tuned up to ~98.06% at 300 K by a tiny in-plane electric field that is 2-5 orders of magnitude smaller than that of other ferromagnetic systems. Moreover, the critical current density and power dissipation for room-temperature magnetization switching in 2D Fe$_3$GaTe$_2$ are down to ~1.7E5 A cm$^{-2}$ and ~4E12 W m$^{-3}$, respectively. Such switching power dissipation is 2-6 orders of magnitude lower than that of other 2D ferromagnetic systems. Meanwhile, multi-states magnetization switching are presented by continuously controlling the current, which can dramatically enhance the information storage capacity and develop new computing methodology. This work opens the avenue for room-temperature electrical control of ferromagnetism and potential applications for vdW-integrated 2D spintronics.

5.Oxygen-Terminated (1x1) Reconstruction of Reduced Magnetite Fe$_3$O$_4$(111)

Authors:Florian Kraushofer, Matthias Meier, Zdeněk Jakub, Johanna Hütner, Jan Balajka, Jan Hulva, Michael Schmid, Cesare Franchini, Ulrike Diebold, Gareth S. Parkinson

Abstract: The (111) facet of magnetite (Fe$_3$O$_4$) has been studied extensively by experimental and theoretical methods, but controversy remains regarding the structure of its low-energy surface terminations. Using density functional theory (DFT) computations, we demonstrate three reconstructions that are more favorable than the accepted Fe$_{\rm oct2}$ termination in reducing conditions. All three structures change the coordination of iron in the kagome Fe$_{\rm oct1}$ layer to tetrahedral. With atomically-resolved microscopy techniques, we show that the termination that coexists with the Fe$_{\rm tet1}$ termination consists of tetrahedral iron capped by three-fold coordinated oxygen atoms. This structure explains the inert nature of the reduced patches.

6.Tailoring magnetism of nanographenes via tip-controlled dehydrogenation

Authors:Chenxiao Zhao, Qiang Huang, Leoš Valenta, Kristjan Eimre, Lin Yang, Aliaksandr V. Yakutovich, Wangwei Xu, Ji Ma, Xinliang Feng, Michal Jurí{č}ek, Roman Fasel, Pascal Ruffieux, Carlo A. Pignedoli

Abstract: Atomically precise graphene nanoflakes, called nanographenes, have emerged as a promising platform to realize carbon magnetism. Their ground state spin configuration can be anticipated by Ovchinnikov-Lieb rules based on the mismatch of {\pi}-electrons from two sublattices. While rational geometrical design achieves specific spin configurations, further direct control over the {\pi}-electrons offers a desirable extension for efficient spin manipulations and potential quantum device operations. To this end, we apply a site-specific dehydrogenation using a scanning tunneling microscope tip to nanographenes deposited on a Au(111) substrate, which shows the capability of precisely tailoring the underlying {\pi}-electron system and therefore efficiently manipulating their magnetism. Through first-principles calculations and tight-binding mean-field-Hubbard modelling, we demonstrate that the dehydrogenation-induced Au-C bond formation along with the resulting hybridization between frontier {\pi}-orbitals and Au substrate states effectively eliminate the unpaired {\pi}-electron. Our results establish an efficient technique for controlling the magnetism of nanographenes.

7.Symmetry indicator-free unconventionality, obstructed edge states and Majorana engineering in 1T-PtSe2 family

Authors:Haohao Sheng, Yue Xie, Quansheng Wu, Hongming Weng, Xi Dai, B. Andrei Bernevig, Zhong Fang, Zhijun Wang

Abstract: Unconventional materials with mismatch between electronic centers and atomic positions can be diagnosed by symmetry eigenvalues at several high-symmetry $k$ points. Their electronic states are decomposed into a sum of elementary band representations (EBRs), but not a sum of atomic valence-electron band representations (ABRs). In this work, we propose a new kind of symmetry indicator-free (SI-free) unconventional insulators, whose unconventionality has no symmetry eigenvalue indication. Instead, it is identified directly by the computed charge centers by using the one-dimensional (1D) Wilson loop method. We demonstrate that 1T-PtSe$_2$ is an SI-free unconventional insulator, whose unconventional nature originates from orbital hybridization between Pt-$d$ and Se-$p_{x,y}$ states. The SI-free unconventionality widely exists in the members of PtSe$_2$ family ($MX_2$: $M=$ Ni,Pd,Pt; $X=$ S, Se,Te).The obstructed electronic states are obtained on the edges, which exhibit large Rashba splitting. By introducing superconducting proximity and external magnetic field, we propose that the Majorana zero modes (MZM) can be generated on the corners of 1T-PtSe$_2$ monolayer.

8.Rationally Correcting Impurity Levels Positions Based on Electrostatic Potential Strategy for Photocatalytic Overall Water Splitting

Authors:Dazhong Sun, Wentao Li, Anqi Shi, Wenxia Zhang, Huabing Shu, Fengfeng Chi, Bing Wang, Xiuyun Zhang, Xianghong Niu

Abstract: Doping to induce suitable impurity levels is an effective strategy to achieve highly efficient photocatalytic overall water splitting (POWS). However, to predict the position of impurity levels, it is not enough to only depend on the projected density of states of the substituted atom in the traditional method. Herein, taking in phosphorus-doped g-C3N5 as a sample, we find that the impurity atom can change electrostatic potential gradient and polarity, then significantly affect the spatial electron density around the substituted atom, which further adjusts the impurity level position. Based on the redox potential requirement of POWS, we not only obtain suitable impurity levels, but also expand the visible light absorption range. Simultaneously, the strengthened polarity induced by doping further improve the redox ability of photogenerated carriers. Moreover, the enhanced surface dipoles obviously promote the adsorption and subsequent splitting of water molecules. Our study provides a more comprehensive view to realize accurate regulation of impurity levels in doping engineering and gives reasonable strategies for designing an excellent catalyst of POWS.

9.Plastic deformation mechanisms during nanoindentation of W, Mo, V body-centered cubic single crystals and their corresponding W-Mo, W-V equiatomic random solid solutions

Authors:F. J. Dominguez-Gutierrez, S. Papanikolaou, S. Bonfanti, M. J. Alava

Abstract: Deformation plasticity mechanisms in alloys and compounds may unveil the material capacity towards optimal mechanical properties. We conduct a series of molecular dynamics (MD) simulations to investigate plasticity mechanisms due to nanoindentation in pure tungsten, molybdenum and vanadium body-centered cubic single crystals, as well as the also body-centered cubic, equiatomic, random solid solutions (RSS) of tungsten--molybdenum and tungsten--vanadium alloys. Our analysis focuses on a thorough, side-by-side comparison of dynamic deformation processes, defect nucleation, and evolution, along with corresponding stress--strain curves. We also check the surface morphology of indented samples through atomic shear strain mapping. As expected, the presence of Mo and V atoms in W matrices introduces lattice strain and distortion, increasing material resistance to deformation and slowing down dislocation mobility of dislocation loops with a Burgers vector of 1/2 $\langle 111 \rangle$. Our side-by-side comparison displays a remarkable suppression of the plastic zone size in equiatomic W--V RSS, but not in equiatomic W--Mo RSS alloys, displaying a clear prediction for optimal hardening response equiatomic W--V RSS alloys. If the small-depth nanoindentation plastic response is indicative of overall mechanical performance, it is possible to conceive a novel MD-based pathway towards material design for mechanical applications in complex, multi-component alloys.

10.Fast near-infrared photodetectors based on nontoxic and solution-processable AgBiS2

Authors:Yi-Teng Huang, Davide Nodari, Francesco Furlan, Youcheng Zhang, Marin Rusu, Linjie Dai, Zahra Andaji-Garmaroudi, Samuel D. Stranks, Henning Sirringhaus, Akshay Rao, Nicola Gasparini, Robert L. Z. Hoye

Abstract: Solution-processable near-infrared (NIR) photodetectors are urgently needed for a wide range of next-generation electronics, including sensors, optical communications and bioimaging. However, there is currently a compromise between low toxicity and slow (<300 kHz cut-off frequency) organic materials versus faster detectors (>300 kHz cut-off frequency) based on compounds containing toxic lead or cadmium. Herein, we circumvent this trade-off by developing solution-processed AgBiS2 photodetectors with high cut-off frequencies under both white light (>1 MHz) and NIR (approaching 500 kHz) illumination. These high cut-off frequencies are due to the short transit distances of charge-carriers in the AgBiS2 photodetectors, which arise from the strong light absorption of these materials, such that film thicknesses well below 120 nm are adequate to absorb >65% of near-infrared to visible light. By finely controlling the thickness of the photoactive layer, we can modulate the charge-collection efficiency, achieve low dark current densities, and minimize the effects of ion migration to realize fast photodetectors that are stable in air. These outstanding characteristics enable real-time heartbeat sensors based on NIR AgBiS2 photodetectors. # equal contribution, * corresponding authors

11.Quantum bath augmented stochastic nonequilibrium atomistic simulations for molecular heat conduction

Authors:Renai Chen, Mohammadhasan Dinpajooh, Abraham Nitzan

Abstract: Classical molecular dynamics (MD) has been shown to be effective in simulating heat conduction in certain molecular junctions since it inherently takes into account some essential methodological components which are lacking with quantum Landauer-type transport model, such as many-body full force-field interactions, anharmonicity effects and nonlinear responses for large temperature biases. However, the classical mechanics reaches its limit in the environments where the quantum effects are significant (e.g. with low-temperatures substrates, presence of extremely high frequency molecular modes). Here, we present an atomistic simulation methodology for molecular heat conduction that incorporates the quantum Bose-Einstein statistics into an effective temperature in the form of modified Langevin equation. We show that the results from such a quasi-classical effective temperature (QCET) MD method deviates drastically when the baths temperature approaches zero from classical MD simulations and the results converge to the classical ones when the bath approaches the high-temperature limit, which makes the method suitable for full temperature range. In addition, we show that our quasi-classical thermal transport method can be used to model the conducting substrate layout and molecular composition (e.g. anharmonicities, high-frequency modes). Anharmonic models are explicitly simulated via the Morse potential and compared to pure harmonic interactions, to show the effects of anharmonicities under quantum colored bath setups. Finally, the chain length dependence of heat conduction is examined for one-dimensional polymer chains placed in between quantum augmented baths.

1.Controlling the 2D magnetism of CrBr$_3$ by van der Waals stacking engineering

Authors:Shiqi Yang, Xiaolong Xu, Bo Han, Pingfan Gu, Roger Guzman, Yiwen Song, Zhongchong Lin, Peng Gao, Wu Zhou, Jinbo Yang, Zuxin Chen, Yu Ye

Abstract: The manipulation of two-dimensional (2D) magnetic order is of significant importance to facilitate future 2D magnets for low-power and high-speed spintronic devices. Van der Waals stacking engineering makes promises for controllable magnetism via interlayer magnetic coupling. However, directly examining the stacking order changes accompanying magnetic order transitions at the atomic scale and preparing device-ready 2D magnets with controllable magnetic orders remain elusive. Here, we demonstrate effective control of interlayer stacking in exfoliated CrBr$_3$ via thermally assisted strain engineering. The stable interlayer ferromagnetic (FM), antiferromagnetic (AFM), and FM-AFM coexistent ground states confirmed by the magnetic circular dichroism measurements are realized. Combined with the first-principles calculations, the atomically-resolved imaging technique reveals the correlation between magnetic order and interlay stacking order in the CrBr$_3$ flakes unambiguously. A tunable exchange bias effect is obtained in the mixed phase of FM and AFM states. This work will introduce new magnetic properties by controlling the stacking order, and sequence of 2D magnets, providing ample opportunities for their application in spintronic devices.

2.Ferroelectric Domain and Switching Dynamics in Curved In2Se3: First Principle and Deep Learning Molecular Dynamics Simulations

Authors:Dongyu Bai, Yihan Nie, Jing Shang, Minghao Liu, Yang Yang, Haifei Zhan, Liangzhi Kou, Yuantong Gu

Abstract: Complex strain status can exist in 2D materials during their synthesis process, resulting in significant impacts on the physical and chemical properties. Despite their prevalence in experiments, their influence on the material properties and the corresponding mechanism are often understudied due to the lack of effective simulation methods. In this work, we investigated the effects of bending, rippling, and bubbling on the ferroelectric domains in In2Se3 monolayer by density functional theory (DFT) and deep learning molecular dynamics (DLMD) simulations. The analysis of the tube model shows that bending deformation imparts asymmetry into the system, and the polarization direction tends to orient towards the tensile side, which has a lower energy state than the opposite polarization direction. The energy barrier for polarization switching can be reduced by compressive strain according DFT results. The dynamics of the polarization switching is investigated by the DLMD simulations. The influence of curvature and temperature on the switching time follows the Arrhenius-style function. For the complex strain status in the rippling and bubbling model, the lifetime of the local transient polarization is analyzed by the autocorrelation function, and the size of the stable polarization domain is identified. Local curvature and temperature can influence the local polarization dynamics following the proposed Arrhenius-style equation. Through cross-scale simulations, this study demonstrates the capability of deep-learning potentials in simulating polarization for ferroelectric materials. It further reveals the potential to manipulate local polarization in ferroelectric materials through strain engineering.

3.Perforated red blood cells enable compressible and injectable hydrogels as therapeutic vehicles

Authors:Oncay Yasa, Fikru M. Tiruneh, Miriam Filippi, Aiste Balciunaite, Robert K. Katzschmann

Abstract: Hydrogels engineered for medical use within the human body need to be delivered in a minimally invasive fashion without altering their biochemical and mechanical properties to maximize their therapeutic outcomes. In this regard, key strategies applied for creating such medical hydrogels include formulating precursor solutions that can be crosslinked in situ with physical or chemical cues following their delivery or forming macroporous hydrogels at sub-zero temperatures via cryogelation prior to their delivery. Here, we present a new class of injectable composite materials with shape recovery ability. The shape recovery is derived from the physical properties of red blood cells (RBCs) that are first modified via hypotonic swelling and then integrated into the hydrogel scaffolds before polymerization. The RBCs' hypotonic swelling induces the formation of nanometer-sized pores on their cell membranes, which enable fast liquid release under compression. The resulting biocomposite hydrogel scaffolds display high deformability and shape-recovery ability. The scaffolds can repeatedly compress up to ~87% of their original volumes during injection and subsequent retraction through syringe needles of different sizes; this cycle of injection and retraction can be repeated up to ten times without causing any substantial mechanical damage to the scaffolds. Our biocomposite material system and fabrication approach for injectable materials will be foundational for the minimally invasive delivery of drug-loaded scaffolds, tissue-engineered constructs, and personalized medical platforms that could be administered to the human body with conventional needle-syringe systems.

4.Theory of defect-induced crystal field perturbations in rare earth magnets

Authors:Christopher E. Patrick, Yixuan Huang, Laura H. Lewis, Julie B. Staunton

Abstract: We present a theory describing the single-ion anisotropy of rare earth (RE) magnets in the presence of point defects. Taking the RE-lean 1:12 magnet class as a prototype, we use first-principles calculations to show how the introduction of Ti substitutions into SmFe$_{12}$ perturbs the crystal field, generating new coefficients due to the lower symmetry of the RE environment. We then demonstrate that these perturbations can be described extremely efficiently using a screened point charge model. We provide analytical expressions for the anisotropy energy which can be straightforwardly implemented in atomistic spin dynamics simulations, meaning that such simulations can be carried out for an arbitrary arrangement of point defects. The significant crystal field perturbations calculated here demonstrate that a sample which is single-phase from a structural point of view can nonetheless have a dramatically varying anisotropy profile at the atomistic level if there is compositional disorder, which may influence localized magnetic objects like domain walls or skyrmions.

5.The electrocaloric effect of lead-free Ba$_{1-y}$Ca$_y$Ti$_{1-x}$Hf$_x$O$_3$ from direct and indirect measurements

Authors:David Gracia, Sara Lafuerza, Javier Blasco, Marco Evangelisti

Abstract: We report on the dielectric and electrocaloric properties of Ba$_{1-y}$Ca$_y$Ti$_{1-x}$Hf$_x$O$_3$ for compositions $0.12<x<0.18$ and $y=0.06$, as well as $x=0.15$ and $0<y<0.15$, synthesized by the conventional solid-state reaction method. The addition of Hf/Ca broadens the ferroelectric-paraelectric phase transition, while moving it toward room temperature. Two interferroelectric transitions are seen to converge, together with the ferroelectric-paraelectric phase transition, at ca. 335 K for $0.12<x_c<0.135$ and $y=0.06$. Consistently with the dielectric properties, the electrocaloric effect maximizes closer to room temperature with increasing Hf/Ca substitutions, which promote larger temperature spans. The electrocaloric responsivity gradually decreases from 0.2 to 0.1 K$~$mm$~$kV$^{-1}$ with the addition of Hf/Ca. A homemade quasi-adiabatic calorimeter is employed to measure "directly" the electrocaloric data, which are also calculated from polarization-versus-electric-field cycles using "indirect" standard procedures. The comparison between measured and calculated values highlights the importance of having access to direct methods for a reliable determination of the electrocaloric effect.

6.A Multi-Technique Study of C2H4 Adsorption on Fe3O4(001)

Authors:Lena Puntscher, Panukorn Sombut, Chunlei Wang, Manuel Ulreich, Jiri Pavelec, Ali Rafsanjani-Abbasi, Matthias Meier, Adam Lagin, Martin Setvin, Ulrike Diebold, Cesare Franchini, Michael Schmid, Gareth S. Parkinson

Abstract: The adsorption/desorption of ethene (C2H4), also commonly known as ethylene, on Fe3O4(001) was studied under ultrahigh vacuum conditions using temperature programmed desorption (TPD), scanning tunneling microscopy, x-ray photoelectron spectroscopy, and density functional theory (DFT) based computations. To interpret the TPD data, we have employed a new analysis method based on equilibrium thermodynamics. C2H4 adsorbs intact at all coverages and interacts most strongly with surface defects such as antiphase domain boundaries and Fe adatoms. On the regular surface, C2H4 binds atop surface Fe sites up to a coverage of 2 molecules per (rt2xrt2)R45{\deg} unit cell, with every second Fe occupied. A desorption energy of 0.36 eV is determined by analysis of the TPD spectra at this coverage, which is approximately 0.1-0.2 eV lower than the value calculated by DFT + U with van der Waals corrections. Additional molecules are accommodated in between the Fe rows. These are stabilized by attractive interactions with the molecules adsorbed at Fe sites. The total capacity of the surface for C2H4 adsorption is found to be close to 4 molecules per (rt2xrt2)R45{\deg} unit cell.

7.Water Structures Reveal Local Hydrophobicity on the In2O3(111) Surface

Authors:Hao Chen, Matthias A. Blatnik, Christian L. Ritterhoff, Igor Sokolović, Francesca Mirabella, Giada Franceschi, Michele Riva, Michael Schmid, Jan Čechal, Bernd Meyer, Ulrike Diebold, Margareta Wagner

Abstract: Clean oxide surfaces are generally hydrophilic. Water molecules anchor at undercoordinated surface metal atoms that act as Lewis-acid sites, and they are stabilized by H bonds to undercoordinated surface oxygens. The large unit cell of In2O3(111) provides surface atoms in various configurations, which leads to chemical heterogeneity and a local deviation from this general rule. Experiments (TPD, XPS, ncAFM) agree quantitatively with DFT calculations and show a series of distinct phases. The first three water molecules dissociate at one specific area of the unit cell and desorb above room temperature. The next three adsorb as molecules in the adjacent region. Three more water molecules rearrange this structure and an additional nine pile up above the OH groups. Despite offering undercoordinated In and O sites, the rest of the unit cell is unfavorable for adsorption and remains water-free. The first water layer thus shows ordering into nanoscopic 3D water clusters separated by hydrophobic pockets.

8.Adsorption configurations of Co-phthalocyanine on In2O3(111)

Authors:Margareta Wagner, Fabio Calcinelli, Andreas Jeindl, Michael Schmid, Oliver T. Hofmann, Ulrike Diebold

Abstract: Indium oxide offers optical transparency paired with electric conductivity, a combination required in many optoelectronic applications. The most-stable In2O3(111) surface has a large unit cell (1.43 nm lattice constant). It contains a mixture of both bulk-like and undercoordinated O and In atoms and provides an ideal playground to explore the interaction of surfaces with organic molecules of similar size as the unit cell. Non-contact atomic force microscopy (nc-AFM), scanning tunneling microscopy (STM), and density functional theory (DFT) were used to study the adsorption of Co-phthalocyanine (CoPc) on In2O3(111). Isolated CoPc molecules adsorb at two adsorption sites in a 7:3 ratio. The Co atom sits either on top of a surface oxygen ('F configuration') or indium atom ('S configuration'). This subtle change in adsorption site induces bending of the molecules, which is reflected in their electronic structure. According to DFT the lowest unoccupied molecular orbital of the undistorted gas-phase CoPc remains mostly unaffected in the F configuration but is filled by one electron in S configuration. At coverages up to one CoPc molecule per substrate unit cell, a mixture of domains with molecules in F and S configuration are found. Molecules at F sites first condense into a F-(2x2) structure and finally rearrange into a F-(1x1) symmetry with partially overlapping molecules, while S-sited molecules only assume a S-(1x1) superstructure.

9.Neural-Network Force Field Backed Nested Sampling: Study of the Silicon p-T Phase Diagram

Authors:N. Unglert, J. Carrete, L. B. Pártay, G. K. H. Madsen

Abstract: Nested sampling is a promising method for calculating phase diagrams of materials, however, the computational cost limits its applicability if ab-initio accuracy is required. In the present work, we report on the efficient use of a neural-network force field in conjunction with the nested-sampling algorithm. We train our force fields on a recently reported database of silicon structures and demonstrate our approach on the low-pressure region of the silicon pressure-temperature phase diagram between 0 and \SI{16}{GPa}. The simulated phase diagram shows a good agreement with experimental results, closely reproducing the melting line. Furthermore, all of the experimentally stable structures within the investigated pressure range are also observed in our simulations. We point out the importance of the choice of exchange-correlation functional for the training data and show how the meta-GGA r2SCAN plays a pivotal role in achieving accurate thermodynamic behaviour using nested-sampling. We furthermore perform a detailed analysis of the exploration of the potential energy surface and highlight the critical role of a diverse training data set.

10.Direct assessment of the proton affinity of individual surface hydroxyls with non-contact atomic force microscopy

Authors:Margareta Wagner, Bernd Meyer, Martin Setvin, Michael Schmid, Ulrike Diebold

Abstract: The state of protonation/deprotonation of surfaces has far-ranging implications in all areas of chemistry: from acid-base catalysis$^1$ and the electro- and photocatalytic splitting of water$^2$, to the behavior of minerals$^3$ and biochemistry$^4$. The acidity of a molecule or a surface site is described by its proton affinity (PA) and pK$_\mathrm{a}$ value (the negative logarithm of the equilibrium constant of the proton transfer reaction in solution). For solids, in contrast to molecules, the acidity of individual sites is difficult to assess. For mineral surfaces such as oxides they are estimated by semi-empirical concepts such as bond-order valence sums$^5$, and also increasingly modeled with first-principles molecular dynamics simulations$^{6,7}$. Currently such predictions cannot be tested - the experimental measures used for comparison are typically average quantities integrated over the whole surface or, in some cases, individual crystal facets$^8$, such as the point of zero charge (pzc)$^9$. Here we assess individual hydroxyls on In$_2$O$_3$(111), a model oxide with four different types of surface oxygen atoms, and probe the strength of their hydrogen bond with the tip of a non-contact atomic force microscope (AFM). The force curves are in quantitative agreement with density-functional theory (DFT) calculations. By relating the results to known proton affinities and pK$_\mathrm{a}$ values of gas-phase molecules, we provide a direct measure of proton affinity distributions at the atomic scale.

11.Salt-assisted vapor-liquid-solid growth of one-dimensional van der Waals materials

Authors:Thang Pham, Kate Reidy, Joachim D. Thomsen, Baoming Wang, Nishant Deshmukh, Michael A. Filler, Frances M. Ross

Abstract: We have combined the benefits of two catalytic growth phenomena to form nanostructures of transition metal trichalcogenides (TMTs), materials that are challenging to grow in a nanostructured form by conventional techniques, as required to exploit their exotic physics. Our growth strategy combines the benefits of vapor-liquid-solid (VLS) growth in controlling dimension and growth location, and salt-assisted growth for fast growth at moderate temperatures. This salt-assisted VLS growth is enabled through use of a catalyst that includes Au and an alkali metal halide. We demonstrate high yields of NbS3 1D nanostructures with sub-ten nanometer diameter, tens of micrometers length, and distinct 1D morphologies consisting of nanowires and nanoribbons with [010] and [100] growth orientations, respectively. We present strategies to control the growth location, size, and morphology. We extend the growth method to synthesize other TMTs, NbSe3 and TiS3, as nanowires. Finally, we discuss the growth mechanism based on the relationships we measure between the materials characteristics (growth orientation, morphology and dimensions) and the growth conditions (catalyst volume and growth time). Our study introduces opportunities to expand the library of emerging 1D vdW materials and their heterostructures with controllable nanoscale dimensions.

12.The prototypical organic-oxide interface: intra-molecular resolution of sexiphenyl on In$_2$O$_3$(111)

Authors:Margareta Wagner, Jakob Hofinger, Martin Setvín, Lynn A. Boatner, Michael Schmid, Ulrike Diebold

Abstract: The performance of an organic-semiconductor device is critically determined by the geometric alignment, orientation, and ordering of the organic molecules. While an organic multilayer eventually adopts the crystal structure of the organic material, the alignment and configuration at the interface with the substrate/electrode material is essential for charge injection into the organic layer. This work focuses on the prototypical organic semiconductor para-sexiphenyl (6P) adsorbed on In$_2$O$_3$(111), the thermodynamically most stable surface of the material that the most common transparent conducting oxide, indium tin oxide (ITO) is based on. The onset of nucleation and formation of the first monolayer are followed with atomically-resolved scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM). Annealing to 200$^\circ$C provides sufficient thermal energy for the molecules to orient themselves along the high-symmetry directions of the surface, leading to a single adsorption site. The AFM data suggests a twisted adsorption geometry. With increasing coverage, the 6P molecules first form a loose network with poor long-range order. Eventually the molecules re-orient and form an ordered monolayer. This first monolayer has a densely packed, well-ordered (2$\times$1) structure with one 6P per In$_2$O$_3$(111) substrate unit cell, i.e., a molecular density of 5.64$\times$10$^{13}$ cm$^{-2}$.

1.Interplay Between Mixed and Pure Exciton States Controls Singlet Fission in Rubrene Single Crystals

Authors:Dmitry R. Maslennikov, Marios Maimaris, Haoqing Ning, Xijia Zheng, Navendu Mondal, Vladimir V. Bruevich, Saied Md Pratik, Andrew J. Musser, Vitaly Podzorov, Jean-Luc Bredas, Veaceslav Coropceanu, Artem A. Bakulin

Abstract: Singlet fission (SF) is a multielectron process in which one singlet exciton S converts into a pair of triplet excitons T+T. SF is widely studied as it may help overcome the Shockley-Queisser efficiency limit for semiconductor photovoltaic cells. To elucidate and control the SF mechanism, great attention has been given to the identification of intermediate states in SF materials, which often appear elusive due to the complexity and fast timescales of the SF process. Here, we apply 10fs-1ms transient absorption techniques to high-purity rubrene single crystals to disentangle the intrinsic fission dynamics from the effects of defects and grain boundaries and to identify reliably the fission intermediates. We show that above-gap excitation directly generates a hybrid vibronically assisted mixture of singlet state and triplet-pair multiexciton [S:TT], which rapidly (<100fs) and coherently branches into pure singlet or triplet excitations. The relaxation of [S:TT] to S is followed by a relatively slow and temperature-activated (48 meV activation energy) incoherent fission process. The SF competing pathways and intermediates revealed here unify the observations and models presented in previous studies of SF in rubrene and propose alternative strategies for the development of SF-enhanced photovoltaic materials.

2.Band gap reduction in highly-strained silicon beams predicted by first-principles theory and validated using photoluminescence spectroscopy

Authors:Nicolas Roisin, Marie-Stéphane Colla, Romain Scaffidi, Thomas Pardoen, Denis Flandre, Jean-Pierre Raskin

Abstract: A theoretical study of the band gap reduction under tensile stress is performed and validated through experimental measurements. First-principles calculations based on density functional theory (DFT) are performed for uniaxial stress applied in the [001], [110] and [111] directions. The calculated band gap reductions are equal to 126, 240 and 100 meV at 2$\%$ strain, respectively. Photoluminescence spectroscopy experiments are performed by deformation applied in the [110] direction. Microfabricated specimens have been deformed using an on-chip tensile technique up to ~1$\%$ as confirmed by back-scattering Raman spectroscopy. A fitting correction based on the band gap fluctuation model has been used to eliminate the specimen interference signal and retrieve reliable values. Very good agreement is observed between first-principles theory and experimental results with a band gap reduction of, respectively, 93 and 91 meV when the silicon beam is deformed by 0.95$\%$ along the [110] direction.

3.Thermoelectric properties and electronic structure of Cr(Mo,V)Nx thin films studied by synchrotron and lab-based X-ray spectroscopy

Authors:Susmita Chowdhury, Victor Hjort, Rui Shu, Grzegorz Greczynski, Arnaud le Febvrier, Per Eklund, Martin Magnuson

Abstract: Chromium-based nitrides are used in hard, resilient coatings, and show promise for thermoelectric applications due to their combination of structural, thermal, and electronic properties. Here, we investigated the electronic structures and chemical bonding correlated to the thermoelectric properties of epitaxially grown chromium-based multicomponent nitride Cr(Mo,V)Nx thin films. Due to minuscule N vacancies, finite population of Cr 3d and N 2p states appear at the Fermi level and diminishes the band opening for Cr0.51N0.49. Incorporating holes by alloying V in N deficient CrN matrix results in enhanced thermoelectric power factor with marginal change in the charge transfer of Cr to N compared to Cr0.51N0.49. Further alloying Mo isoelectronic to Cr increases the density of states across the Fermi level due to hybridization of the (Cr, V) 3d and Mo 4d-N 2p states in Cr(Mo,V)Nx. The hybridization effect with reduced N 2p states off from stoichiometry drives the system towards metal like electrical resistivity and reduction in Seebeck coefficient compensating the overall power factor still comparable to Cr0.51N0.49. The N deficiency also depicts a critical role in reduction of the charge transfer from metal to N site. The present work envisages ways for enhancing thermoelectric properties through electronic band engineering by alloying and competing effects of N vacancies.

4.Coupling Between Magnetic and Transport Properties in Magnetic Layered Material Mn2-xZnxSb

Authors:Md Rafique Un Nabi, Rabindra Basnet, Krishna Pandey, Santosh Karki Chhetri, Dinesh Upreti, Gokul Acharya, Fei Wang, Arash Fereidouni, Hugh O. H. Churchill, Yingdong Guan, Zhiqiang Mao, Jin Hu

Abstract: We synthesized single crystals for Mn2-xZnxSb and studied their magnetic and electronic transport properties. This material system displays rich magnetic phase tunable with temperature and Zn composition. In addition, two groups of distinct magnetic and electronic properties, separated by a critical Zn composition of x = 0.6, are discovered. The Zn-less samples are metallic and characterized by a resistivity jump at the magnetic ordering temperature, while the Zn-rich samples lose metallicity and show a metal-to-insulator transition-like feature tunable by magnetic field. Our findings establish Mn2-xZnxSb as a promising material platform that offers opportunities to study how the coupling of spin, charge, and lattice degrees of freedom governs interesting transport properties in 2D magnets, which is currently a topic of broad interest.

5.Magnon-Phonon coupling in Fe$_3$GeTe$_2$

Authors:Namrata Bansal, Qili Li, Paul Nufer, Lichuan Zhang, Amir-Abbas Haghighirad, Yuriy Mokrousov, Wulf Wulfhekel

Abstract: We study the dynamic coupling of magnons and phonons in single crystals of Fe3GeTe2 (FGT) using inelastic scanning tunneling spectroscopy (ISTS) with an ultra-low temperature scanning tunneling microscope. Inelastic scattering of hot carriers off phonons or magnons has been widely studied using ISTS, and we use it to demonstrate strong magnon-phonon coupling in FGT. We show a strong interaction between magnons and acoustic phonons which leads to formation of van Hove singularities originating in avoided level crossings and hybridization between the magnonic and phononic bands in this material. We identify these additional hybridization points in experiments and compare their energy with density functional theory calculations. Our findings provide a platform for designing the properties of dynamic magnon-phonon coupling in two-dimensional materials.

6.Breaking Rayleigh's law with spatially correlated disorder to control phonon transport

Authors:Simon Thébaud, Lucas Lindsay, Tom Berlijn

Abstract: Controlling thermal transport in insulators and semiconductors is crucial for many technological fields such as thermoelectrics and thermal insulation, for which a low thermal conductivity ($\kappa$) is desirable. A major obstacle for realizing low $\kappa$ materials is Rayleigh's law, which implies that acoustic phonons, which carry most of the heat, are insensitive to scattering by point defects at low energy. We demonstrate, with large scale simulations on tens of millions of atoms, that isotropic long-range spatial correlations in the defect distribution can dramatically reduce phonon lifetimes of important low-frequency heat-carrying modes, leading to a large reduction of $\kappa$ -- potentially an order of magnitude at room temperature. We propose a general and quantitative framework for controlling thermal transport in complex functional materials through structural spatial correlations, and we establish the optimal functional form of spatial correlations that minimize $\kappa$. We end by briefly discussing experimental realizations of various correlated structures.

1.Catalogue of topological electrons and phonons in all allotropes of carbon

Authors:Qing-Bo Liu, Xiang-Feng Yang, Zhe-Qi Wang, Ziyang Yu, Lun Xiong, Hua-Hua Fu

Abstract: Carbon, as one of the most common element in the earth, constructs hundreds of allotropic phases to present rich physical nature. In this work, by combining the ab inito calculations and symmetry analyses method, we systematically study a large number of allotropes of carbon (703), and discovered 315 ideal topological phononic materials and 32 topological electronic materials. The ideal topological phononic nature includes single, charge-two, three, four Weyl honons, the Dirac or Weyl nodal lines phonons, and nodal surfaces phonons. And the topological electron nature ncludes topological insulator, (Type-II) Dirac points, triple nodal points, the Dirac (Weyl) nodal lines, quadratic nodal lines and so on. For convenience, we take the uni in SG 178 and pbg in SG 230 as the examples to describe the topological features in the main. We find that it is the coexistence of single pair Weyl phonons and one-nodal surfaces phonons in the uni in SG 178, which can form the single surface arc in the (100) surface BZ and isolated double-helix surface states (IDHSSs)in the (110) surface BZ. In topological semimetal pbg in SG 230, we find that the perfect triple degenerate nodal point can be found in the near Fermi level, and it can form the clear surface states in the (001) and (110) surface BZ. Our work not only greatly expands the topological features in all allotropes of carbon, but also provide many ideal platforms to study the topological electrons and phonons.

2.Magnetoresistance anomaly during the electrical triggering of a metal-insulator transition

Authors:Pavel Salev, Lorenzo Frantino, Dayne Sasaki, Soumen Bag, Yayoi Takamura, Marcelo Rozenberg, Ivan K. Schuller

Abstract: Phase separation naturally occurs in a variety of magnetic materials and it often has a major impact on both electric and magnetotransport properties. In resistive switching systems, phase separation can be created on demand by inducing local switching, which provides an opportunity to tune the electronic and magnetic state of the device by applying voltage. Here we explore the magnetotransport properties in the ferromagnetic oxide (La,Sr)MnO3 (LSMO) during the electrical triggering of an intrinsic metal-insulator transition (MIT) that produces volatile resistive switching. This switching occurs in a characteristic spatial pattern, i.e., the formation of an insulating barrier perpendicular to the current flow, enabling an electrically actuated ferromagnetic-paramagnetic-ferromagnetic phase separation. At the threshold voltage of the MIT triggering, both anisotropic and colossal magnetoresistances exhibit anomalies including a large increase in magnitude and a sign flip. Computational analysis revealed that these anomalies originate from the coupling between the switching-induced phase separation state and the intrinsic magnetoresistance of LSMO. This work demonstrates that driving the MIT material into an out-of-equilibrium resistive switching state provides the means to electrically control of the magnetotransport phenomena.

3.Raman and IR spectra of water under graphene nanoconfinement at ambient and extreme pressure-temperature conditions: a first-principles study

Authors:Rui Hou, Chu Li, Ding Pan

Abstract: The nanoconfinement of water can result in dramatic differences in its physical and chemical properties compared to bulk water. However, a detailed molecular-level understanding of these properties is still lacking. Vibrational spectroscopy, such as Raman and infrared, is a popular experimental tool for studying the structure and dynamics of water, and is often complemented by atomistic simulations to interpret experimental spectra, but there have been few theoretical spectroscopy studies of nanoconfined water using first-principles methods at ambient conditions, let alone under extreme pressure-temperature conditions. Here, we computed the Raman and IR spectra of water nanoconfined by graphene at ambient and extreme pressure-temperature conditions using ab intio simulations. Our results revealed alterations in the Raman stretching and low-frequency bands due to the graphene confinement. We also found spectroscopic evidence indicating that nanoconfinement considerably changes the tetrahedral hydrogen bond network, which is typically found in bulk water. Furthermore, we observed an unusual bending band in the Raman spectrum at ~10 GPa and 1000 K, which is attributed to the unique molecular structure of confined ionic water. Additionally, we found that at ~20 GPa and 1000 K, confined water transformed into a superionic fluid, making it challenging to identify the IR stretching band. Finally, we computed the ionic conductivity of confined water in the ionic and superionic phases. Our results highlight the efficacy of Raman and IR spectroscopy in studying the structure and dynamics of nanoconfined water in a large pressure-temperature range. Our predicted Raman and IR spectra can serve as a valuable guide for future experiments.

4.Ab initio quantum approach to electron-hole exchange for semiconductors hosting Wannier excitons

Authors:Monique Combescot, Thierry Amand, Shiue-Yuan Shiau

Abstract: We propose a quantum approach to "electron-hole exchange", better named electron-hole pair exchange, that makes use of the second quantization formalism to describe the problem in terms of Bloch-state electron operators. This approach renders transparent the fact that such singular effect comes from interband Coulomb processes. We first show that, due to the sign change when turning from valence-electron destruction operator to hole creation operator, the interband Coulomb interaction only acts on spin-singlet electron-hole pairs, just like the interband electron-photon interaction, thereby making these spin-singlet pairs optically bright. We then show that when written in terms of reciprocal lattice vectors ${\bf G}_m$, the singularity of the interband Coulomb scattering in the small wave-vector transfer limit entirely comes from the ${\bf G}_m = 0$ term, which renders its singular behavior easy to calculate. Comparison with the usual real-space formulation in which the singularity appears through a sum of "long-range processes" over all ${\bf R}\not= 0$ lattice vectors once more proves that periodic systems are easier to handle in terms of reciprocal vectors ${\bf G}_m$ than in terms of lattice vectors $\bf R$. Well-accepted consequences of the electron-hole exchange on excitons and polaritons are reconsidered and refuted for different major reasons.

5.Sustainability-Driven Exploration of Topological Material

Authors:Artittaya Boonkird, Nathan Drucker, Manasi Mandal, Thanh Nguyen, Jingjie Yeo, Vsevolod Belosevich, Ellan Spero, Christine Ortiz, Qiong Ma, Liang Fu, Tomas Palacios, Mingda Li

Abstract: Topological materials are at the forefront of quantum materials research, offering tremendous potential for next-generation energy and information devices. However, current investigation of these materials remains largely focused on performance and often neglects the crucial aspect of sustainability. Recognizing the pivotal role of sustainability in addressing global pollution, carbon emissions, resource conservation, and ethical labor practices, we present a comprehensive evaluation of topological materials based on their sustainability and environmental impact. Our approach involves a hierarchical analysis encompassing cost, toxicity, energy demands, environmental impact, social implications, and resilience to imports. By applying this framework to over 16,000 topological materials, we establish a sustainable topological materials database. Our endeavor unveils environmental-friendly topological materials candidates which have been previously overlooked, providing insights into their environmental ramifications and feasibility for industrial scalability. The work represents a critical step toward industrial adoption of topological materials, offering the potential for significant technological advancements and broader societal benefits.

6.Berry Curvature Signatures in Chiroptical Excitonic Transitions

Authors:Samuel Beaulieu, Shuo Dong, Viktor Christiansson, Philipp Werner, Tommaso Pincelli, Jonas D. Ziegler, Takashi Taniguchi, Kenji Watanabe, Alexey Chernikov, Martin Wolf, Laurenz Rettig, Ralph Ernstorfer, Michael Schüler

Abstract: The topology of the electronic band structure of solids can be described by its Berry curvature distribution across the Brillouin zone. We theoretically introduce and experimentally demonstrate a general methodology based on the measurement of energy- and momentum-resolved optical transition rates, allowing to reveal signatures of Berry curvature texture in reciprocal space. By performing time- and angle-resolved photoemission spectroscopy of atomically thin WSe$_2$ using polarization-modulated excitations, we demonstrate that excitons become an asset in extracting the quantum geometrical properties of solids. We also investigate the resilience of our measurement protocol against ultrafast scattering processes following direct chiroptical transitions.

7.Critical enhancement of the spin Hall effect by spin fluctuations

Authors:Satoshi Okamoto, Naoto Nagaosa

Abstract: The spin Hall (SH) effect, the conversion of the electric current to the spin current along the transverse direction, relies on the relativistic spin-orbit coupling (SOC). Here, we develop microscopic mechanisms of the SH effect in magnetic metals, where itinerant electrons are coupled with localized magnetic moments via the Hund exchange interaction and the SOC. Both antiferromagnetic metals and ferromagnetic metals are considered. It is shown that the spin Hall conductivity can be significantly enhanced by the spin fluctuation when approaching the magnetic transition temperature of both cases. For antiferromagnetic metals, the pure SHE appears in entire temperature range, while for ferromagnetic metals, the pure SHE is expected to be replaced by the anomalous Hall effect below the transition temperature. We also discuss possible experimental realizations and the effect of the quantum criticality when the antiferromagnetic transition temperature is tuned to zero temperature.

8.Shift current with Gaussian basis sets $\&$ general prescription for maximally-symmetric summations in the irreducible Brillouin zone

Authors:M. A. García-Blázquez, J. J. Esteve-Paredes, A. J. Uría, J. J. Palacios

Abstract: The bulk photovoltaic effect is an experimentally verified phenomenon by which a direct charge current is induced within a non-centrosymmetric material by light illumination. Calculations of its intrinsic contribution, the shift current, are nowadays amenable from first-principles employing plane-waves bases. In this work we present a general method for evaluating the shift conductivity in the framework of localized Gaussian basis sets that can be employed in both the length and velocity gauges, carrying the idiosyncrasies of the quantum-chemistry approach. The (possibly magnetic) symmetry of the system is exploited in order to fold the reciprocal space summations to the representation domain, allowing to reduce computation time and unveiling the complete symmetry properties of the conductivity tensor under general light polarization.

9.Pressure-induced softening in bulk modulus due to magneto-elastic coupling in Nd$_2$CoFeO$_6$ double Perovskite

Authors:Bidisha Mukherjee, Mrinmay Sahu, Debabrata Samanta, Bishnupada Ghosh, Boby Joseph, Goutam Dev Mukherjee

Abstract: Double perovskite oxide materials have garnered tremendous interest due to their strong spin-lattice-charge coupling. Interesting in their own right, rare-earth-based DPOs have yet to be subjected to high-pressure studies. In this paper, we have investigated the structural response of Nd$_2$CoFeO$_6$ to pressure by XRD and Raman spectroscopic measurements. From XRD data, we have observed pressure-induced structural transition from the orthorhombic phase to the monoclinic phase at about 13.8~\si{\giga\pascal}. An anomalous increase in compressibility at a much lower pressure($\sim$1.1~\si{\giga\pascal}) is seen where no structural transition occurs. At about the same pressure, a sudden drop in the slope of Raman modes is observed. Further investigation at low temperatures reveals that the B$_g$ Raman mode is strongly affected by magnetic interactions. Additional high-pressure Raman experiments with the application of a magnetic field indicated that the mentioned anomaly around 1.1~\si{\giga\pascal} can be explained by a high-spin to low-spin transition of Co$^{3+}$.

10.Revealing process and material parameter effects on densification via phase-field studies

Authors:Marco Seiz, Henrik Hierl, Britta Nestler, Wolfgang Rheinheimer

Abstract: Sintering is an important processing step in both ceramics and metals processing. The microstructure resulting from this process determines many materials properties of interest. Hence the accurate prediction of the microstructure, depending on processing and materials parameters, is of great importance. The phase-field method offers a way of predicting this microstructural evolution on a mesoscopic scale. The present paper employs this method to investigate concurrent densification and grain growth and the influence of stress on densification. Furthermore, the method is applied to simulate the entire freeze-casting process chain for the first time ever by simulating the freezing and sintering processes separately and passing the frozen microstructure to the present sintering model.

11.Magnon Diffusion Length and Longitudinal Spin Seebeck Effect in Vanadium Tetracyanoethylene (V[TCNE]$_x$, $x \sim 2$)

Authors:Seth W. Kurfman, Denis R. Candido, Brandi Wooten, Yuanhua Zheng, Michael J. Newburger, Shuyu Cheng, Roland K. Kawakami, Joseph P. Heremans, Michael E. Flatté, Ezekiel Johnston-Halperin

Abstract: Spintronic, spin caloritronic, and magnonic phenomena arise from complex interactions between charge, spin, and structural degrees of freedom that are challenging to model and even more difficult to predict. This situation is compounded by the relative scarcity of magnetically-ordered materials with relevant functionality, leaving the field strongly constrained to work with a handful of well-studied systems that do not encompass the full phase space of phenomenology predicted by fundamental theory. Here we present an important advance in this coupled theory-experiment challenge, wherein we extend existing theories of the spin Seebeck effect (SSE) to explicitly include the temperature-dependence of magnon non-conserving processes. This expanded theory quantitatively describes the low-temperature behavior of SSE signals previously measured in the mainstay material yttrium iron garnet (YIG) and predicts a new regime for magnonic and spintronic materials that have low saturation magnetization, $M_S$, and ultra-low damping. Finally, we validate this prediction by directly observing the spin Seebeck resistance (SSR) in the molecule-based ferrimagnetic semiconductor vanadium tetracyanoethylene (V[TCNE]$_x$, $x \sim 2$). These results validate the expanded theory, yielding SSR signals comparable in magnitude to YIG and extracted magnon diffusion length ($\lambda_m>1$ $\mu$ m) and magnon lifetime for V[TCNE]$_x$ ($\tau_{th}\approx 1-10$ $\mu$ s) exceeding YIG ($\tau_{th}\sim 10$ ns). Surprisingly, these properties persist to room temperature despite relatively low spin wave stiffness (exchange). This identification of a new regime for highly efficient SSE-active materials opens the door to a new class of magnetic materials for spintronic and magnonic applications.

12.Theoretical study of conventional semiconductors as transducers to increase power and efficiency in betavoltaic batteries

Authors:Davood Ghasemabadi, Hosein Zaki Dizaji, Masoud Abdollahzadeh

Abstract: Semiconductor materials play an important role as transducers of electrical energy in betavoltaic batteries. Optimal selection of effective factors will increase the efficiency of these batteries. In this study, based on common semiconductors and relying on increasing the maximum efficiency of betavoltaic batteries and the possibility of using 3H, 63Ni, and 147Pm beta sources, the indicators and criteria for optimal selection of semiconductor materials are determined. Evaluation criteria include the backscattering coefficient of beta particles from semiconductors, efficiency of electron-hole pairs generation, electronic specifications and properties, radiation damage threshold, radiation yield, stopping power and penetration of beta particles in semiconductors, physical characteristics, temperature tolerance, accessibility, and fabrication are considered. Conventional semiconductors have been quantitatively evaluated based on these criteria and compared with silicon semiconductors. 10 semiconductors, , diamond, 2H-SiC, 3C-SiC, 4H-SiC, AlN, MgO, B4C with effective atomic number less than 14 and bandgap energy above 1.12 eV at room temperature (300K) compared to Silicon semiconductors are evaluated. Finally, according to the evaluation indicators, Diamond, c-BN, and 4H-SiC are more suitable semiconductors in terms of efficiency have selected, respectively. The results indicate that for planar batteries, a betavoltaic semiconductor type junction for Schottky diamond with 147pm radioisotope, and 4H-SiC semiconductors with 63Ni or 3H radioisotopes, and for three-dimensional structures of betavoltaic batteries, Si combination with 147pm or 63Ni radioisotopes is recommended.

13.Accelerating force calculation for dislocation dynamics simulations

Authors:Rasool Ahmad, Wei Cai

Abstract: Discrete dislocation dynamics (DDD) simulations offer valuable insights into the plastic deformation and work-hardening behavior of metals by explicitly modeling the evolution of dislocation lines under stress. However, the computational cost associated with calculating forces due to the long-range elastic interactions between dislocation segment pairs is one of the main causes that limit the achievable strain levels in DDD simulations. These elastic interaction forces can be obtained either from the integral of the stress field due to one segment over the other segment, or from the derivatives of the elastic interaction energy. In both cases, the results involve a double-integral over the two interacting segments. Currently, existing DDD simulations employ the stress-based approach with both integrals evaluated either from analytical expressions or from numerical quadrature. In this study, we systematically analyze the accuracy and computational cost of the stress-based and energy-based approaches with different ways of evaluating the integrals. We find that the stress-based approach is more efficient than the energy-based approach. Furthermore, the stress-based approach becomes most cost-effective when one integral is evaluated from analytic expression and the other integral from numerical quadrature. For well-separated segment pairs whose center distances are more than three times their lengths, this one-analytic-integral and one-numerical-integral approach is more than three times faster than the fully analytic approach, while the relative error in the forces is less than $10^{-3}$. Because the vast majority of segment pairs in a typical simulation cell are well-separated, we expect the hybrid analytic/numerical approach to significantly boost the numerical efficiency of DDD simulations of work hardening.

1.Torsional Force Microscopy of Van der Waals Moirés and Atomic Lattices

Authors:Mihir Pendharkar, Steven J. Tran, Gregory Zaborski Jr., Joe Finney, Aaron L. Sharpe, Rupini V. Kamat, Sandesh S. Kalantre, Marisa Hocking, Nathan J. Bittner, Kenji Watanabe, Takashi Taniguchi, Bede Pittenger, Christina J. Newcomb, Marc A. Kastner, Andrew J. Mannix, David Goldhaber-Gordon

Abstract: In a stack of atomically-thin Van der Waals layers, introducing interlayer twist creates a moir\'e superlattice whose period is a function of twist angle. Changes in that twist angle of even hundredths of a degree can dramatically transform the system's electronic properties. Setting a precise and uniform twist angle for a stack remains difficult, hence determining that twist angle and mapping its spatial variation is very important. Techniques have emerged to do this by imaging the moir\'e, but most of these require sophisticated infrastructure, time-consuming sample preparation beyond stack synthesis, or both. In this work, we show that Torsional Force Microscopy (TFM), a scanning probe technique sensitive to dynamic friction, can reveal surface and shallow subsurface structure of Van der Waals stacks on multiple length scales: the moir\'es formed between bilayers of graphene and between graphene and hexagonal boron nitride (hBN), and also the atomic crystal lattices of graphene and hBN. In TFM, torsional motion of an AFM cantilever is monitored as the it is actively driven at a torsional resonance while a feedback loop maintains contact at a set force with the surface of a sample. TFM works at room temperature in air, with no need for an electrical bias between the tip and the sample, making it applicable to a wide array of samples. It should enable determination of precise structural information including twist angles and strain in moir\'e superlattices and crystallographic orientation of VdW flakes to support predictable moir\'e heterostructure fabrication.

2.Dynamic tight binding for large-scale electronic-structure calculations of semiconductors at finite temperatures

Authors:Martin Schwade, Maximilian J. Schilcher, Christian Reverón Baecker, Manuel Grumet, David A. Egger

Abstract: Calculating the electronic structure of materials at finite temperatures is important for rationalizing their physical properties and assessing their technological capabilities. However, finite-temperature calculations typically require large system sizes or long simulation times. This is challenging for non-empirical theoretical methods because the involved bottleneck of performing many first-principles calculations can pose a steep computational barrier for larger systems. While machine-learning molecular dynamics enables large-scale/long-time simulations of the structural properties, the difficulty of computing in particular the electronic structure of large and disordered materials still remains. In this work, we suggest an adaptation of the tight-binding formalism which allows for computationally efficient calculations of temperature-dependent properties of semiconductors. Our dynamic tight-binding approach utilizes hybrid-orbital basis functions and a modeling of the distance dependence of matrix elements via numerical integration of atomic orbitals. We show that these design choices lead to a dynamic tight-binding model with a minimal amount of parameters which are straightforwardly optimized using density functional theory. Combining dynamic tight-binding with machine learning molecular dynamics and hybrid density functional theory, we find that it accurately describes finite-temperature electronic properties in comparison to experiment for the prototypical semiconductor gallium-arsenide.

3.On the role of selective nucleation and growth to recrystallization texture development in a Mg-Gd-Zn alloy

Authors:F. Mouhib, B. Gao, T. Al-Samman

Abstract: One of the main material properties altered by rare earth additions in magnesium alloys is texture, which can be specifically adjusted to enhance ductility and formability. The current study aims at illuminating the texture selection process in a Mg-0.073at%Gd-0.165at%Zn alloy by investigating recrystallization nucleation and early nucleus growth during static recrystallization. An as-cast sample of the investigated alloy was deformed in uniaxial compression at 200{\deg}C till 40% strain and was then cut into two halves for subsequent microstructure characterization via ex-situ and quasi in-situ EBSD investigations. In order to gain insights into the evolution of texture during recrystallization, the contributions from dynamic and static recrystallization were initially separated and the origin of the non-basal orientation of recrystallization nuclei was traced back to several potential nucleation sites within the deformed matrix. Considering the significant role of double-twin band recrystallization in determining the recrystallization texture, this type of recrystallization nucleation was further investigated via quasi-in-situ EBSD on a deformed sample, annealed at 400{\deg} for different annealing times. With progressive annealing a noticeable trend was observed, in which the basal nuclei gradually diminished and eventually vanished from the annealed microstructure. In contrast, the off-basal nuclei exhibited continuous growth, ultimately becoming the dominant contributors to the recrystallization texture. The study therefore emphasizes the importance of particular nucleation sites that generate favorably oriented off-basal nuclei, which over the course of recrystallization outcompete the neighboring basal-oriented nuclei in terms of growth, and thereby dominate the recrystallization texture.

4.Origins of limited non-basal plasticity in μ-phase at room temperature

Authors:W. Luo, C. Gasper, S. Zhang, P. L. Sun, Z. Xie, S. Korte-Kerzel

Abstract: We unveil a new non-basal slip mechanism in the {\mu}-phase at room temperature using nanomechanical testing, transmission electron microscopy and atomistic simulations. The (1-105) planar faults with a displacement vector of 0.07[-5502] can be formed by dislocation glide. They do not disrupt the Frank-Kasper packing and therefore enable the accommodation of plastic strain at low temperatures without requiring atomic diffusion. The intersections between the (1-105) planar faults and basal slip result in stress concentration and crack nucleation during loading.

5.Magnetic Order and Crystallographic Disorder in Cu-Doped MnBi Crystals

Authors:Gina Angelo, Jeremy G. Philbrick, Jian Zhang, Tai Kong, Xin Gui

Abstract: Permanent magnets are of great importance due to their vast applications. MnBi has been proposed to be a potential permanent magnet that can be widely used while past efforts have been focused on optimizing the ferromagnetic low-temperature phase of MnBi. Herein, we report a series of new materials, CuxMn1-xBi, crystallizing in a high-temperature-phase (HTP) MnBi-related structure. We synthesized single crystals of CuxMn1-xBi and found that they crystallize in an unreported trigonal structure (P -31c). Magnetic properties measurements imply high-temperature antiferromagnetic (AFM) ordering and low-temperature ferromagnetic or ferrimagnetic (FM/FiM) ordering. By analyzing the doping effect on crystal structure and magnetic properties, we established a magnetic phase diagram for Cu-doped MnBi and attributed the AFM and FM/FiM to two different atomic sites of Mn. The newly found materials can help interpret the structure-magnetism relation in HTP-MnBi and open a new way for investigating future MnBi permanent magnets.

6.Intrinsic defects and mid-gap states in quasi-one-dimensional Indium Telluride

Authors:Meryem Bouaziz, Aymen Mahmoudi, Geoffroy Kremer, Julien Chaste, Cesar Gonzalez, Yannick J. Dappe, Francois Bertran, Patrick Le Fevre, Marco Pala, Fabrice Oehler, Jean-Christophe Girard, Abdelkarim Ouerghi

Abstract: Recently, intriguing physical properties have been unraveled in anisotropic semiconductors, in which the in-plane electronic band structure anisotropy often originates from the low crystallographic symmetry. The atomic chain is the ultimate limit in material downscaling for electronics, a frontier for establishing an entirely new field of one-dimensional quantum materials. Electronic and structural properties of chain-like InTe are essential for better understanding of device applications such as thermoelectrics. Here, we use scanning tunneling microscopy/spectroscopy (STM/STS) measurements and density functional theory (DFT) calculations to directly image the in-plane structural anisotropy in tetragonal Indium Telluride (InTe). As results, we report the direct observation of one-dimensional In1+ chains in InTe. We demonstrate that InTe exhibits a band gap of about 0.40 +-0.02 eV located at the M point of the Brillouin zone. Additionally, line defects are observed in our sample, were attributed to In1+ chain vacancy along the c-axis, a general feature in many other TlSe-like compounds. Our STS and DFT results prove that the presence of In1+ induces localized gap state, located near the valence band maximum (VBM). This acceptor state is responsible for the high intrinsic p-type doping of InTe that we also confirm using angle-resolved photoemission spectroscopy.

7.Heat-conserving three-temperature model for ultrafast demagnetization of 3d ferromagnets

Authors:M. Pankratova, I. P. Miranda, D. Thonig, M. Pereiro, E. Sjoqvist, A. Delin, P. Scheid, O. Eriksson, A. Bergman

Abstract: We study the ultrafast magnetization dynamics of bcc Fe and fcc Co using the recently suggested heat-conserving three-temperature model (HC3TM), together with atomistic spin- and lattice dynamics simulations. It is shown that this type of Langevin-based simulation is able to reproduce observed trends of the ultrafast magnetization dynamics of fcc Co and bcc Fe, in agreement with previous findings for fcc Ni. The simulations are performed by using parameters that to as large extent as possible are obtained from electronic structure theory. The one parameter that was not calculated in this way, was the damping term used for the lattice dynamics simulations, and here a range of parameters were investigated. It is found that this term has a large influence on the details of the magnetization dynamics. The dynamics of iron and cobalt is compared with previous results for nickel and similarities and differences in the materials' behavior are analysed following the absorption of a femtosecond laser pulse. Importantly, for all elements investigated so far with this model, we obtain a linear relationship between the value of the maximally demagnetized state and the fluence of the laser pulse, which is in agreement with experiments.

8.Efficient Quantum Transduction Using Anti-Ferromagnetic Topological Insulators

Authors:Haowei Xu, Changhao Li, Guoqing Wang, Hao Tang, Paola Cappellaro, Ju Li

Abstract: Transduction of quantum information between distinct quantum systems is an essential step in various applications, including quantum networks and quantum computing. However, quantum transduction needs to mediate between photons with vastly different frequencies, making it challenging to design high-performance transducers, due to multifaceted and sometimes conflicting requirements. In this work, we first discuss some general principles for quantum transducer design, and then propose solid-state anti-ferromagnetic topological insulators to serve as highly effective transducers. First, topological insulators exhibit band-inversion, which can greatly enhance their optical responses. Coupled with their robust spin-orbit coupling and high spin density, this property leads to strong nonlinear interaction in topological insulators, thereby substantially improving transduction efficiency. Second, the anti-ferromagnetic order can minimize the detrimental influence on other neighboring quantum systems due to magnetic interactions. Using $\rm MnBi_2Te_4$ as an example, we showcase that unit transduction fidelity can be achieved with modest experimental requirements, while the transduction bandwidth can reach the GHz range. The strong nonlinear interaction in magnetic topological insulators can find diverse applications, including the generation of entanglement between photons of distinct frequencies.

9.Surface Second Harmonic Generation from Topological Dirac Semimetal PdTe$_2$

Authors:Syed Mohammed Faizanuddin, Ching-Hang Chien, Yao-Jui Chan, Si-Tong Liu, Chia-Nung Kuo, Chin Shuan Lue, Yu-Chieh Wen

Abstract: Recent experiments and calculations in topological semimetals have observed anomalously strong second-order optical nonlinearity, but yet whether the enhancement also occurs at surfaces of topological semimetals in general remains an open question. In this work, we tackle this problem by measuring polarization-dependent and rotational-anisotropy optical second harmonic generation (SHG) from centrosymmetric type-II Dirac semimetal PdTe$_2$. We found the SHG to follow C$_{3v}$ surface symmetry with a time-varying intensity dictated by the oxidation kinetics of the material after its surface cleavage, indicating the surface origin of SHG. Quantitative characterization of the surface nonlinear susceptibility indicates a large out-of-plane response of PdTe$_2$ with $|\chi_{ccc}^{(2)}|$ up to 25 $\times$ 10$^{-18}$ m$^2$/V. Our results support the topological surfaces/interfaces as a new route toward applications of nonlinear optical effects with released symmetry constraints, and demonstrate SHG as a viable means to in situ study of kinetics of topological surfaces.

10.Transient Ellipsometry Measurements of the Specular Inverse Faraday Effect in Transition Metals

Authors:Víctor H. Ortiz, Shashi B. Mishra, Luat Vuong, Sinisa Coh, Richard B. Wilson

Abstract: The inverse Faraday effect is an opto-magnetic phenomenon that describes the ability of circularly polarized light to induce magnetism in solids. The capability of light to control magnetic order in solid state materials and devices is of interest for a variety of applications, such as magnetic recording, quantum computation and spintronic technologies. However, significant gaps in understanding about the effect persist, such as what material properties govern the magnitude of the effect in metals. In this work, we report time-resolved measurements of the specular inverse Faraday effect in non-magnetic metals, i.e., the magneto-optic Kerr effect induced by circularly polarized light. We measure this specular inverse Faraday effect in Cu, Pd, Pt, W, Ta, and Au at a laser wavelength of 783 nm. For Ta and W, we investigate both {\alpha} and \{beta} phases. We observe that excitation of these metals with circularly polarized light induces significant circular dichroism. This nonlinear magneto-optical response to circularly polarized light is an order of magnitude larger in {\alpha}-W than other metals, e.g., Pt, Au, and is greater than nearly all other reported values for IFE in other materials. Our results benchmark the range of IFE that can be observed in non-magnetic metals and provide insight into what material properties govern the inverse Faraday effect in metals.

11.Dielectric Screening and Electric Field Control of Ferromagnetism at the CaMnO$_3$/CaRuO$_3$ Interface

Authors:Churna Bhandari, S Satpathy

Abstract: Control of magnetism by an applied electric field is a desirable technique for the functionalization of magnetic materials. Motivated by recent experiments, we study the electric field control of the interfacial magnetism of CaRuO$_3$/CaMnO$_3$ (CRO/CMO) (001), a prototype interface between a non-magnetic metal and an antiferromagnetic insulator. Even without the electric field, the interfacial CMO layer acquires a ferromagnetic moment due to a spin-canted state, caused by the Anderson-Hasegawa double exchange (DEX) between the Mn moments and the leaked electrons from the CRO side. An electric field would alter the carrier density at the interface, leading to the possibility of controlling the magnetism, since DEX is sensitive to the carrier density. We study this effect quantitatively usingdensity-functional calculations in the slab geometry. We find a text-book like dielectric screening of the electric field, which introduces polarization charges at the interfaces and the surfaces. The extra charge at the interface enhances the ferromagnetism via the DEX interaction, while away from the interface the original AFM state of the Mn layers remains unchanged. The effect could have potential application in spintronics devices.

12.Rare-earth Engineering of the Magnetocaloric Effect in RMn6Sn6

Authors:Kyle Fruhling, Xiaohan Yao, Alenna Streeter, Fazel Tafti

Abstract: We present a comprehensive study of the magnetocaloric effect (MCE) in a family of kagome magnets with formula RMn6Sn6 (R=Tb, Ho, Er, and Lu). These materials have a small rare-earth content and tunable magnetic ordering, hence they provide a venue to study the fundamentals of the MCE. We examine the effect of different types of order (ferromagnetic, ferrimagnetic, and antiferromagnetic) and the presence of a metamagnetic transition on the MCE. We extend the study to a high-entropy rare-earth alloys of the family, and conclude with several guidelines for enhancing the MCE in tunable magnetic materials with a small rare-earth content.

13.Quasicrystal structure prediction: A review

Authors:Michael Widom, Marek Mihalkovic

Abstract: Predicting quasicrystal structures is a multifaceted problem that can involve predicting a previously unknown phase, predicting the structure of an experimentally observed phase, or predicting the thermodynamic stability of a given structure. We survey the history and current state of these prediction efforts with a focus on methods that have improved our understanding of the structure and stability of known metallic quasicrystal phases. Advances in the structural modeling of quasicrystals, along with first principles total energy calculation and statistical mechanical methods that enable the calculation of quasicrystal thermodynamic stability, are illustrated by means of cited examples of recent work.

1.Biaxial strain modulated electronic structures of layered two-dimensional MoSiGeN4 Rashba systems

Authors:Puxuan Li, Xuan Wang, Haoyu Wang, Qikun Tian, Jinyuan Xu, Linfeng Yu, Guangzhao Qin, Zhenzhen Qin

Abstract: The two-dimensional (2D) MA2Z4 family has received extensive attention in manipulating its electronic structure and achieving intriguing physical properties. However, engineering the electronic properties remains a challenge. Herein, based on first-principles calculations, we systematically investigate the effect of biaxial strains on the electronic structures of 2D Rashba MoSiGeN4 (MSGN), and further explore how the interlayer interactions affect the Rashba spin splitting in such strained layered MSGNs. After applying biaxial strains, the band gap decreases monotonically with increasing tensile strains but increases when the compressive strains are applied. An indirect-direct-indirect band gap transition is induced by applying a moderate compressive strain (< 5%) in the MSGNs. Due to the symmetry breaking and moderate spin-orbit coupling (SOC), the monolayer MSGN possess an isolated Rashba spin splitting (R) near the Fermi level, which could be effectively regulated to the Lifshitz transition (L) by biaxial strain. For instance, a L-R-L transformation of Fermi surface is presented in monolayer and a more complex and changeable L-R-L-R evolution is observed in bilayer and trilayer MSGNs as the biaxial strain vary from -8% to 12%, which actually depend on the appearance, variation, and vanish of the Mexican hat band in the absence of SOC under different strains. The contribution of Mo-dz2 orbital hybridized with N-pz orbital in the highest valence band plays a dominant role on the band evolution under biaxial strains, where the R-L evolution corresponds to the decreased Mo-dz2 orbital contribution. Our study highlights the biaxial strain controllable Rashba spin splitting, in particular the introduction and even the evolution of Lifshitz transition near Fermi surface, which makes the strained MSGNs as promising candidates for future applications in spintronic devices.

2.Dynamic motion of polar skyrmions in oxide heterostructures

Authors:Lizhe Hu, Yongjun Wu, Yuhui Huang, He Tian, Zijian Hong

Abstract: Polar skyrmions have been widely investigated in oxide heterostructure recently, due to their exotic properties and intriguing physical insights. Meanwhile, so far, the external field-driven motion of the polar skyrmion, akin to the magnetic counterpart, has yet to be discovered. Here, using phase-field simulations, we demonstrate the dynamic motion of the polar skyrmions with integrated external thermal, electrical, and mechanical stimuli. The external heating reduces the spontaneous polarization hence the skyrmion motion barrier, while the skyrmions shrink under the electric field, which could weaken the lattice pinning and interactions between the skyrmions. The mechanical force transforms the skyrmions into c-domain in the vicinity of the indenter center under the electric field, providing the space and driving force needed for the skyrmions to move. This study confirmed that the skyrmions are quasi-particles that can move collectively, while also providing concrete guidance for the further design of polar skyrmion-based electronic devices.

3.Growth of millimeter-sized high-quality CuFeSe$_2$ single crystals by the molten salt method and study of their semiconducting behavior

Authors:Mingwei Ma, Binbin Ruan, Menghu Zhou, Yadong Gu, Qingxin Dong, Qingsong Yang, Qiaoyu Wang, Lewei Chen, Yunqing Shi, Junkun Yi, Genfu Chen, Zhian Ren

Abstract: An eutectic AlCl$_3$/KCl molten salt method in a horizontal configuration was employed to grow millimeter-sized and composition homogeneous CuFeSe$_2$ single crystals due to the continuous growth process in a temperature gradient induced solution convection. The typical as-grown CuFeSe$_2$ single crystals in cubic forms are nearly 1.6$\times$1.2$\times$1.0 mm3 in size. The chemical composition and homogeneity of the crystals was examined by both inductively coupled plasma atomic emission spectroscopy and energy dispersive spectrometer with Cu:Fe:Se = 0.96:1.00:1.99 consistent with the stoichiometric composition of CuFeSe$_2$. The magnetic measurements suggest a ferrimagnetic or weak ferromagnetic transition below T$_C$ = 146 K and the resistivity reveals a semiconducting behavior and an abrupt increase below T$_C$.

4.Solute Segregation in a Moving Grain Boundary: A Novel Phase-Field Approach

Authors:Sandip Guin, Miral Verma, Soumya Bandyopadhyay, Yu-Chieh Lo, Rajdip Mukherjee

Abstract: We present a novel phase-field approach for investigating solute segregation in a moving grain boundary. In our model, the correct choice of various parameters can control the solute-grain boundary interaction potential, resulting in various segregation profiles that agree with Cahn solute drag theory. Furthermore, we explore how different segregation profiles evolve at varying GB velocities owing to the inequality of the atomic flux of solute between the front and back faces of the moving grain boundary. We highlight velocity variations among segregation profiles in low and high-velocity regimes. This model reveals how grain boundary segregation affects grain growth, providing insights for future alloy design

5.Multiple antiferromagnetic phases and magnetic anisotropy in exfoliated CrBr$_3$ multilayers

Authors:Fengrui Yao, Volodymyr Multian, Zhe Wang, Nicolas Ubrig, Jérémie Teyssier, Fan Wu, Enrico Giannini, Marco Gibertini, Ignacio Gutiérrez-Lezama, Alberto F. Morpurgo

Abstract: In twisted two-dimensional (2D) magnets, the stacking dependence of the magnetic exchange interaction can lead to regions of ferromagnetic and antiferromagnetic interlayer order, separated by non-collinear, skyrmion-like spin textures. Recent experimental searches for these textures have focused on CrI$_3$, known to exhibit either ferromagnetic or antiferromagnetic interlayer order, depending on layer stacking. However, the very strong uniaxial anisotropy of CrI$_3$ disfavors smooth non-collinear phases in twisted bilayers. Here, we report the experimental observation of three distinct magnetic phases -- one ferromagnetic and two antiferromagnetic -- in exfoliated CrBr$_3$ multilayers, and reveal that the uniaxial anisotropy is significantly smaller than in CrI$_3$. These results are obtained by magnetoconductance measurements on CrBr$_3$ tunnel barriers and Raman spectroscopy, in conjunction with density functional theory calculations, which enable us to identify the stackings responsible for the different interlayer magnetic couplings. The detection of all locally stable magnetic states predicted to exist in CrBr$_3$ and the excellent agreement found between theory and experiments, provide complete information on the stacking-dependent interlayer exchange energy and establish twisted bilayer CrBr$_3$ as an ideal system to deterministically create non-collinear magnetic phases.

6.Bulk photovoltaic effect in two-dimensional ferroelectric semiconductor $α$-In$_2$Se$_3$

Authors:Xiaojuan Chen, Kang Xu, Tingxiao Qin, Yubing Wang, Yuzhong Chen, Haiyun Liu, Qihua Xiong

Abstract: Bulk photovoltaic effect, which arises from crystal symmetry-driven charge carrier separation, is an intriguing physical phenomenon that has attracted extensive interest in photovoltaic application due to its junction-free photovoltaic and potential to surpass Shockley-Queisser limit. Whereas conventional ferroelectric materials mostly suffer from extremely low photocurrent density and weak photovoltaic response at visible light wavelengths. Emerging two-dimensional ferroelectric semiconductors with coupled visible light absorption and spontaneous polarization characteristics are a promising alternative for making functional photoferroelectrics. Herein, we report the experimental demonstration of the bulk photovoltaic effect behavior based on the 2D ferroelectric semiconductor {$\alpha$-InSe caused by an out-of-plane polarization induced depolarization field. The {$\alpha$-InSe device exhibits enhanced bulk photovoltaic response in the visible light spectrum owing to its narrow bandgap. It was demonstrated that the generated photovoltaic current density was nearly two orders of magnitude greater than conventional bulk ferroelectric materials. These findings highlight the potential of 2D ferroelectric semiconductor materials for bulk photovoltaic applications in a broad spectral region.

7.Interplay between altermagnetism and nonsymmorphic symmetries generating large anomalous Hall conductivity by semi-Dirac points induced anticrossings

Authors:Amar Fakhredine, Raghottam M. Sattigeri, Giuseppe Cuono, Carmine Autieri

Abstract: We investigate the interplay between altermagnetic spin-splitting and nonsymmorphic symmetries using the space group no. 62 as a testbed. Studying different magnetic orders by means of first-principles calculations, we find that the altermagnetism (AM) is present in the C-type magnetic configuration while it is absent for the G-type and A-type configurations due to different magnetic space group types. The nonsymmorphic symmetries constrain the system to a four-fold degeneracy at the border of the Brillouin zone with semi-Dirac dispersion. In the case of large hybridization as for transition metal pnictides, the interplay between AM and nonsymmorphic symmetries generates an intricate network of several crossings and anticrossings that we describe in terms of semi-Dirac points and glide symmetries. When we add the spin-orbit coupling (SOC), we find a Neel-vector dependent spin-orbit splitting at the time-reversal invariant momenta points since the magnetic space groups depend on the Neel vector. The magnetic space group type-I produces antiferromagnetic hourglass electrons that disappear in the type-III. When the Neel vector is along x, we observe a glide-protected crossing that could generate a nodal-line in the altermagnetic phase. The SOC splits the remaining band crossings and band anticrossings producing a large anomalous Hall effect in all directions excluding the Neel-vector direction

8.Surface Phase Diagrams from Nested Sampling

Authors:Mingrui Yang, Livia B. Pártay, Robert B. Wexler

Abstract: Atomic-scale modeling of surface phase equilibria often focuses on temperatures near zero Kelvin due to the difficulty in computing the free energy of surfaces at finite temperatures. The Bayesian-inference-based nested sampling (NS) algorithm allows modeling surface phase equilibria at arbitrary temperatures by directly and efficiently calculating the partition function, whose relationship with free energy is well known. In this work, we extend NS to calculate surface phase diagrams, including all relevant translational, rotational, and vibrational contributions to the free energy. We apply NS to the surfaces of the Lennard-Jones solid, recording energies through the iterative compression of surface phase space rather than a specific cooling schedule. We construct the partition function from these recorded energies to calculate ensemble averages of thermodynamic properties, such as the constant-volume heat capacity and temperature-dependent order parameters that characterize the surface structure. Key results include determining the nature of phase transitions on flat and stepped surfaces, which typically feature an enthalpy-driven condensation at higher temperatures and an entropy-driven reordering process at lower temperatures, and the presence of critical points on the phase diagrams of most of the flatter facets. Overall, we demonstrate the ability and potential of NS for surface modeling and, ultimately, materials discovery.

9.Towards Layer-Selective Quantum Spin Hall Channels in Weak Topological Insulator Bi4Br2I2

Authors:Jingyuan Zhong, Ming Yang, Zhijian Shi, Yaqi Li, Dan Mu, Yundan Liu, Ningyan Cheng, Wenxuan Zhao, Weichang Hao, Jianfeng Wang, Lexian Yang, Jincheng Zhuang, Yi Du

Abstract: Weak topological insulators, constructed by stacking quantum spin Hall insulators with weak interlayer coupling, offer promising quantum electronic applications through topologically nontrivial edge channels. However, the currently available weak topological insulators are stacks of the same quantum spin Hall layer with translational symmetry in the out-of-plane direction, leading to the absence of the channel degree of freedom for edge states. Here, we study a candidate weak topological insulator, Bi4Br2I2, which is alternately stacked by three different quantum spin Hall insulators, each with tunable topologically non-trivial edge states. Our angle-resolved photoemission spectroscopy and first-principles calculations show that an energy gap opens at the crossing points of different Dirac cones correlated with different layers due to the interlayer interaction. This is essential to achieve the tunability of topological edge states as controlled by varying the chemical potential. Our work offers a perspective for the construction of tunable quantized conductance devices for future spintronic applications.

1.Impact of Oxygen Pressure on Ferroelectric Stability of La-doped Hafnia Grown by PLD

Authors:Badari Narayana Rao Center for Frontier Science, Chiba University, Shintaro Yasui Institute of Innovative Research, Tokyo Institute of Technology, Hiroko Yokota Department of Physics, Chiba University Department of Materials Science and Engineering, Tokyo Institute of Technology

Abstract: Thin films of HfO2 doped with 4% La were fabricated on LSMO/STO (100) substrates using pulsed laser deposition. The stability of the ferroelectric orthorhombic phase in the hafnia films was investigated with respect to varying oxygen pressure during deposition. X-ray diffraction and X-ray photoelectron spectroscopy measurements were carried out to analyze the structure and composition of the films and correlated with their ferroelectric properties. Surprisingly, the ferroelectricity of the hafnia films showed a dependence on oxygen pressure during deposition of LSMO bottom electrode as well. The reason for this dependence is discussed in terms of the active role of non-lattice oxygen in the ferroelectric switching of hafnia.

2.Reflective, polarizing, and magnetically soft amorphous Fe/Si multilayer neutron optics with isotope-enriched 11B4C inducing atomically flat interfaces

Authors:A. Zubayer, N. Ghafoor, K. A. Thórarinsdóttir, S. Stendahl, A. Glavic, J. Stahn, G. Nagy, G. Greczynski, M. Schwartzkopf, A. Le Febvrier, P. Eklund, J. Birch, F. Magnus, F. Eriksson

Abstract: The utilization of polarized neutrons is of great importance in scientific disciplines spanning materials science, physics, biology, and chemistry. Polarization analysis offers insights into otherwise unattainable sample information such as magnetic domains and structures, protein crystallography, composition, orientation, ion-diffusion mechanisms, and relative location of molecules in multicomponent biological systems. State-of-the-art multilayer polarizing neutron optics have limitations, particularly low specular reflectivity and polarization at higher scattering vectors/angles, and the requirement of high external magnetic fields to saturate the polarizer magnetization. Here, we show that by incorporating 11B4C into Fe/Si multilayers, amorphization and smooth interfaces can be achieved, yielding higher neutron reflectivity, less diffuse scattering and higher polarization. Magnetic coercivity is eliminated, and magnetic saturation can be reached at low external fields (>2 mT). This approach offers prospects for significant improvement in polarizing neutron optics, enabling; nonintrusive positioning of the polarizer, enhanced flux, increased data accuracy, and further polarizing/analyzing methods at neutron scattering facilities.

3.A primitive machine learning tool for the mechanical property prediction of multiple principal element alloys

Authors:R. Tan, Z. Li, S. Zhao, N. Birbilis

Abstract: Multi-principal element alloys (MPEAs) are produced by combining metallic elements in what is a diverse range of proportions. MPEAs reported to date have revealed promising performance due to their exceptional mechanical properties. Training a machine learning (ML) model on known performance data is a reasonable method to rationalise the complexity of composition dependent mechanical properties of MPEAs. This study utilises data from a specifically curated dataset, that contains information regarding six mechanical properties of MPEAs. A parser tool was introduced to convert chemical composition of alloys into the input format of the ML models, and a number of ML models were applied. Finally, Gradio was used to visualise the ML model predictions and to create a user-interactive interface. The ML model presented is an initial primitive model (as it does not factor in aspects such as MPEA production and processing route), however serves as a an initial user tool, whilst also providing a workflow for other researchers.

4.Enhancement in Li-ion Conductivity through Co-doping of Ge and Ta in Garnet Li$_7$La$_3$Zr$_2$O$_{12}$ Solid Electrolyte

Authors:Muktai Aote, A. V. Deshpandea

Abstract: For being used as an electrolyte in All Solid State Batteries (ASSB), a solid electrolyte must possess ionic conductivity comparable to that of conventional liquid electrolytes. To achieve this conductivity range, the series Li$_{6.8-y}$Ge$_{0.05}$La$_3$Zr$_{2-y}$Ta$_y$O$_{12}$ ($y = 0, 0.15, 0.25, 0.35, 0.45$) has been synthesized using solid-state reaction method and studied using various characterization techniques. The highly conducting cubic phase is confirmed from XRD analysis. Structural information was collected using SEM and density measurements. The prepared ceramic sample containing 0.25 Ta, sintered at 1050$^\circ$C for 7.30 hrs shows the maximum ionic conductivity of 6.61 x 10$^{-4}$ S/cm at 25$^\circ$C. The air stability of the same ceramic has also been evaluated after exposure for 5 months. The minimum activation energy associated with the maximum conductivity of 0.25 Ta is 0.25 eV. The DC conductivity measurements were done to confirm the ionic nature of conductivity for all ceramic samples. The stable result of ionic conductivity makes the 0.25 Ta containing ceramic sample a promising candidate for solid electrolytes for ASSB applications.

5.Microstructural and material property changes in severely deformed Eurofer-97

Authors:Kay Song, Guanze He, Abdallah Reza, Tamas Ungár, Phani Karamched, David Yang, Ivan Tolkachev, Kenichiro Mizohata, David E J Armstrong, Felix Hofmann

Abstract: Severe plastic deformation changes the microstructure and properties of steels, which may be favourable for their use in structural components of nuclear reactors. In this study, high-pressure torsion (HPT) was used to refine the grain structure of Eurofer-97, a ferritic/ martensitic steel. Electron microscopy and X-ray diffraction were used to characterise the microstructural changes. Following HPT, the average grain size reduced by a factor of $\sim$ 30, with a marked increase in high-angle grain boundaries. Dislocation density also increased by more than one order of magnitude. The thermal stability of the deformed material was investigated via in-situ annealing during synchrotron X-ray diffraction. This revealed substantial recovery between 450 K - 800 K. Irradiation with 20 MeV Fe-ions to $\sim$ 0.1 dpa caused a 20% reduction in dislocation density compared to the as-deformed material. However, HPT deformation prior to irradiation did not have a significant effect in mitigating the irradiation-induced reductions in thermal diffusivity and surface acoustic wave velocity of the material. These results provide a multi-faceted understanding of the changes in ferritic/martensitic steels due to severe plastic deformation, and how these changes can be used to alter material properties.

6.Electronic and optical properties of boron containing GaN alloys: The role boron atom clustering

Authors:Cara-Lena Nies, Thomas P. Sheerin, Stefan Schulz

Abstract: Boron (B) containing III-nitride materials, such as wurtzite (B,Ga)N alloys, have recently attracted significant interest to tailor the electronic and optical properties of optoelectronic devices operating in the visible and ultraviolet spectral range. However, the growth of high quality samples is challenging and B atom clustering is often observed in (B,Ga)N alloys. To date, fundamental understanding of the impact of such clustering on electronic and optical properties of these alloys is sparse. In this work we employ density functional theory (DFT) in the framework of the meta generalized gradient approximation (modified Becke Johnson (mBJ) functional) to provide insight into this question. We use mBJ DFT calculations, benchmarked against state-of-the-art hybrid functional DFT, on (B,Ga)N alloys in the experimentally relevant B content range of up to 7.4%. Our results reveal that B atom clustering can lead to a strong reduction in the bandgap of such an alloy, in contrast to alloy configurations where B atoms are not forming clusters, thus not sharing nitrogen (N) atoms. We find that the reduction in bandgap is linked mainly to carrier localization effects in the valence band, which stem from local strain and polarization field effects. However, our study also reveals that the alloy microstructure of a B atom cluster plays an important role: B atom chains along the wurtzite c-axis impact the electronic structure far less strongly when compared to a chain formed within the c-plane. This effect is again linked to local polarization field effects and the orbital character of the involved valence states in wurtzite BN and GaN. Overall, our calculations show that controlling the alloy microstructure of (B,Ga)N alloys is of central importance when it comes to utilizing these systems in future optoelectronic devices with improved efficiencies.

7.Structural transformations in Cu, Ag, and Au metal nanoclusters

Authors:Manoj Settem, Cesare Roncaglia, Riccardo Ferrando, Alberto Giacomello

Abstract: Finite-temperature structures of Cu, Ag, and Au metal nanoclusters are calculated in the entire temperature range from 0 K to melting using a computational methodology that we proposed recently [Settem \emph{et al.}, Nanoscale, 2022, 14, 939]. In this method, Harmonic Superposition Approximation (HSA) and Parallel Tempering Molecular Dynamics (PTMD) are combined in a complementary manner. HSA is accurate at low temperatures and fails at higher temperatures. PTMD, on the other hand, effectively samples the high temperature region and melting. This method is used to study the size- and system-dependent competition between various structural motifs of Cu, Ag, and Au nanoclusters in the size range 1 to 2 nm. Results show that there are mainly three types of structural changes in metal nanoclusters depending on whether a solid-solid transformation occurs. In the first type, global minimum is the dominant motif in the entire temperature range. In contrast, when a solid-solid transformation occurs, the global minimum transforms either completely to a different motif or partially resulting in a co-existence of multiple motifs. Finally, nanocluster structures are analyzed to highlight the system-specific differences across the three metals.

8.Phases and magnetism at microscale in compounds containing nominal Pb$_{10-x}$Cu$_x$(PO$_4$)$_6$O

Authors:Chang Liu, Wenxin Cheng, Xiaoxiao Zhang, Juan Xu, Jiaxin Li, Qiuyan Shi, Changhong Yuan, Li Xu, Honglin Zhou, Shilin Zhu, Jianping Sun, Wei Wu, Jianlin Luo, Kui Jin, Yangmu Li

Abstract: Achieving superconductivity at room temperature can lead to substantially advancements in industry and technology. Recently, a compound known as Cu-doped lead-apatite Pb$_{10-x}$Cu$_x$(PO$_4$)$_6$O ($0.9 < x < 1.1$), referred to as LK-99, has been reported to exhibit unusual electrical and magnetic behaviors that appear to resemble a "superconducting transition" above room temperature. We collected compound samples containing the nominal Pb$_{10-x}$Cu$_x$(PO$_4$)$_6$O phase, which were synthesized by three independent groups, and studied their chemical, magnetic, and electrical properties at the microscale to overcome difficulties in bulk measurements. Through the utilization of optical, scanning electron, atomic force, and scanning diamond nitrogen-vacancy microscopy techniques, we are able to establish a link between local magnetic properties and specific microscale chemical phases. Our findings indicate that while the Pb$_{10-x}$Cu$_x$(PO$_4$)$_6$O phase seems to have a mixed magnetism contribution, a significant fraction of the diamagnetic response can be attributed to Cu-rich regions (e.g., Cu$_2$S from chemical reaction). Additionally, our micro-region electrical measurements reveal a phenomenon of current path jumping and a change in resistance states of Cu$_2$S. This provides a potential explanation for the electrical behavior observed in compounds related to Pb$_{10-x}$Cu$_x$(PO$_4$)$_6$O.

9.Explainable Machine Learning for Hydrogen Diffusion in Metals and Random Binary Alloys

Authors:Grace M. Lu Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA, Matthew Witman Sandia National Laboratories, Livermore, California 94551, USA, Sapan Agarwal Sandia National Laboratories, Livermore, California 94551, USA, Vitalie Stavila Sandia National Laboratories, Livermore, California 94551, USA, Dallas R. Trinkle Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA

Abstract: Hydrogen diffusion in metals and alloys plays an important role in the discovery of new materials for fuel cell and energy storage technology. While analytic models use hand-selected features that have clear physical ties to hydrogen diffusion, they often lack accuracy when making quantitative predictions. Machine learning models are capable of making accurate predictions, but their inner workings are obscured, rendering it unclear which physical features are truly important. To develop interpretable machine learning models to predict the activation energies of hydrogen diffusion in metals and random binary alloys, we create a database for physical and chemical properties of the species and use it to fit six machine learning models. Our models achieve root-mean-squared-errors between 98-119 meV on the testing data and accurately predict that elemental Ru has a large activation energy, while elemental Cr and Fe have small activation energies.By analyzing the feature importances of these fitted models, we identify relevant physical properties for predicting hydrogen diffusivity. While metrics for measuring the individual feature importances for machine learning models exist, correlations between the features lead to disagreement between models and limit the conclusions that can be drawn. Instead grouped feature importances, formed by combining the features via their correlations, agree across the six models and reveal that the two groups containing the packing factor and electronic specific heat are particularly significant for predicting hydrogen diffusion in metals and random binary alloys. This framework allows us to interpret machine learning models and enables rapid screening of new materials with the desired rates of hydrogen diffusion.

10.Tilt-induced charge localisation in phosphide antiperovskite photovoltaics

Authors:Ruiqi Wu, Alex M. Ganose

Abstract: Antiperovskites are a rich family of compounds with applications in battery cathodes, superconductors, solid-state lighting, and catalysis. Recently, a novel series of antimonide phosphide antiperovskites (A$_3$SbP, where A = Ca, Sr, Ba) were proposed as candidate photovoltaic absorbers due to their ideal band gaps, small effective masses and strong optical absorption. In this work, we explore this series of compounds in more detail using relativistic hybrid density functional theory. We reveal that the proposed cubic structures are dynamically unstable and instead identify a tilted orthorhombic Pnma phase as the ground state. Tilting is shown to induce charge localisation that widens the band gap and increases the effective masses. Despite this, we demonstrate that the predicted maximum photovoltaic efficiencies remain high (24-31% for 200 nm thin films) by bringing the band gaps into the ideal range for a solar absorber. Finally, we assess the band alignment of the series and suggest hole and electron contact materials for efficient photovoltaic devices.

11.Probabilistic Phase Labeling and Lattice Refinement for Autonomous Material Research

Authors:Ming-Chiang Chang, Sebastian Ament, Maximilian Amsler, Duncan R. Sutherland, Lan Zhou, John M. Gregoire, Carla P. Gomes, R. Bruce van Dover, Michael O. Thompson

Abstract: X-ray diffraction (XRD) is an essential technique to determine a material's crystal structure in high-throughput experimentation, and has recently been incorporated in artificially intelligent agents in autonomous scientific discovery processes. However, rapid, automated and reliable analysis method of XRD data matching the incoming data rate remains a major challenge. To address these issues, we present CrystalShift, an efficient algorithm for probabilistic XRD phase labeling that employs symmetry-constrained pseudo-refinement optimization, best-first tree search, and Bayesian model comparison to estimate probabilities for phase combinations without requiring phase space information or training. We demonstrate that CrystalShift provides robust probability estimates, outperforming existing methods on synthetic and experimental datasets, and can be readily integrated into high-throughput experimental workflows. In addition to efficient phase-mapping, CrystalShift offers quantitative insights into materials' structural parameters, which facilitate both expert evaluation and AI-based modeling of the phase space, ultimately accelerating materials identification and discovery.

12.Modulating thermoelectric properties in oxygen-passivated Sb2Te3 thin film through grain boundary engineering

Authors:Abhishek Ghosh, Chandan Kumar Vishwakarma, Prashant Bisht, Narinder Kaur, Mujeeb Ahmad, Bodh Raj Mehta

Abstract: The present study demonstrates the effectiveness of incorporating oxygen atoms into the Sb2Te3 thin film, leading to an improved power factor and reduction in thermal conductivity. Based on the experimental evidence, it can be inferred that oxygen-related impurities preferentially wet the grain boundary (GB) and introduce a double Schottky barrier at the GB interface, promoting energy-dependent carrier scattering, ultimately leading to a rise in the Seebeck coefficient. Additionally, the introduction of chemisorbed oxygen creates a high mobility state within the valence band of Sb2Te3, as corroborated by theoretical calculations, resulting in a significantly increased electrical mobility. These factors collectively contribute to improved thermoelectric performance. A set of Scanning probe (SPM) techniques is used to experimentally confirm the alteration in charge transport resulting from the oxygen-passivated grain boundary. Additionally, Scanning Thermal Microscopy (SThM) is employed to observe the spatial variations of thermal conductivity at the nanoscale regime. This study presents a comprehensive microscopic investigation of the impact of oxygen on the phonon and charge carrier transport characteristics of Sb2Te3 thermoelectric materials and indicates that incorporating oxygen may represent a feasible approach to improve the thermoelectric efficiency of these materials.

1.Ni cluster embedded (111)NiO layers grown on (0001)GaN films using pulsed laser deposition technique

Authors:Simran Arora, Shivesh Yadav, Amandeep Kaur, Bhabani Prasad Sahu, Zainab Hussain, Subhabrata Dhar

Abstract: (111) NiO epitaxial layers embedded with crystallographically oriented Ni-clusters are grown on c-GaN/Sapphire templates using pulsed laser deposition technique. Structural and magnetic properties of the films are examined by a variety of techniques including high resolution x-ray diffraction, precession-electron diffraction and superconducting quantum interference device magnetometry. The study reveals that the inclusion, orientation, shape, size, density and magnetic properties of these clusters depend strongly on the growth temperature (TG). Though, most of the Ni-clusters are found to be crystallographically aligned with the NiO matrix with Ni(111) parallel to NiO(111), clusters with other orientations also exist, especially in samples grown at lower temperatures. Average size and density of the clusters increase with TG . Proportion of the Ni(111) parallel to NiO(111) oriented clusters also improves as TG is increased. All cluster embedded films show ferromagnetic behaviour even at room temperature. Easy-axis is found to be oriented in the layer plane in samples grown at relatively lower temperatures. However, it turns perpendicular to the layer plane for samples grown at sufficiently high temperatures. This reversal of easy-axis has been attributed to the size dependent competition between the shape, magnetoelastic and the surface anisotropies of the clusters. This composite material thus has great potential to serve as spin-injector and spinstorage medium in GaN based spintronics of the future.

2.On (not) deriving the entropy of barocaloric phase transitions from crystallography and neutron spectroscopy

Authors:Anthony E. Phillips, Helen C. Walker

Abstract: We review well-known signatures of disorder in crystallographic and inelastic neutron scattering data. We show that these can arise from different types of disorder, corresponding to different values of the system entropy. Correlating the entropy of a material with its atomistic structure and dynamics is in general a difficult problem that requires correlating information between multiple experimental techniques including crystallography, spectroscopy, and calorimetry. These comments are illustrated with particular reference to barocalorics, but are relevant to a broad range of calorics and other disordered crystalline materials.

3.Nanomechanical inhomogeneities in CVA-deposited titanium nitride thin films: Nanoindentation and Finite Element Method Investigations

Authors:Neeraj Kumar Sharma, Anchal Rana, O. S. Panwar, Abhimanyu Singh Rana

Abstract: Refractory metals that can withstand at high temperatures and harsh conditions are of utmost importance for solar-thermal and energy storage applications. Thin films of TiN have been deposited using cathodic vacuum arc deposition (CVA) at relatively low temperatures ~ 300 oC using the substrate bias ~ -60V. The nanomechanical properties of these films were investigated using nanoindentation and the spatial fluctuations were observed. The nanoindentation results were simulated using finite element method (FEM) through Johnson-Cook model. We have found the local nitridation plays an important role on nanomechanical properties of TiN thin films and confirms that the nitrogen deficient regions are ductile with low yield stress and hardening modulus. This study further opens the opportunities of modelling the nanoscale system using FEM analysis.

4.Controlling Magnonic Spin Current through Magnetic Anisotropy and Gilbert Damping

Authors:Amit Chanda, Christian Holzmann, Noah Schulz, Aladin Ullrich, Manfred Albrecht, Miela J. Gross, Caroline A. Ross, Dario. A. Arena, Manh-Huong Phan, Hariharan Srikanth

Abstract: The magnon propagation length, (MPL) of a ferro/ferrimagnet (FM) is one of the key factors that controls the generation and propagation of thermally-driven spin current in FM/heavy metal (HM) bilayer based spincaloritronic devices. Theory predicts that for the FM layer, MPL is inversely proportional to the Gilbert damping (alpha) and the square root of the effective magnetic anisotropy constant (K_eff). However, direct experimental evidence of this relationship is lacking. To experimentally confirm this prediction, we employ a combination of longitudinal spin Seebeck effect (LSSE), transverse susceptibility, and ferromagnetic resonance experiments to investigate the temperature evolution of MPL and establish its correlation with the effective magnetic anisotropy field, H_K^eff (proportional to K_eff) and alpha in Tm3Fe5O12 (TmIG)/Pt bilayers. We observe concurrent drops in the LSSE voltage and MPL below 200 K in TmIG/Pt bilayers regardless of TmIG film thickness and substrate choice and attribute it to the noticeable increases in H_K^eff and alpha that occur within the same temperature range. This study not only highlights the ability to manipulate MPL by controlling H_K^eff and alpha in FM/HM based spincaloritronic nanodevices, but also shows that the tuning of alpha is more effective than H_K^eff in controlling MPL and, hence, the spincaloritronic efficiency.

5.Quantum MASALA: Quantum MAterialS Ab initio eLectronic-structure pAckage

Authors:Shri Hari Soundararaj, Agrim Sharma, Manish Jain

Abstract: We present QuantumMASALA, a compact package that implements different electronic structure methods in Python. Within just 8000 lines of pure Python code, we have implemented Density Functional Theory (DFT), Time dependent Density Functional Theory (TD-DFT) and the GW Method. The program can run across multiple process cores and in Graphical Processing Units (GPU) with the help of easily-accessible Python libraries. With QuantumESPRESSO and BerkeleyGW I/O interfaces implemented, it can also be used as a substitute for small scale calculations, making it a perfect learning tool for ab initio methods. The package is aimed to provide a framework with its modular and simple code design to rapidly build and test new methods for first-principles calculation.

6.Stability, mechanisms and kinetics of emergence of Au surface reconstructions using Bayesian force fields

Authors:Cameron J. Owen, Yu Xie, Anders Johansson, Lixin Sun, Boris Kozinsky

Abstract: Metal surfaces have long been known to reconstruct, significantly influencing their structural and catalytic properties. Many key mechanistic aspects of these subtle transformations remain poorly understood due to limitations of previous simulation approaches. Using active learning of Bayesian machine-learned force fields trained from ab initio calculations, we enable large-scale molecular dynamics simulations to describe the thermodynamics and time evolution of the low-index mesoscopic surface reconstructions of Au (e.g., the Au(111)-`Herringbone,' Au(110)-(1$\times$2)-`Missing-Row,' and Au(100)-`Quasi-Hexagonal' reconstructions). This capability yields direct atomistic understanding of the dynamic emergence of these surface states from their initial facets, providing previously inaccessible information such as nucleation kinetics and a complete mechanistic interpretation of reconstruction under the effects of strain and local deviations from the original stoichiometry. We successfully reproduce previous experimental observations of reconstructions on pristine surfaces and provide quantitative predictions of the emergence of spinodal decomposition and localized reconstruction in response to strain at non-ideal stoichiometries. A unified mechanistic explanation is presented of the kinetic and thermodynamic factors driving surface reconstruction. Furthermore, we study surface reconstructions on Au nanoparticles, where characteristic (111) and (100) reconstructions spontaneously appear on a variety of high-symmetry particle morphologies.

1.Design of Sn-doped cadmium chalcogenide based monolayers for valleytronics properties

Authors:Sutapa Chattopadhyay, Anjali Kshirsagar

Abstract: Valleytronics, that uses the valley index or valley pseudospin to encode information, has emerged as an interesting field of research in two-dimensional (2D) systems with promising device applications. Spin-orbit coupling (SOC) and inversion symmetry breaking leads to spin-splitting of bands near the energy extrema (valleys). In order to find a new 2D material useful for valleytronics, we have designed hexagonal planar monolayers of cadmium chalcogenides (CdX, X = S, Se, Te) from the (111) surface of bulk CdX zinc blende structure. Band structure study reveals valence band local maxima at symmetry point K and its time reversal conjugate point K$\textquotesingle$. Application of SOC initiates spin-splitting in the valleys that lifts the energy degeneracy and shows strong valley-spin coupling character. We have substituted two Cd atoms in the planar monolayers by Sn atoms which increases the spin-splitting significantly. The structural, dynamic, mechanical and thermal stability of all the monolayers has been confirmed. Values of formation energies indicate that it may be feasible to synthesize the Sn-doped CdSe and CdTe monolayers using bottom-up approach. Zeeman-type spin-splitting is observed in the valley region and Rashba spin-splitting is observed at the $\Gamma$ point for Sn-doped CdSe and CdTe monolayers. Berry curvature values are more in all the Sn-doped monolayers than the pristine monolayers. These newly designed monolayers are thus found to be suitable for valleytronics applications. Sn-doped monolayers show band inversion deep in the valence and conduction bands between Sn~$s$ and $p$ and X~$p$ states but lack topological properties.

2.Polarization sensitivity in scattering-type scanning near-field optical microscopy -- towards nanoellipsometry

Authors:Felix G. Kaps 1 ad 2, Susanne C. Kehr Institute of Applied Physics TUD Dresden University of Technology, Lukas M. Eng Institute of Applied Physics TUD Dresden University of Technology Würzburg-Dresden Cluster of Excellence - EXC 2147

Abstract: Electric field enhancement mediated through sharp tips in scattering-type scanning near-field optical microscopy (s-SNOM) enables optical material analysis down to the 10-nm length scale, and even below. Nevertheless, mostly the out-of-plane electric field component is considered here due to the lightning rod effect of the elongated s-SNOM tip being orders of magnitude stronger as compared to any in-plane field component. Nonetheless, the fundamental understanding of resonantly excited near-field coupled systems clearly allows us to take profit from all vectorial components, especially also from the in-plane ones. In this paper, we theoretically and experimentally explore how linear polarization control of both near-field illumination and detection, can constructively be implemented to (non-)resonantly couple to selected sample permittivity tensor components, e.g. explicitly also to the in-plane directions. When applying the point-dipole model, we show that resonantly excited samples respond with a strong near-field signal, to all linear polarization angles. We then experimentally investigate the polarization-dependent responses for both non-resonant (Au) and phonon-resonant (3C-SiC) sample excitations at a 10.6~$\mu$m and 10.7~$\mu$m incident wavelength using a tabletop CO$_2$ laser. Varying the illumination polarization angle thus allows for quantitatively comparing the scattered near-field signatures for the two wavelengths. Finally, we compare our experimental data to simulation results, and thus gain the fundamental understanding of the polarization's influence on the near-field interaction. As a result, the near-field components parallel and perpendicular to the sample surface can be easily disentangled and quantified through their polarization signatures, connecting them directly to the sample's local permittivity.

3.Role of higher-order spin interactions in the emergence of chiral magnetic configurations in lithium-decorated monolayer CrTe$_{2}$

Authors:Weiyi Pan, Changsong Xu, Xueyang Li, Zhiming Xu, Boyu Liu, Bing-Lin Gu, Wenhui Duan

Abstract: Chiral magnetic states in two-dimensional (2D) layered noncentrosymmetric magnets, which are of promising advanced spintronic applications, are usually attributed to Dzyaloshinskii-Moriya interaction (DMI), yet the role of underlying higher-order spin couplings on the emergence of chiral spin textures is rarely reported. In this work, taking lithium-decorated monolayer CrTe$_{2}$ (LiCrTe$_{2}$) as an example, we proposed a comprehensive first-principles-based spin model using the symmetry-adapted cluster expansion method. Based on this spin model, we identified the ground state of monolayer LiCrTe$_{2}$ to be a chiral labyrinth domain (LD) state, and various higher-order spin interactions are essentially responsible for stabilizing this LD state. Meanwhile, some higher-order couplings are identified to play the role of DMI due to their nontrivial spin spiral chirality selectivity. In addition, skyrmions emerge under either external magnetic field or finite temperature. Our study sheds light on the complex magnetic couplings in 2D magnets.

4.Enhanced optical conductivity and many-body effects in strongly-driven photo-excited semi-metallic graphite

Authors:T. P. H. Sidiropoulos, N. Di Palo, D. E. Rivas, A. Summers, S. Severino, M. Reduzzi, J. Biegert

Abstract: The excitation of quasi-particles near the extrema of the electronic band structure is a gateway to electronic phase transitions in condensed matter. In a many-body system, quasi-particle dynamics are strongly influenced by the electronic single-particle structure and have been extensively studied in the weak optical excitation regime. Yet, under strong optical excitation, where light fields coherently drive carriers, the dynamics of many-body interactions that can lead to new quantum phases remain largely unresolved. Here, we induce such a highly non-equilibrium many-body state through strong optical excitation of charge carriers near the van Hove singularity in graphite. We investigate the system's evolution into a strongly-driven photo-excited state with attosecond soft X-ray core-level spectroscopy. Surprisingly, we find an enhancement of the optical conductivity of nearly ten times the quantum conductivity and pinpoint it to carrier excitations in flat bands. This interaction regime is robust against carrier-carrier interaction with coherent optical phonons acting as an attractive force reminiscent of superconductivity. The strongly-driven non-equilibrium state is markedly different from the single-particle structure and macroscopic conductivity and is a consequence of the non-adiabatic many-body state.

5.Goodenough-Kanamori-Anderson rules in 2D magnet: A chemical trend in MCl2 with M=V, Mn, and Ni

Authors:Thi Phuong Thao Nguyen, Kunihiko Yamauchi

Abstract: Density-functional-theory calculations were performed to investigate the magnetism in a series of triangular-lattice monolayer MCl2 (M=V, Mn, and Ni). The magnetic stability manifests a distinct chemical trend; VCl2 and MnCl2 show the antiferromagnetic ground states and NiCl2 shows the ferromagnetic ground state. The microscopic mechanism behind the magnetic interaction is explained by the so-called Goodenough-Kanamori-Anderson rules and by the virtual-hopping process through the hopping integrals between the 3d-orbital maximally localized Wannier functions. Our result highlights the role of the direct exchange interaction and the superexchange interaction in the magnetic stabilization in two-dimensional magnets.

6.Growth of aligned and twisted hexagonal boron nitride on Ir(110)

Authors:Thomas Michely, Jason Bergelt, Affan Safeer, Alexander Bäder, Tobias Hartl, Jeison Fischer

Abstract: The growth of monolayer hexagonal boron nitride (h-BN) on Ir(110) through low-pressure chemical vapor deposition is investigated using low energy electron diffraction and scanning tunneling microscopy. We find that the growth of aligned single hexagonal boron nitride on Ir(110) requires a growth temperature of 1500 K, whereas lower growth temperatures result in coexistence of aligned h-BN with twisted h-BN The presence of the h-BN overlayer suppresses the formation of the nano-faceted ridge pattern known from clean Ir(110). Instead, we observe the formation of a (1 $\times$ n) reconstruction, with n such that the missing rows are in registry with the h-BN/Ir(110) moir\'{e} pattern. Our moir\'{e} analysis showcases a precise methodology for determining both the moir\'{e} periodicity and the h-BN lattice parameter on an fcc(110) surface.

7.Observation of broadening Rashba-type band in AuSb surface alloy

Authors:Jinbang Hu, Xiansi Wang, Justin Wells

Abstract: Here, we report a novel AuSb 2D superstructure on Au(111) that shows agreements and discrepancies to the expected electronic features of the ideal 2D surface alloys with $\sqrt{3}\times\sqrt{3}$ periodicity. Using spin- and angle-resolved photoemission spectroscopy, we find a significant spin splitting of the alloy bands with antiparallel spin polarization. The band structure originates from the hybridization between the Sb and the Au orbitals at the 2D Sb-Au interface. Taking advantage of the good agreement between the experimental results and DFT calculations, we find the broadening of the band is due to the perturbations introduced by the 3-pointed-star-shaped defects as nonresonant impurities in the $8\times8$ superstructure. The periodic defect can properly adjust the energy position of the Rashba band while not breaking the in-plane symmetry.

8.Interfacial spintronic THz emission

Authors:Piyush Agarwal, Rohit Medwal, Keynesh Dongol, John Rex Mohan, Yingshu Yang, Hironori Asada, Yasuhiro Fukuma, Ranjan Singh

Abstract: The broken inversion symmetry at the ferromagnet (FM)/heavy-metal (HM) interface leads to spin-dependent degeneracy of the energy band, forming spin-polarized surface states. As a result, the interface serves as an effective medium for converting spin accumulation into two-dimensional charge current through the inverse Rashba-Edelstein effect. Exploring and assessing this spin-to-charge conversion (SCC) phenomenon at the FM/HM interface could offer a promising avenue to surpass the presumed limits of SCC in bulk HM layers. We utilize spintronic heterostructures as a platform to measure the spin-to-charge conversion (SCC) experienced by photoexcited spin currents. These heterostructures emit terahertz electric field when illuminated by femtosecond laser pulses, enabling us to quantitatively assess the ultrafast SCC process. Our results demonstrate a robust interfacial spin-to-charge conversion (iSCC) within a synthetic antiferromagnetic heterostructure, specifically for the NiFe/Ru/NiFe configuration, by isolating the SCC contribution originating from the interface itself, separate from the bulk heavy-metal (HM) region. Moreover, the iSCC at the NiFe/Ru interface is discovered to be approximately 27% of the strength observed in the highest spin-Hall conducting heavy-metal, Pt. Our results thus highlight the significance of interfacial engineering as a promising pathway for achieving efficient ultrafast spintronic devices.

1.Self-consistent convolutional density functional approximations: Formulation and application to adsorption at metal surfaces

Authors:Sushree Jagriti Sahoo, Qimen Xu, Xiangyun Lei, Daniel Staros, Gopal R. Iyer, Brenda Rubenstein, Phanish Suryanarayana, Andrew J. Medford

Abstract: The exchange-correlation (XC) functional in density functional theory is used to approximate multi-electron interactions. A plethora of different functionals is available, but nearly all are based on the hierarchy of inputs commonly referred to as "Jacob's ladder." This paper introduces an approach to construct XC functionals with inputs from convolutions of arbitrary kernels with the electron density, providing a route to move beyond Jacob's ladder. We derive the variational derivative of these functionals, showing consistency with the generalized gradient approximation (GGA), and provide equations for variational derivatives based on multipole features from convolutional kernels. A proof-of-concept functional, PBEq, which generalizes the PBE$\alpha$ framework where $\alpha$ is a spatially-resolved function of the monopole of the electron density, is presented and implemented. It allows a single functional to use different GGAs at different spatial points in a system, while obeying PBE constraints. Analysis of the results underlines the importance of error cancellation and the XC potential in data-driven functional design. After testing on small molecules, bulk metals, and surface catalysts, the results indicate that this approach is a promising route to simultaneously optimize multiple properties of interest.

2.Perovskite solar cells at radiative detailed balance limit

Authors:Kashimul Hossain, Dinesh Kabra, Pradeep R. Nair

Abstract: Here, we report the first experimental demonstration of perovskite solar cells at radiative detailed balance limit. To conclusively establish this claim, we theoretically identified a set of quantitative benchmark characteristics expected from solar cells at radiative detailed balance limits. Transient as well as steady state intensity dependent measurements indicate that our solar cells are indeed operating at such limits with interface passivation comparable to the champion c-Si technology. Remarkably, our analysis also facilitates novel characterization schemes which enable consistent back extraction of important recombination parameters from opto-electrical measurements. These results have significant implications towards fundamental electronic processes in perovskite solar cells and further efficiency optimization towards Shockeley-Queisser limits.

3.Reactivity of Stone-Wales defect in graphene lattice -- DFT study

Authors:Aleksandar Z. Jovanović University of Belgrade - Faculty of Physical Chemistry, Belgrade, Serbia, Ana S. Dobrota University of Belgrade - Faculty of Physical Chemistry, Belgrade, Serbia, Natalia V. Skorodumova Department of Materials Science and Engineering, School of Industrial Engineering and Management, KTH - Royal Institute of Technology, Stockholm, Sweden Applied Physics, Division of Materials Science, Department of Engineering Sciences and Mathematics, Luleå University of Technology, Sweden, Igor A. Pašti University of Belgrade - Faculty of Physical Chemistry, Belgrade, Serbia

Abstract: Understanding the reactivity of carbon surfaces is crucial for the development of advanced functional materials. In this study, we systematically investigate the reactivity of graphene surfaces with the Stone-Wales (SW) defect using Density Functional Theory calculations. We explore the atomic adsorption of various elements, including rows 1-3 of the Periodic Table, potassium, calcium, and selected transition metals. Our results demonstrate that the SW defect enhances binding with the studied adsorbates when compared to pristine graphene, with carbon and silicon showing the most significant differences. Additionally, we examine the effects of mechanical deformation on the lattice by constraining the system with the SW defect to the pristine graphene cell. Interestingly, these constraints lead to even stronger binding interactions. Furthermore, for carbon, nitrogen, and oxygen adsorbates, we observe that mechanical deformation triggers the incorporation of adatoms into the carbon bond network, leading to the reorganization of the SW defect structure. This work establishes a foundation for future studies in the defect and strain engineering of graphene, opening avenues for developing advanced materials and catalysts with enhanced reactivity and performance.

4.Hexagonal boron-carbon fullerene heterostructures; Stable two-dimensional semiconductors with remarkable stiffness, low thermal conductivity and flat bands

Authors:Bohayra Mortazavi, Yves Remond, Hongyuan Fang, Timon Rabczuk, Xiaoying Zhuang

Abstract: Among exciting recent advances in the field of two-dimensional (2D) materials, the successful fabrications of the C60 fullerene networks has been a particularly inspiring accomplishment. Motivated by the recent achievements, herein we explore the stability and physical properties of novel hexagonal boron-carbon fullerene 2D heterostructures, on the basis of already synthesized B40 and C36 fullerenes. By performing extensive structural minimizations of diverse atomic configurations using the density functional theory method, for the first time, we could successfully detect thermally and dynamically stable boron-carbon fullerene 2D heterostructures. Density functional theory results confirm that the herein predicted 2D networks exhibit very identical semiconducting electronic natures with topological flat bands. Using the machine learning interatomic potentials, we also investigated the mechanical and thermal transport properties. Despite of different bonding architectures, the room temperature lattice thermal conductivity of the predicted nanoporous fullerene heterostructures was found to range between 4 to 10 W/mK. Boron-carbon fullerene heterostructures are predicted to show anisotropic but also remarkable mechanical properties, with tensile strengths and elastic modulus over 8 and 70 GPa, respectively. This study introduces the possibility of developing a novel class of 2D heterostructures based on the fullerene cages, with attractive electronic, thermal and mechanical features.

5.Finite-temperature ductility-brittleness and electronic structures of Al$_{n}$Sc (n=1, 2 and 3)

Authors:Xue-Qian Wang, Ying Zhao, Hao-Xuan Liu, Shuchen Sun, Hongbo Yang, Jiamin Zhong, Ganfeng Tu, Song Li, Hai-Le Yan, Liang Zuo

Abstract: Finite-temperature ductility-brittleness and electronic structures of Al$_3$Sc, Al$_2$Sc and AlSc are studied comparatively by first-principles calculations and ab-initio molecular dynamics. Results show that Al$_3$Sc and Al$_2$Sc are inherently brittle at both ground state and finite temperatures. By contrast, AlSc possesses a significantly superior ductility evaluated from all Pugh's, Pettifor's and Poisson's ductility-brittleness criteria. At ground state, AlSc meets the criteria of ductile according to Pugh's and Poisson's theories, while it is categorized as the brittle in the frame of Pettifor's picture. With the increasing temperature, the ductility of all the studied compounds exhibits a noticeable improvement. In particular, as the temperature rises, the Cauchy pressure of AlSc undergoes a transition from negative to positive. Thus, at high temperatures (T > 600 K), AlSc is unequivocally classified as the ductile from all criteria considered. In all Al$_3$Sc, Al$_2$Sc and AlSc, the Al-Al bond, originated from s-p and p-p orbital hybridizations, and the Al-Sc bond, dominated by p-d covalent hybridization, are the first and second strongest chemical bonds, respectively. To explain the difference in mechanical properties of the studied compounds, the mean bond strength (MBS) is evaluated. The weaker Al-Al bond in AlSc, leading to a smaller MBS, could be the origin for the softer elastic stiffness and superior intrinsic ductility. The longer length of the Al-Al bond in AlSc is responsible for its weaker bond strength. Furthermore, the enhanced metallicity of the Al-Al bond in AlSc would also contribute to its exceptional ductility.

6.Topological soliton molecule in quasi 1D charge density wave

Authors:Taehwan Im, Sun Kyu Song, Jae Whan Park, Han Woong Yeom

Abstract: Soliton molecules, bound states of two solitons, can be important for the informatics using solitons and the quest for exotic particles in a wide range of physical systems from unconventional superconductors to nuclear matter and Higgs field, but have been observed only in temporal dimension for classical wave optical systems. Here, we identify a topological soliton molecule formed spatially in an electronic system, a quasi 1D charge density wave of indium atomic wires. This system is composed of two coupled Peierls chains, which are endowed with a Z$_4$ topology and three distinct, right-chiral, left-chiral, and non-chiral, solitons. Our scanning tunneling microscopy measurements identify a bound state of right- and left-chiral solitons with distinct in-gap states and net zero phase shift. Our density functional theory calculations reveal the attractive interaction of these solitons and the hybridization of their electronic states. This result initiates the study of the interaction between solitons in electronic systems, which can provide novel manybody electronic states and extra data-handling capacity beyond the given soliton topology.

7.Observation of low-frequency Raman peak in layered WTe$_2$

Authors:Hirofumi Nema, Yasuhiro Fujii, Eiichi Oishi, Akitoshi Koreeda

Abstract: WTe$_2$ recently attracted considerable attention as a layered material exhibiting ferroelectricity, giant magnetoresistance, and pressure-induced superconductivity. In this study, we performed Raman spectroscopy on bulk WTe$_2$, including the unreported low frequency region. A novel Raman peak (P0) was found at approximately 9 cm$^{-1}$ in addition to the seven already known peaks. Furthermore, the angular and polarization dependence of the spectra revealed that the novel peak had $A_1$ symmetry. The existence of this novel peak is consistent with first principles calculations by another group. Our work paves the way for studying the low frequency vibration modes of atomic layer ferrolectric films.

8.Thermal and mechanical properties of AlSi7Mg matrix syntactic foams reinforced by Al$_2$O$_3$ or SiC particles in matrix

Authors:Fehér Anna, Maróti János, Takács Donát, Orbulov Imre, Kovács Róbert

Abstract: Materials with complex inner structure can be challenging to characterize in an effective way. First, it is difficult to determine the representative volume for such a heterogeneous material. Second, the effective material parameters significantly depend on the structure, and thus on the interface properties. In the present paper, we focus on composite metal foams, and we attempt to determine the effective thermal parameters. We use the heat pulse experiment to study its transient thermal response. We observed deviation from Fourier's law, and thus we propose an evaluation procedure for such experimental data using the Guyer--Krumhansl heat equation. Furthermore, we studied the effective parameters, the specific heat, mass density, thermal conductivity and thermal diffusivity, and we propose a method for deducing a more reliable thermal diffusivity and thermal conductivity based on the transient temperature history.

9.Surface recombination and out of plane diffusivity of free excitons in hexagonal boron nitride

Authors:Sébastien Roux, Christophe Arnold, Etienne Carré, Eli Janzen, James H. Edgard, Camille Maestre, Bérangère Toury, Catherine Journet, Vincent Garnier, Philippe Steyer, Takashi Taniguchi, Kenji Watanabe, Annick Loiseau, Julien Barjon

Abstract: We present a novel experimental protocol using Cathodoluminescence measurements as a function of the electron incident energy to study both exciton diffusion in a directional way and surface exciton recombination. Our approach overcomes the challenges of anisotropic diffusion and the limited applicability of existing methods to the bulk counterparts of 2D materials. The protocol is then applied at room and at cryogenic temperatures to four bulk hexagonal boron nitride crystals grown by different synthesis routes. The exciton diffusivity depends on the sample quality but not on the temperature, indicating it is limited by defect scattering even in the best quality crystals. The lower limit for the diffusivity by phonon scattering is 0.2 cm$^{2}$.s$^{-1}$. Diffusion lengths were as much as 570 nm. Finally, the surface recombination velocity exceeds 10$^{5}$ cm$^{2}$.s$^{-1}$, at a level similar to silicon or diamond. This result reveals that surface recombination could strongly limit light-emitting devices based on 2D materials.

10.First-principles calculation on the electronic structures, phonon dynamics, and electrical conductivities of Pb$_{10}$(PO$_4$)$_6$O and Pb$_9$Cu(PO$_4$)$_6$O compounds

Authors:Liyu Hao, Engang Fu

Abstract: Superconducting materials with high critical temperature have the potential to revolutionize many fields, including military, electronic communications, and power energy. Therefore, Scientists around the world have been tirelessly working with the ultimate goal of achieving high temperature superconductivity. In 2023, a preprint by S. Lee et al in South Korea claimed the discovery of ultra-high-temperature superconductivity with a critical temperature of up to 423 K in Cu-doped lead-apatite (LK-99) (arXiv:2307.12008, arXiv:2307.12037), which caused a worldwide sensation and attention. Herein, the electronic structures, phonon dynamics, and electrical conductivities of LK-99 and its parent compound lead-apatite have been calculated using first-principles methods. The results show that the lead-apatite compound and the LK-99 compound are insulator and half-metal respectively. The flat band characteristic is consistent with previous calculations. The electrical conductivity of LK-99 compound shows two extreme point, and the electrical conductivity along the C-axis increases significantly after 400 K. The phonon dispersion spectra of the compounds were investigated, demonstrating their dynamic instability.

11.High-performance Thermoelectric Monolayer γ-GeSe and its Group-IV Monochalcogenide Isostructural Family

Authors:Zheng Shu, Bowen Wang, Xiangyue Cui, Xuefei Yan, Hejin Yan, Huaxian Jia, Yongqing Cai

Abstract: Recently synthesized novel phase of germanium selenide ({\gamma}-GeSe) adopts a hexagonal lattice and a surprisingly high conductivity than graphite. This triggers great interests in exploring its potential for thermoelectric applications. Herein, we explored the thermoelectric performance of monolayer {\gamma}-GeSe and other isostructural {\gamma}-phase of group-IV monochalcogenides {\gamma}-GeX (X = S, Se and Te) using the density functional theory and the Boltzmann transport theory. A superb thermoelectric performance of monolayer {\gamma}-GeSe is revealed with figure of merit ZT value up to 1.13-2.76 for n-type doping at a moderate carrier concentration of 4.73-2.58x10^12 cm-2 between 300 and 600 K. This superb performance is rooted in its rich pocket states and flat plateau levels around the electronic band edges, leading to promoted concentrations and electronic conductivity, and limited thermal conductivity. Our work suggests that monolayer {\gamma}-GeSe is a promising candidate for high performance medium-temperature thermoelectric applications.

1.Direct and in situ examination of Li+ transport kinetics in isotope labelled solid electrolyte interphase

Authors:Xiaofei Yu, Stefany Angarita-Gomez, Yaobin Xu, Peiyuan Gao, Jun-Gang Wang, Xin Zhang, Hao Jia, Wu Xu, Xiaolin Li, Yingge Du, Zhijie Xu, Janet S. Ho, Kang Xu, Perla B. Balbuena, Chongmin Wang, Zihua Zhu

Abstract: Here, using unique in-situ liquid secondary ion mass spectroscopy on isotope-labelled solid-electrolyte-interphase (SEI), assisted by cryogenic transmission electron microscopy and constrained ab initio molecular dynamics simulation, for the first time we answer the question regarding Li+ transport mechanism across SEI, and quantitatively determine the Li+-mobility therein. We unequivocally unveil that Li+ transport in SEI follows a mechanism of successive displacement, rather than "direct-hopping". We further reveal, in accordance with spatial-dependence of SEI structure across the thickness, the apparent Li+ self-diffusivity varies from 6.7*10-19 m2/s to 1.0*10-20 m2/s, setting a quantitative gauging of ionic transport behavior of SEI layer against the underlining electrode as well as the rate limiting step of battery operation. This direct study on Li+ kinetics in SEI fills part of the decade-long knowledge gap about the most important component in advanced batteries and provides more precise guidelines to the tailoring of interphasial chemistries for future battery chemistries.

2.Kinetic Monte Carlo Simulations of Sodium Ion Transport in NaSICON Electrodes

Authors:Ziliang Wang, Tara P. Mishra, Weihang Xie, Zeyu Deng, Gopalakrishnan Sai Gautam, Anthony K. Cheetham, Pieremanuele Canepa

Abstract: The development of high-performance sodium (Na) ion batteries requires improved electrode materials. The energy and power densities of Na superionic conductor (NaSICON) electrode materials are promising for large-scale energy storage applications. However, several practical issues limit the full utilization of the theoretical energy densities of NaSICON electrodes. A pressing challenge lies in the limited sodium extraction in low Na content NaSICONs, e.g., $\rm Na_1V^{IV}V^{IV}(PO_4)_3 \leftrightarrow V^{V}V^{IV}(PO_4)_3 + 1e^- + 1Na^+$. Hence, it is important to quantify the Na-ion mobility in a broad range of NaSICON electrodes. Using a kinetic Monte Carlo approach bearing the accuracy of first-principles calculations, we elucidate the variability of Na-ion transport vs. Na content in three important NaSICON electrodes, Na$_{\rm x}$Ti$_{2}$(PO$_{4}$)$_{3}$, Na$_{\rm x}$V$_{2}$(PO$_{4}$)$_{3}$, and Na$_{\rm x}$Cr$_{2}$(PO$_{4}$)$_{3}$. Our study suggests that Na$^+$ transport in NaSICON electrodes is almost entirely determined by the local electrostatic and chemical environment set by the transition metal and the polyanionic scaffold. The competition with the ordering-disordering phenomena of Na-vacancies also plays a role in influencing Na-transport. We link the variations in the Na$^+$ kinetic properties by analyzing the competition of ligand field stabilization transition metal ions and their ionic radii. We interpret the limited Na-extraction at $x = 1$ observed experimentally by gaining insights into the local Na-vacancy interplay. We propose that targeted chemical substitutions of transition metals disrupting local charge arrangements will be critical to reducing the occurrence of strong Na$^+$-vacancy orderings at low Na concentrations, thus, expanding the accessible capacities of these electrode materials.

3.Linear response theories for interatomic exchange interactions

Authors:I. V. Solovyev

Abstract: In 1987, Liechtenstein et al. came up with the idea to formulate the problem of interatomic exchange interactions, which would describe the energy change caused by the infinitesimal rotations of spins, in terms of the magnetic susceptibility. The formulation appears to be very generic and, for isotropic systems, expresses the energy change in the form of the Heisenberg model, irrespectively on which microscopic mechanism stands behind the interaction parameters. Moreover, this approach establishes the relationship between the exchange interactions and the electronic structure obtained, for instance, in the first-principles calculations based on the density functional theory. The purpose of this review is to elaborate basic ideas of the linear response theories for the exchange interactions as well as more resent developments. The special attention is paid to the approximations underlying the original method of Liechtenstein et al. in comparison with its more recent and more rigorous extensions, the roles of the on-site Coulomb interactions and the ligand states, and calculations of antisymmetric Dzyaloshinskii-Moriya interactions, which can be performed alongside with the isotropic exchange, within one computational scheme. The abilities of the linear response theories as well as many theoretical nuances, which may arise in the analysis of interatomic exchange interactions, are illustrated on magnetic van der Walls materials Cr$X_3$ ($X$$=$ Cl, I), half-metallic ferromagnet CrO$_2$, ferromagnetic Weyl semimetal Co$_3$Sn$_2$S$_2$, and orthorhombic manganites $A$MnO$_3$ ($A$$=$ La, Ho), known for the peculiar interplay of the lattice distortion, spin, and orbital ordering.

4.Quantum Confinement and Electronic Structure at the Surface of van der Waals Ferroelectric α-In$_{2}$Se$_{3}$

Authors:Geoffroy Kremer, Aymen Mahmoudi, Adel M'Foukh, Meryem Bouaziz, Mehrdad Rahimi, Maria Luisa Della Rocca, Patrick Le Fèvre, Jean-Francois Dayen, François Bertran, Sylvia Matzen, Marco Pala, Julien Chaste, Fabrice Oehler, Abdelkarim Ouerghi

Abstract: Two-dimensional (2D) ferroelectric (FE) materials are promising compounds for next-generation nonvolatile memories, due to their low energy consumption and high endurance. Among them, {\alpha}-In$_{2}$Se$_{3}$ has drawn particular attention due to its in- and out-of-plane ferroelectricity, whose robustness has been demonstrated down to the monolayer limit. This is a relatively uncommon behavior since most bulk FE materials lose their ferroelectric character at the 2D limit due to depolarization field. Using angle resolved photoemission spectroscopy (ARPES), we unveil another unusual 2D phenomena appearing in 2H \alpha-In$_{2}$Se$_{3}$ single crystals, the occurrence of a highly metallic two-dimensional electron gas (2DEG) at the surface of vacuum-cleaved crystals. This 2DEG exhibits two confined states which correspond to an electron density of approximatively 10$^{13}$ electrons/cm$^{3}$, also confirmed by thermoelectric measurements. Combination of ARPES and density functional theory (DFT) calculations reveals a direct band gap of energy equal to 1.3 +/- 0.1 eV, with the bottom of the conduction band localized at the center of the Brillouin zone, just below the Fermi level. Such strong n-type doping further supports the quantum confinement of electrons and the formation of the 2DEG.

5.Strong Exciton-Phonon Coupling as a Fingerprint of Magnetic Ordering in van der Waals Layered CrSBr

Authors:Kaiman Lin, Xiaoxiao Sun, Florian Dirnberger, Yi Li, Jiang Qu, Peiting Wen, Zdenek Sofer, Aljoscha Söll, Stephan Winnerl, Manfred Helm, Shengqiang Zhou, Yaping Dan, Slawomir Prucnal

Abstract: The layered, air-stable van der Waals antiferromagnetic compound CrSBr exhibits pronounced coupling between its optical, electronic, and magnetic properties. As an example, exciton dynamics can be significantly influenced by lattice vibrations through exciton-phonon coupling. Using low-temperature photoluminescence spectroscopy, we demonstrate the effective coupling between excitons and phonons in nanometer-thick CrSBr. By careful analysis, we identify that the satellite peaks predominantly arise from the interaction between the exciton and an optical phonon with a frequency of 118 cm-1 (~14.6 meV) due to the out-of-plane vibration of Br atoms. Power-dependent and temperature-dependent photoluminescence measurements support exciton-phonon coupling and indicate a coupling between magnetic and optical properties, suggesting the possibility of carrier localization in the material. The presence of strong coupling between the exciton and the lattice may have important implications for the design of light-matter interactions in magnetic semiconductors and provides new insights into the exciton dynamics in CrSBr. This highlights the potential for exploiting exciton-phonon coupling to control the optical properties of layered antiferromagnetic materials.

6.Towards the Distribution of a Class of Polycrystalline Materials with an Equilibrium Defect Structure by Grain Diameters: Temperature Behavior of the Yield Strength

Authors:Alexander A. Reshetnyak, Varvara V. Shamshutdinova

Abstract: We modify a theory of flow stress introduced in [arXiv:1803.08247[cond-mat.mtrl-sci]], [arXiv:1809.03628[cond-mat.mes-hall]], [arXiv:1908.09338[cond-mat.mtrl-sci]] for a class of polycrystalline materials with equilibrium and quasy-equilibrium defect structure under quasi-static plastic deformations. We suggest, in addition to modified Bose-Einstein distribution, Maxwell-like distribution law for defects (within dislocation-disclination mechanism) in the grains of polycrystalline samples with respect to grain's diameter. Polycrystalline aggregates are considered within single- and two-phase models that correspond to the presence of crystalline and grain-boundary (porous) phases. The scalar dislocation density is derived. Analytic and graphic forms of the generalized Hall-Petch relations for yield strength are produced for single-mode samples with BCC ($\alpha$-Fe), FCC (Cu, Al, Ni) and HCP ($\alpha$-Ti, Zr) crystal lattices at T=300 K with different values of the grain-boundary phase. We derived new form of the temperature-dimensional effect. The values of extremal grain and maximum of yield strength are decreased with raising the temperature in accordance with experiments up to NC region.

7.Neural network potentials for modeling nonstoichiometric materials: a case of Chromium Sulfides Cr$_{(1-x)}$S

Authors:Akram Ibrahim, Daniel Wines, Can Ataca

Abstract: Deviation from stoichiometry can yield a diverse range of stable phases with distinct physical and chemical properties. To comprehensively explore nonstoichiometric materials, it is crucial to investigate their compositional and structural domains with precision and cost-effectiveness. However, the extensive diversity in these domains render first-principles methods, such as density functional theory (DFT), inappropriate for such endeavors. In this study, we propose a generic framework that utilizes neural network potentials (NNPs) to model nonstoichiometric materials with chemical accuracy at realistic length and time scales. We apply our framework to analyze nonstoichiometric Cr$_{(1-x)}$S materials, a compelling material category with significant potential in the field of two-dimensional (2D) magnetic materials applications. The efficacy of the NNP model is shown to outperform the conventional cluster expansion (CE) model, exhibiting near-DFT accuracy and robust transferability to unexplored crystal structures and compositions. Furthermore, we employ the NNP model in simulated annealing (SA) optimizations to predict the low-energy Cr$_{(1-x)}$S structures across diverse compositions. A notable structural transition is discerned at the Cr$_{0.5}$S composition, characterized by a preferential migration of half of the Cr atoms to the van der Waals (vdW) gaps. This highlights the experimentally observed non-vdW nature of CrS$_2$ and emphasizes the pivotal role of excess Cr atoms beyond the composition ratio of Cr/S = $1/2$ in stabilizing the vdW gaps. Additionally, we employ the NNP model in a large-scale vacancy diffusion Monte Carlo (MC) simulation to emphasize the impact of lateral compressive strains in catalyzing the formation of vdW gaps within 2D CrS$_2$ slabs. This provides a direct pathway for more facile exfoliation of ultrathin CrS$_2$ nanosheets through strain engineering.

1.Free energy conservation in ab initio molecular dynamics simulations and homogeneous melt nucleation

Authors:Ming Geng, Chris E. Mohn

Abstract: The Z method is a popular atomistic simulation method for determining the melting temperature of solids by using a sequence of molecular dynamics(MD) runs in the microcanonical(NVE) ensemble to target the lowest system energy where the solid always melts. Homogeneous melting at the superheating critical limit($T_h$), is accompanied by a temperature drop to the equilibrium melting temperature($T_m$). Implementation of the Z method interfaced with modern {\it ab initio} electronic structure packages use Hellman-Faynman dynamics to propagate the ions in the NVE ensemble with the Mermin free energy plus the ionic kinetic energy conserved. So the electronic temperature($T_{el}$) is kept fixed along the trajectory which may introduce some spurious ion-electron interactions in MD runs with large temperature changes. We estimate possible systematic errors in evaluating melting temperature with different choices of $T_{el}$. MD runs with the $T_{el}$ = $T_h$ and $T_{el}$ = $T_m$ shows that the difference in melting temperature can be 200-300 K (3-5\% of the melting temperature) for our two test systems. Our results are in good agreement with previous studies with different methods, suggesting the CaSiO$_3$ and SiO$_2$ melts at around 6500 at 100 GPa and 6000 K at 160 GPa. The melting temperature decreases with increasing $T_{el}$ due to the increasing entropic stabilisation of the liquid and the system melts about 3 times faster with $T_{el} = T_h$ than with $T_{el} = T_m$. A careful choice of $T_{el}$ in BOMD is essential for the critical evaluation of the Z method especially at very high temperatures. Inspection of the homogeneous melting process shows that melting occurs via a two-step mechanism: 1) melting of the anion sublattice is accompanied by a small drop in temperature and 2) the formation of small defects which trigger the formation of small liquid clusters and fully melted.

2.Nonempirical Range-Separated Hybrid Functional with Spatially Dependent Screened Exchange

Authors:Jiawei Zhan, Marco Govoni, Giulia Galli

Abstract: Electronic structure calculations based on Density Functional Theory have successfully predicted numerous ground state properties of a variety of molecules and materials. However, exchange and correlation functionals currently used in the literature, including semi-local and hybrid functionals, are often inaccurate to describe the electronic properties of heterogeneous solids, especially systems composed of building blocks with large dielectric mismatch. Here, we present a dielectric-dependent range-separated hybrid functional, SE-RSH, for the investigation of heterogeneous materials. We define a spatially dependent fraction of exact exchange inspired by the static Coulomb-hole and screened-exchange (COHSEX) approximation used in many body perturbation theory, and we show that the proposed functional accurately predicts the electronic structure of several non-metallic interfaces, three- and two-dimensional, pristine and defective solids and nanoparticles.

3.Impact of Cr-O hyrbidization in ACrO3 (A=La, Y): A Theoretical Investigation

Authors:Jeel Swami, Ambesh Dixit, Brajesh Tiwari

Abstract: Electronic properties of spin polarized antiferromagnetic ACrO3 (A = La, Y) are explored with Hubbard Model using Density Functional Theory (DFT). These two isostructural systems are investigated using the different Hubbard energy and analyzed the hybridization of chromium 3d orbitals and oxygen 2p orbitals and the change in energy band gaps against the Hubbard energy. The bond length and bond angle affect significantly the orbital contributions of Cr-3d and O-2p electrons for both the system. We noticed that the Cr-O hybridization affects the orbital degeneracy and is substantiated with partial density of states. These results emphasize the contribution of Hubbard energy in correlated electron systems.

4.Designing optoelectronic properties by on-surface synthesis: formation and electronic structure of an iron-terpyridine macromolecular complex

Authors:Agustin Schiffrin, Martina Capsoni, Gelareh Farahi, Chen-Guang Wang, Cornelius Krull, Marina Castelli, Tanya S. Roussy, Katherine A. Cochrane, Yuefeng Yin, Nikhil Medhekar, Adam Q. Shaw, Wei Ji, Sarah A. Burke

Abstract: Supramolecular chemistry protocols applied on surfaces offer compelling avenues for atomic scale control over organic-inorganic interface structures. In this approach, adsorbate-surface interactions and two-dimensional confinement can lead to morphologies and properties that differ dramatically from those achieved via conventional synthetic approaches. Here, we describe the bottom-up, on-surface synthesis of one-dimensional coordination nanostructures based on an iron (Fe)-terpyridine (tpy) interaction borrowed from functional metal-organic complexes used in photovoltaic and catalytic applications. Thermally activated diffusion of sequentially deposited ligands and metal atoms, and intra-ligand conformational changes, lead to Fe-tpy coordination and formation of these nanochains. Low-temperature Scanning Tunneling Microscopy and Density Functional Theory were used to elucidate the atomic-scale morphology of the system, providing evidence of a linear tri-Fe linkage between facing, coplanar tpy groups. Scanning Tunneling Spectroscopy reveals highest occupied orbitals with dominant contributions from states located at the Fe node, and ligand states that mostly contribute to the lowest unoccupied orbitals. This electronic structure yields potential for hosting photo-induced metal-to-ligand charge transfer in the visible/near-infrared. The formation of this unusual tpy/tri-Fe/tpy coordination motif has not been observed for wet chemistry synthesis methods, and is mediated by the bottom-up on-surface approach used here.

5.Fully epitaxial fcc(111) magnetic tunnel junctions with a Co90Fe10/MgAlO/Co90Fe10 structure

Authors:Jieyuan Song, Thomas Scheike, Cong He, Zhenchao Wen, Tadakatsu Ohkubo, Kazuhiro Hono, Hiroaki Sukegawa, Seiji Mitani

Abstract: Magnetic tunnel junctions (MTJs) with bcc(001)-type structures such as Fe(001)/MgO(001)/Fe(001), have been widely used as the core of various spintronic devices such as magnetoresistive memories; however, the limited material selection of (001)-type MTJs hinders the further development of spintronic devices. Here, as an alternative to the (001)-type MTJs, an fcc(111)-type MTJ using a fully epitaxial CoFe/rock-salt MgAlO (MAO)/CoFe is explored to introduce close-packed lattice systems into MTJs. Using an atomically flat Ru(0001) epitaxial buffer layer, fcc(111) epitaxial growth of the CoFe/MAO/CoFe trilayer is achieved. Sharp CoFe(111)/MAO(111) interfaces are confirmed due to the introduction of periodic dislocations by forming a 5:6 in-plane lattice matching structure. The fabricated (111) MTJ exhibits a tunnel magnetoresistance ratio of 37% at room temperature (47% at 10 K). Symmetric differential conductance curves with respect to bias polarity are observed, indicating the achievement of nearly identical upper and lower MAO interface qualities. Despite the charge-uncompensated (111) orientation for a rock-salt-like MAO barrier, the achievement of flat, stable, and spin-polarized barrier interfaces opens a promising avenue for expanding the design of MTJ structures.

6.Spin polarization gate device based on the chirality-induced spin selectivity and robust nonlocal spin polarization

Authors:Hiroaki Shishido, Yuta Hosaka, Kenta Monden, Akito Inui, Taisei Sayo, Yusuke Kousaka, Yoshihiko Togawa

Abstract: Nonlocal spin polarization phenomena are thoroughly investigated in the devices made of chiral metallic single crystals of CrNb$_3$S$_6$ and NbSi$_2$ as well as of polycrystalline NbSi$_2$. We demonstrate that simultaneous injection of charge currents in the opposite ends of the device with the nonlocal setup induces the switching behavior of spin polarization in a controllable manner. Such a nonlocal spin polarization appears regardless of the difference in the materials and device dimensions, implying that the current injection in the nonlocal configuration splits spin-dependent chemical potentials throughout the chiral crystal even though the current is injected into only a part of the crystal. We show that the proposed model of the spin dependent chemical potentials explains the experimental data successfully. The nonlocal double-injection device may offer significant potential to control the spin polarization to large areas because of the nature of long-range nonlocal spin polarization in chiral materials.

7.Shock-driven nucleation and self-organization of dislocations in the dynamical Peierls model

Authors:Yves-Patrick Pellegrini, Marc Josien

Abstract: Dynamic nucleation of dislocations caused by a stress front ('shock') of amplitude $\sigma_{\rm a}$ moving with speed $V$ is investigated by solving numerically the Dynamic Peierls Equation with an efficient method. Speed $V$ and amplitude $\sigma_{\rm a}$ are considered as independent variables, with $V$ possibly exceeding the longitudinal wavespeed $c_{\rm L}$. Various reactions between dislocations take place such as scattering, dislocation-pair nucleation, annihilation, and crossing. Pairs of edge dislocation are always nucleated with speed $v\gtrsim c_{\rm L}$ (and likewise for screws with $c_{\rm L}$ replaced by $c_{\rm S}$, the shear wavespeed). The plastic wave exhibits self-organization, forming distinct `bulk' and `front' zones. Nucleations occur either within the bulk or at the zone interface, depending on the value of $V$. The front zone accumulates dislocations that are expelled from the bulk or from the interface. In each zone, dislocation speeds and densities are measured as functions of simulation parameters. The densities exhibit a scaling behavior with stress, given by $((\sigma_a/\sigma_{\rm th})^2-1)^\beta$, where $\sigma_{\rm th}$ represents the nucleation threshold and $0<\beta<1$.

8.Ionically-Driven Synthesis and Exchange Bias in Mn$_{4}$N/MnN$_{x}$ Heterostructures

Authors:Zhijie Chen, Christopher J. Jensen, Chen Liu, Xixiang Zhang, Kai Liu

Abstract: Ferrimagnets have received renewed attention as a promising platform for spintronic applications. Of particular interest is the Mn4N from the ${\epsilon}$-phase of the manganese nitride as an emergent rare-earth-free spintronic material due to its perpendicular magnetic anisotropy, small saturation magnetization, high thermal stability, and large domain wall velocity. We have achieved high-quality (001)-ordered Mn$_{4}$N thin film by sputtering Mn onto ${\eta}$-phase Mn$_{3}$N$_{2}$ seed layers on Si substrates. As the deposited Mn thickness varies, nitrogen ion migration across the Mn$_{3}$N$_{2}$/Mn layers leads to a continuous evolution of the layers to Mn$_{3}$N$_{2}$/Mn$_{2}$N/Mn$_{4}$N, Mn$_{2}$N/Mn$_{4}$N, and eventually Mn$_{4}$N alone. The ferrimagnetic Mn$_{4}$N indeed exhibits perpendicular magnetic anisotropy, and forms via a nucleation-and-growth mechanism. The nitrogen ion migration is also manifested in a significant exchange bias, up to 0.3 T at 5 K, due to the interactions between ferrimagnetic Mn$_{4}$N and antiferromagnetic Mn$_{3}$N$_{2}$ and Mn$_{2}$N. These results demonstrate a promising all-nitride magneto-ionic platform with remarkable tunability for device applications.

9.Unveiling the effect of Ni on the formation and structure of Earth's inner core

Authors:Yang Sun, Mikhail I. Mendelev, Feng Zhang, Xun Liu, Bo Da, Cai-Zhuang Wang, Renata M. Wentzcovitch, Kai-Ming Ho

Abstract: Ni is the second most abundant element in the Earth's core. Yet, its effects on the inner core's structure and formation process are usually disregarded because of its similar atomic numbers with Fe. Using ab initio molecular dynamics simulations, we find that the bcc phase can spontaneously crystallize in liquid Ni at temperatures above Fe's melting point at inner core pressures. The melting temperature of Ni is shown to be 700-800 K higher than that of Fe at 323-360 GPa. Phase relations among hcp, bcc, and liquid differ between Fe and Ni. Ni can be a bcc stabilizer for Fe at high temperatures and inner core pressures. A small amount of Ni can accelerate Fe's crystallization under core pressure. These results suggest Ni may substantially impact the structure and formation process of the solid inner core.

10.Automated all-functionals infrared and Raman spectra

Authors:Lorenzo Bastonero, Nicola Marzari

Abstract: Infrared and Raman spectroscopies are ubiquitous techniques employed in many experimental laboratories, thanks to their fast and non-destructive nature able to capture materials' features as spectroscopic fingerprints. Nevertheless, these measurements frequently need theoretical support in order to unambiguously decipher and assign complex spectra. Linear-response theory provides an effective way to obtain the higher-order derivatives needed, but its applicability to modern exchange-correlation functionals remains limited. Here, we devise an automated, open-source, user-friendly approach based on ground-state density-functional theory and the electric enthalpy functional to allow seamless calculations of first-principles infrared and Raman spectra. By employing a finite-displacement and finite-field approach, we allow for the use of any functional, as well as an efficient treatment of large low-symmetry structures. Additionally, we propose a simple scheme for efficiently sampling the Brillouin zone with different electric fields. To demonstrate the capabilities of our approach, we provide illustrations using the ferroelectric LiNbO$_3$ crystal as a paradigmatic example. We predict infrared and Raman spectra using various (semi)local, Hubbard corrected, and hybrid functionals. Our results also show how PBE0 and extended Hubbard functionals yield in this case the best match in term of peak positions and intensities, respectively.

11.Room temperature reversible colossal volto-magnetic effect in all-oxide metallicmagnet/topotactic-phase-transition material heterostructures

Authors:Sourav Chowdhury, Supriyo Majumder, Rajan Mishra, Arup Kumar Mandal, Anita Bagri, Satish Yadav, Suman Karmarkar, D. M. Phase, R. J. Choudhary

Abstract: Multiferroic materials have undergone extensive research in the past two decades in an effort to produce a sizable room-temperature magneto-electric (ME) effect in either exclusive or composite materials for use in a variety of electronic or spintronic devices. These studies have looked into the ME effect by switching the electric polarization by the magnetic field or switching the magnetism by the electric field. Here, an innovative way is developed to knot the functional properties based on the tremendous modulation of electronics and magnetization by the electric field of the topotactic phase transitions (TPT) in heterostructures composed of metallic-magnet/TPT-material. It is divulged that application of a nominal potential difference of 2-3 Volts induces gigantic changes in magnetization by 100-250% leading to colossal Voltomagnetic effect, which would be tremendously beneficial for low-power consumption applications in spintronics. Switching electronics and magnetism by inducing TPT through applying an electric field requires much less energy, making such TPT-based systems promising for energy-efficient memory and logic applications as well as opening a plethora of tremendous opportunities for applications in different domains.

12.Unraveling the unusually high electrical conductivity of the delafossite metal PdCoO$_2$

Authors:Xiaoping Yao, Yechen Xun, Ziye Zhu, Shu Zhao, Wenbin Li

Abstract: The prototypical delafossite metal PdCoO$_2$ has been the subject of intense interest for hosting exotic transport properties. Using first-principles transport calculations and theoretical modeling, we reveal that the high electrical conductivity of PdCoO$_2$ at room temperature originates from the contributions of both high Fermi velocities, enabled by Pd $4d_{z^2}-5s$ hybridization, and exceptionally weak electron-phonon coupling, which leads to a coupling strength ($\lambda=0.057$) that is nearly an order of magnitude smaller than those of common metals. The abnormally weak electron-phonon coupling in PdCoO$_2$ results from a low electronic density of states at the Fermi level, as well as the large and strongly facetted Fermi surface with suppressed Umklapp electron-phonon matrix elements. We anticipate that our work will inform the design of unconventional metals with superior transport properties.

13.Chirality-induced spin splitting in 1D InSeI

Authors:Shu Zhao, Jiaming Hu, Ziye Zhu, Xiaoping Yao, Wenbin Li

Abstract: Spin-orbit coupling (SOC) in chiral materials can induce chirality-dependent spin splitting, enabling electrical manipulation of spin polarization. Here, we use first-principles calculations to investigate the electronic states of chiral one-dimensional (1D) InSeI, which has two enantiomorphic configurations with left- and right-handedness. We find that opposite spin states exist in the left- and right-handed 1D InSeI with significant spin splitting. Although the spin states at the conduction band minimum (CBM) and valence band maximum (VBM) are both degenerate, a direct-to-indirect bandgap transition occurs when a moderate tensile strain ($\sim$4%) is applied along the 1D chain direction, leading to chirality-dependent and collinear spin-momentum locking at the CBM. These findings indicate that 1D InSeI is a promising material for chiral spintronics.

14.Landau Theory of Altermagnetism

Authors:Paul A. McClarty, Jeffrey G. Rau

Abstract: We formulate a Landau theory for altermagnets, a class of colinear compensated magnets with spin-split bands. Starting from the non-relativistic limit, this Landau theory goes beyond a conventional analysis by including spin-space symmetries, providing a simple framework for understanding the key features of this family of materials. We find a set of multipolar secondary order parameters connecting existing ideas about the spin symmetries of these systems, their order parameters and the effect of non-zero spin-orbit coupling. We account for several features of canonical altermagnets such as RuO$_2$, MnTe and CuF$_2$ that go beyond symmetry alone, relating the order parameter to key observables such as magnetization, anomalous Hall conductivity and magneto-elastic and magneto-optical probes. Finally, we comment on generalizations of our framework to a wider family of exotic magnetic systems deriving from the zero spin-orbit coupled limit.

15.Canted Antiferromagnetism in Polar MnSiN$_2$ with High Néel Temperature

Authors:Linus Kautzsch, Alexandru B. Georgescu, Danilo Puggioni, Greggory Kent, Keith M. Taddei, Aiden Reilly, Ram Seshadri, James M. Rondinelli, Stephen D. Wilson

Abstract: MnSiN$_2$ is a transition metal nitride with Mn and Si ions displaying an ordered distribution on the cation sites of a distorted wurtzite-derived structure. The Mn$^{2+}$ ions reside on a 3D diamond-like covalent network with strong superexchange pathways. We simulate its electronic structure and find that the N anions in MnSiN$_2$ act as $\sigma$- and $\pi$-donors, which serve to enhance the N-mediated superexchange, leading to the high N\'{e}el ordering temperature of $T_N$ = 443 K. Polycrystalline samples of MnSiN$_2$ were prepared to reexamine the magnetic structure and resolve previously reported discrepancies. An additional magnetic canting transition is observed at $T_\mathrm{cant}$ = 433 K and the precise canted ground state magnetic structure has been resolved using a combination of DFT calculations and powder neutron diffraction. The calculations favor a $G$-type antiferromagnetic spin order with lowering to $Pc^\prime$. Irreducible representation analysis of the magnetic Bragg peaks supports the lowering of the magnetic symmetry. The computed model includes a 10$^\circ$ rotation of the magnetic spins away from the crystallographic $c$-axis consistent with measured powder neutron diffraction data modeling and a small canting of 0.6$^\circ$.

16.Decoding the Mechanisms of Reversibility Loss in Rechargeable Zinc-Air Batteries

Authors:Zhibin Yi, Liangyu Li, Cheuk Kai Chan, Yaxin Tang, Zhouguang Lu, Chunyi Zhi, Qing Chen, Guangfu Luo

Abstract: Attaining high reversibility of electrodes and electrolyte is essential for the longevity of secondary batteries. Rechargeable zinc-air batteries (RZABs), however, encounter drastic irreversible changes in the zinc anodes and air cathodes during cycling. To uncover the mechanisms of reversibility loss in RZABs, we investigate the evolution of zinc anode, alkaline electrolyte, and air electrode through experiments and first-principles calculations. Morphology diagrams of zinc anodes under versatile operating conditions reveal that the nano-sized mossy zinc dominates the later cycling stage. Such anodic change is induced by the increased zincate concentration due to hydrogen evolution, which is catalyzed by the mossy structure and results in oxide passivation on electrodes, and eventually leads to low true Coulombic efficiencies and short lifespans of batteries. Inspired by these findings, we finally present a novel overcharge-cycling protocol to compensate the Coulombic efficiency loss caused by hydrogen evolution and significantly extend the battery life.

17.Giant magnetic and optical anisotropy in cerium-substituted M-type strontium hexaferrite driven by 4$f$ electrons

Authors:Churna Bhandari, Durga Paudyal

Abstract: By performing density functional calculations, we find a giant magnetocrystalline anisotropy (MCA) constant in abundant element cerium (Ce) substituted M-type hexaferrite, in the energetically favorable strontium site, assisted by a quantum confined electron transfer from Ce to specific iron (2a) site. Remarkably, the calculated electronic structure shows that the electron transfer leads to the formation of Ce$^{3+}$ and Fe$^{2+}$ at the $2a$ site producing an occupied Ce($4f^1$) state below the Fermi level that adds a significant contribution to MCA and magnetic moment. A half Ce-substitution forms a metallic state, while a full substitution retains the semiconducting state of the strontium-hexaferrite (host). In the latter, the band gap is reduced due to the formation of charge transferred states in the gap region of the host. The optical absorption coefficient shows an enhanced anisotropy between light polarization in parallel and perpendicular directions. Calculated formation energies, including the analysis of probable competing phases, and elastic constants confirm that both compositions are chemically and mechanically stable. With successful synthesis, the Ce-hexaferrite can be a new high-performing critical-element-free permanent magnet material adapted for use in devices such as automotive traction drive motors.

18.Topological interfacial states in ferroelectric domain walls of two-dimensional bismuth

Authors:Wei Luo, Yang Zhong, Hongyu Yu, Muting Xie, Yingwei Chen, Hongjun Xiang, Laurent Bellaiche

Abstract: Using machine learning method, we investigate various domain walls for the recently discovered single-element ferroelectrics bismuth monolayer (Nature 617, 67 (2023)). We find the charged domain wall configuration has a lower energy than the uncharged domain wall structure due to its low electrostatic repusion potential. Two stable charged domain wall configurations exhibit topological interfacial states near their domain walls, which is caused by the change of the Z_2 number between ferroelectric and paraelectric states. Interestingly, different from the edge states of topological insulators, the energies of topological interfacial states for these two structure are splited due to the build-in electric fields in ferroelectrics. We also find a stable uncharged domain wall configutation can reduce band gap which is caused by the domain wall. Our works indicate that domain walls in two-dimensional bismuth may be a good platform for ferroelectric domain wall devices.

1.The effect of substrate temperature on cadmium telluride films in high temperature vapor deposition process

Authors:Wenxiong Zhao, Yufeng Zhang

Abstract: Physical vapor high-temperature deposition of CdTe thin films is one of the main methods for preparing high-efficiency CdTe solar cells, but high-temperature deposition also has an impact on the internal structure of the film. The difference in thermal expansion coefficients between the substrate and CdTe leads to the generation of internal stress in the CdTe thin film during the cooling process. In this work, we prepared thin films with different substrate temperatures using a homemade GVD device, and observed by SEM that the crystallization quality of the film gradually improved with the increase of substrate temperature, but accompanied by the shift of XRD peak position. We calculated the internal stress situation of the film by the shift amount, and the possible causes of stress generation were speculated by the results of TEM and SAED to be the combined effects of the different thermal expansion coefficients between the substrate and the film and the stacking fault defects inside the film.

2.$\textit{In situ}$ electric-field control of ferromagnetic resonance in the low-loss organic-based ferrimagnet V[TCNE]$_{x\sim 2}$

Authors:Seth W. Kurfman, Andrew Franson, Piyush Shah, Yueguang Shi, Hil Fung Harry Cheung, Katherine E. Nygren, Mitchell Swyt, Kristen S. Buchanan, Gregory D. Fuchs, Michael E. Flatté, Gopalan Srinivasan, Michael Page, Ezekiel Johnston-Halperin

Abstract: We demonstrate indirect electric-field control of ferromagnetic resonance (FMR) in devices that integrate the low-loss, molecule-based, room-temperature ferrimagnet vanadium tetracyanoethylene (V[TCNE]$_{x \sim 2}$) mechanically coupled to PMN-PT piezoelectric transducers. Upon straining the V[TCNE]$_x$ films, the FMR frequency is tuned by more than 6 times the resonant linewidth with no change in Gilbert damping for samples with $\alpha = 6.5 \times 10^{-5}$. We show this tuning effect is due to a strain-dependent magnetic anisotropy in the films and find the magnetoelastic coefficient $|\lambda_S| \sim (1 - 4.4)$ ppm, backed by theoretical predictions from DFT calculations and magnetoelastic theory. Noting the rapidly expanding application space for strain-tuned FMR, we define a new metric for magnetostrictive materials, $\textit{magnetostrictive agility}$, given by the ratio of the magnetoelastic coefficient to the FMR linewidth. This agility allows for a direct comparison between magnetostrictive materials in terms of their comparative efficacy for magnetoelectric applications requiring ultra-low loss magnetic resonance modulated by strain. With this metric, we show V[TCNE]$_x$ is competitive with other magnetostrictive materials including YIG and Terfenol-D. This combination of ultra-narrow linewidth and magnetostriction in a system that can be directly integrated into functional devices without requiring heterogeneous integration in a thin-film geometry promises unprecedented functionality for electric-field tuned microwave devices ranging from low-power, compact filters and circulators to emerging applications in quantum information science and technology.

3.Hydrogen Transport Between Layers of Transition Metal-Dichalcogenides

Authors:Ismail Eren, Yun An, Agnieszka B. Kuc

Abstract: Hydrogen is a crucial source of green energy and has been extensively studied for its potential usage in fuel cells. The advent of two-dimensional crystals (2DCs) has taken hydrogen research to new heights, enabling it to tunnel through layers of 2DCs or be transported within voids between the layers, as demonstrated in recent experiments by Geim's group. In this study, we investigate how the composition and stacking of transition-metal dichalcogenide (TMDC) layers influence the transport and self-diffusion coefficients (D) of hydrogen atoms using well-tempered metadynamics simulations. Our findings show that modifying either the transition metal or the chalcogen atoms significantly affects the free energy barriers (Delta F) and, consequently, the self-diffusion of hydrogen atoms between the 2DC layers. In the Hh polytype (2H stacking), MoSe2 exhibits the lowest Delta F, while WS2 has the highest, resulting in the largest D for the former system. Additionally, hydrogen atoms inside the RhM (or 3R) polytype encounter more than twice lower energy barriers and, thus, much higher diffusivity compared to those within the most stable Hh stacking. These findings are particularly significant when investigating twisted layers or homo- or heterostructures, as different stacking areas may dominate over others, potentially leading to directional transport and interesting materials for ion or atom sieving.

4.Electric-field induced half-metal in monolayer CrSBr

Authors:Hao-Tian Guo, San-Dong Guo, Yee Sin Ang

Abstract: Two-dimensional (2D) half-metallic materials are highly desirable for nanoscale spintronic applications. Here, we propose a new mechanism that can achieve half-metallicity in 2D ferromagnetic (FM) material with two-layer magnetic atoms by electric field tuning. We use a concrete example of experimentally synthesized CrSBr monolayer to illustrate our proposal through the first-principle calculations. It is found that the half-metal can be achieved in CrSBr within appropriate electric field range, and the corresponding amplitude of electric field intensity is available in experiment. Janus monolayer $\mathrm{Cr_2S_2BrI}$ is constructed, which possesses built-in electric field due to broken horizontal mirror symmetry. However, $\mathrm{Cr_2S_2BrI}$ without and with applied external electric field is always a FM semiconductor. A possible memory device is also proposed based on CrSBr monolayer. Our works will stimulate the application of 2D FM CrSBr in future spintronic nanodevices.

5.Energy of a many-electron system in an ensemble ground-state, versus electron number and spin: piecewise-linearity and flat plane condition generalized

Authors:Yuli Goshen, Eli Kraisler

Abstract: Description of the total energy of a many-electron system, $E$, as a function of the total number of electrons $N_\textrm{tot}$ (integer or fractional) is of great importance in atomic and molecular physics, theoretical chemistry and materials science. Equally significant is the correct dependence of the energy on the spin of the system, $S_\textrm{tot}$. In this Letter we extend previous work, allowing both $N_\textrm{tot}$ and $S_\textrm{tot}$ to vary continuously, taking on both integer and fractional values, rigorously considering systems with arbitrary values of $N_\textrm{tot}$ and of the equilibrium spin. We describe the ground state of a finite, many-electron system by an ensemble of pure states, and characterize the dependence of the energy and the spin-densities on both $N_\textrm{tot}$ and $S_\textrm{tot}$. Our findings generalize the piecewise-linearity principle of Phys. Rev. Lett. 49, 1691 (1982) and the flat-plane condition of Phys. Rev. Lett. 102, 066403 (2009). We find that the ensemble ground state consists of four pure states at most, provided that the absolute value of the spin is smaller or equal to its equilibrium value, for a given $N_\textrm{tot}$. As a result, a degeneracy in the ensemble ground-state occurs, such that the total energy and the density are unique, but the spin-densities are not. Moreover, we find a new type of a derivative discontinuity, which manifests in the case of spin variation at constant $N_\textrm{tot}$, as a jump in the Kohn-Sham potential at the edges of the variation range. Our findings serve as a basis for development of advanced approximations in density functional theory and other many-electron methods.

6.How to enhance anomalous Hall effects in magnetic Weyl semimetal Co$_3$Sn$_2$S$_2$?

Authors:Shivam Rathod, Megha Malasi, Archana Lakhani, Devendra Kumar

Abstract: Large spin-orbit coupling, kagome lattice, nontrivial topological band structure with inverted bands anti-crossings, and Weyl nodes are essential ingredients, ideally required to obtain maximal anomalous Hall effect (AHE) are simultaneously present in Co$_3$Sn$_2$S$_2$. It is a leading platform to show large intrinsic anomalous Hall conductivity (AHC) and giant anomalous Hall angle (AHA) simultaneously at low fields. The giant AHE in Co$_3$Sn$_2$S$_2$ is robust against small-scale doping-related chemical potential changes. In this work, we unveil a selective and co-chemical doping route to maximize AHEs in Co$_3$Sn$_2$S$_2$. To begin with, in Co$_3$Sn$_{2-x}$In$_x$S$_2$, we brought the chemical potential at the hotspot of Berry curvature along with a maximum of asymmetric impurity scattering in high mobility region. As a result at x=0.05, we found a significant enhancement of AHA (95%) and AHC (190%) from the synergistic enhancement of extrinsic and intrinsic mechanisms from modified Berry curvature of gaped nodal lines. Later, with anticipation of further improvements in AHE, we grew hole-co-doped Co$_{3-y}$Fe$_y$Sn$_{2-x}$In$_x$S$_2$ crystals, where we found rather a suppression of AHEs. The role of dopants in giving extrinsic effects or band broadening can be better understood when chemical potential does not change after doping. By simultaneous and equal co-doping with electrons and holes in Co$_{3-y-z}$Fe$_y$Ni$_z$Sn$_2$S$_2$, we kept the chemical potential unchanged. Henceforth, we found a significant enhancement in intrinsic AHC $\sim$116% due to the disorder broadenings in kagome bands

7.Framework for additive manufacturing of porous Inconel 718 for electrochemical applications

Authors:Ahmad Zafari, Kiran Kiran, Inmaculada Gimenez-Garcia, Antoni Forner-Cuenca, Kenong Xia, Ian Gibson, Davoud Jafari

Abstract: Porous electrodes were developed using laser powder bed fusion of Inconel 718 lattice structures and electrodeposition of a porous nickel catalytic layer. Laser energy densities of 83-333 J/m were used to fabricate 500 um thick electrodes made of body centered cubic unit cells of 200-500 um and strut thicknesses of 100-200 um. Unit cells of 500 um and strut thickness of 200 um were identified as optimum. Despite small changes in feature sizes by the energy input, the porosity of more than 50 percent and pore size of 100 um did not change. Nickel electrodeposition created a network of submicrometer pores. The electrodes' electrochemical efficiency was assessed by analysing hydrogen/oxygen evolution reaction (HER/OER) in a three-electrode setup. For HER, a much larger maximum current density of -372 mA/cm2 at a less negative potential of -0.4 V vs RHE (potential against reversible hydrogen electrode) was produced in the nickel-coated samples, as compared to -240 mA/cm2 at -0.6 V in the bare one, indicating superior performance of the coated sample. For OER, however, both bare and nickel-coated electrodes similarly showed a maximum current density of 350 mA/cm2 at 1.8 V vs RHE due to performance trade-offs arising from sample composition and structure.

8.Quasicrystalline Nanocrystal Superlattice with Partial Matching Rules

Authors:Xingchen Ye, Jun Chen, M. Eric Irrgang, Michael Engel, Angang Dong, Sharon C. Glotzer, Christopher B. Murray

Abstract: Expanding the library of self-assembled superstructures provides insight into the behavior of atomic crystals and supports the development of materials with mesoscale order. Here we build upon recent findings of soft matter quasicrystals and report a quasicrystalline binary nanocrystal superlattice that exhibits correlations in the form of partial matching rules reducing tiling disorder. We determine a three-dimensional structure model through electron tomography and direct imaging of surface topography. The 12-fold rotational symmetry of the quasicrystal is broken in sub-layers, forming a random tiling of rectangles, large triangles, and small triangles with 6-fold symmetry. We analyze the geometry of the experimental tiling and discuss factors relevant for the stabilization of the quasicrystal. Our joint experimental-computational study demonstrates the power of nanocrystal superlattice engineering and further narrows the gap between the richness of crystal structures found with atoms and in soft matter assemblies.

9.Oxide layer formation prevents deteriorating ion migration in thermoelectric Cu$_2$Se during operation in air

Authors:Rasmus S. Christensen, Peter S. Thorup, Lasse R. Jørgensen, Martin Roelsgaard, Karl F. F. Fischer, Ann-Christin Dippel, Bo Brummerstedt Iversen

Abstract: Cu$_2$Se is a mixed ionic-electronic conductor with outstanding thermoelectric performance originally envisioned for space missions. Applications were discontinued due to material instability, where elemental Cu grows at the electrode interfaces during operation in vacuum. Here, we show that when Cu$_2$Se is operating in air, formation of an oxide surface layer suppresses Cu$^+$ migration along the current direction. In operando X-ray scattering and electrical resistivity measurements quantify Cu$^+$ migration through refinement of atomic occupancies and phase composition analysis. Cu deposition can be prevented during operation in air, irrespective of a critical voltage, if the thermal gradient is applied along the current direction. Maximum entropy electron density analysis provides experimental evidence that Cu$^+$ migration pathways under thermal and electrical gradients differ substantially from equilibrium diffusion. The study establishes new promise for inexpensive sustainable Cu$_2$Se in thermoelectric applications, and it underscores the importance of atomistic insight into materials during thermoelectric operating conditions.

10.Structural properties of epitaxial α-U thin films on Ti, Zr, W and Nb

Authors:R. Nicholls, D. A. Chaney, G. H. Lander, R. Springell, C. Bell

Abstract: Thin layers of orthorhombic uranium ({\alpha}-U) have been grown onto buffered sapphire substrates by d.c. magnetron sputtering, resulting in the discovery of new epitaxial matches to Ti(00.1) and Zr(00.1) surfaces. These systems have been characterised by X-ray diffraction and reflectivity and the optimal deposition temperatures have been determined. More advanced structural characterisation of the known Nb(110) and W(110) buffered {\alpha}-U systems has also been carried out, showing that past reports of the domain structures of the U layers are incomplete. The ability of this low symmetry structure to form crystalline matches across a range of crystallographic templates highlights the complexity of U metal epitaxy and points naturally toward studies of the low temperature electronic properties of {\alpha}-U as a function of epitaxial strain.

11.Detection of nontrivial topology driven by charge density wave in a semi-Dirac metal

Authors:Rafiqul Alam, Prasun Boyal, Shubhankar Roy, Ratnadwip Singha, Buddhadeb Pal, Riju Pal, Prabhat Mandal, Priya Mahadevan, Atindra Nath Pal

Abstract: The presence of electron correlations in a system with topological order can lead to exotic ground states. Considering single crystals of LaAgSb2 which has a square net crystal structure, one finds multiple charge density wave transitions (CDW) as the temperature is lowered. We find large planar Hall (PHE) signals in the CDW phase, which are still finite in the high temperature phase though they change sign. Optimising the structure within first-principles calculations, one finds an unusual chiral metallic phase. This is because as the temperature is lowered, the electrons on the Ag atoms get more localized, leading to stronger repulsions between electrons associated with atoms on different layers. This leads to successive layers sliding with respect to each other, thereby stabilising a chiral structure in which inversion symmetry is also broken. The large Berry curvature associated with the low temperature structure explains the low temperature PHE. At high temperature the PHE arises from the changes induced in the tilted Dirac cone in a magnetic field. Our work represents a route towards detecting and understanding the mechanism in a correlation driven topological transition through electron transport measurements, complemented by ab-initio electronic structure calculations.

12.Single crystal growth and characterization of antiferromagnetically ordering EuIn$_2$

Authors:Brinda Kuthanazhi, Simon X. M. Riberolles, Dominic H. Ryan, Philip J. Ryan, Jong-Woo Kim, Lin-Lin Wang, Robert J. McQueeney, Benjamin G. Ueland, Paul C. Canfield

Abstract: We report the single crystal growth and characterization of EuIn$_2$, a magnetic topological semimetal candidate according to our density functional theory (DFT) calculations. We present results from electrical resistance, magnetization, M\"ossbauer spectroscopy, and X-ray resonant magnetic scattering (XRMS) measurements. We observe three magnetic transitions at $T_{\text{N}1}\sim 14.2~$K, $T_{\text{N}2}\sim12.8~$K and $T_{\text{N}3}\sim 11~$K, signatures of which are consistently seen in anisotropic temperature dependent magnetic susceptibility and electrical resistance data. M\"ossbauer spectroscopy measurements on ground crystals suggest an incommensurate sinusoidally modulated magnetic structure below the transition at $T_{\text{N}1}\sim 14~$K, followed by the appearance of higher harmonics in the modulation on further cooling roughly below $T_{\text{N}2}\sim13~$K, before the moment distribution squaring up below the lowest transition around $T_{\text{N}3}\sim 11~$K. XRMS measurements showed the appearance of magnetic Bragg peaks below $T_{\text{N}1}\sim14~$K, with a propagation vector of $\bm{\tau}$ $=(\tau_h,\bar{\tau}_h,0)$, with $\tau_h$varying with temperature, and showing a jump at $T_{\text{N}3}\sim11$~K. The temperature dependence of $\tau_h$ between $\sim11$~K and $14$~K shows incommensurate values consistent with the M\"{o}ssbauer data. XRMS data indicate that $\tau_h$ remains incommensurate at low temperatures and locks into $\tau_h=0.3443(1)$.

13.Recent advances in triboelectric nanogenerators: energy harvest and other applications

Authors:L. J. Zhang

Abstract: Triboelectric nanogenerators (TENG) with triboelectrification and electrostatic induction effects have attracted wide attention in recent decades, for its diversified application scenarios such as power generation, sensing, and so on. Undoubtedly, although still lacks standardized large-scale production, TENG has demonstrated good performance and increasingly promising prospects in fields such as energy harvest, healthcare, and medical monitoring. Here, this minireview provides a brief summary on the latest application progress of TENG, which may offer insights for expanding application fields and developing design concepts for TENG based devices.

14.Designing Materials Acceleration Platforms for Heterogeneous CO2 Photo(thermal)catalysis

Authors:Andrew Wang, Carlota Bozal-Ginesta, Sai Govind Hari Kumar, Alán Aspuru-Guzik, Geoffrey A. Ozin

Abstract: Materials acceleration platforms (MAPs) combine automation and artificial intelligence to accelerate the discovery of molecules and materials. They have potential to play a role in addressing complex societal problems such as climate change. Solar chemicals and fuels generation via heterogeneous CO2 photo(thermal)catalysis is a relatively unexplored process that holds potential for contributing towards an environmentally and economically sustainable future, and therefore a very promising application for MAP science and engineering. Here, we present a brief overview of how design and innovation in heterogeneous CO2 photo(thermal)catalysis, from materials discovery to engineering and scale-up, could benefit from MAPs. We discuss relevant design and performance descriptors and the level of automation of state-of-the-art experimental techniques, and we review examples of artificial intelligence in data analysis. Based on these precedents, we finally propose a MAP outline for autonomous and accelerated discoveries in the emerging field of solar chemicals and fuels sourced from CO2 photo(thermal)catalysis.

15.Possible ferroic properties of copper-substituted lead phosphate apatite

Authors:Jiri Hlinka

Abstract: Paper provides symmetry arguments explaining that charge density wave induced by copper doping to lead phosphate apatite crystal implies a symmetry breaking phase transition from $P6_3/m$ (176) to a polar and chiral phase with $P6_3$ (173) spacegroup symmetry.

16.Static disorder in soft X-ray angle-resolved photoemission spectroscopy: theory and application to ion-bombarded InAs(110)

Authors:Enrico Della Valle, Procopios Constantinou, Thorsten Schmitt, Gabriel Aeppli, Vladimir N. Strocov

Abstract: Angle-resolved photoemission spectroscopy (ARPES) is one of the most ubiquitous characterization techniques utilized in the field of condensed matter physics. The resulting spectral intensity consists of a coherent and incoherent part, whose relative contribution is governed by atomic disorder, where thermal contribution is expressed in terms of the Debye-Waller factor (DWF). In this work, we present a soft-X-ray study on the sputter-induced disorder of InAs(110) surface. We define a new quantity, referred to as the coherence factor FC, which is the analogue of the DWF, extended to static disorder. We show that FC alone can be used to quantify the depletion of coherent intensity with increasing disorder, and, in combination with the DWF, allows considerations of thermal and static disorder effects on the same footing. Our study also unveils an intriguing finding: as disorder increases, the ARPES intensity of quantum well states originating from the conduction band depletes more rapidly compared to the valence bands. This difference can be attributed to the predominance of quasi-elastic defect scattering and the difference in phase space available for such scattering for conduction-band (CB) and valence-band (VB) initial states. Specifically, the absence of empty states well below the Fermi energy (EF) hinders the quasi-elastic scattering of the VB states, while their abundance in vicinity of EF enhances the scattering rate of the CB states. Additionally, we observe no noticeable increase in broadening of the VB dispersions as the sputter-induced disorder increases. This observation aligns with the notion that valence initial states are less likely to experience the quasi-elastic defect scattering, which would shorten their lifetime, and with the random uncorrelated nature of the defects introduced by the ion sputtering.

17.A first-principles approach to closing the "10-100 eV gap" for charge-carrier thermalization in semiconductors

Authors:Dallin O. Nielsen, Chris G. Van de Walle, Sokrates T. Pantelides, Ronald D. Schrimpf, Daniel M. Fleetwood, Massimo V. Fischetti

Abstract: The present work is concerned with studying accurately the energy-loss processes that control the thermalization of hot electrons and holes that are generated by high-energy radiation in wurtzite GaN, using an ab initio approach. Current physical models of the nuclear/particle physics community cover thermalization in the high-energy range (kinetic energies exceeding ~100 eV), and the electronic-device community has studied extensively carrier transport in the low-energy range (below ~10 eV). However, the processes that control the energy losses and thermalization of electrons and holes in the intermediate energy range of about 10-100 eV (the "10-100 eV gap") are poorly known. The aim of this research is to close this gap, by utilizing density functional theory (DFT) to obtain the band structure and dielectric function of GaN for energies up to about 100 eV. We also calculate charge-carrier scattering rates for the major charge-carrier interactions (phonon scattering, impact ionization, and plasmon emission), using the DFT results and first-order perturbation theory. With this information, we study the thermalization of electrons starting at 100 eV using the Monte Carlo method to solve the semiclassical Boltzmann transport equation. Full thermalization of electrons and holes is complete within ~1 and 0.5 ps, respectively. Hot electrons dissipate about 90% of their initial kinetic energy to the electron-hole gas (90 eV) during the first ~0.1 fs, due to rapid plasmon emission and impact ionization at high energies. The remaining energy is lost more slowly as phonon emission dominates at lower energies (below ~10 eV). During the thermalization, hot electrons generate pairs with an average energy of ~8.9 eV/pair (11-12 pairs per hot electron). Additionally, during the thermalization, the maximum electron displacement from its original position is found to be on the order of 100 nm.

18.Amorphous shear bands in crystalline materials as drivers of plasticity

Authors:Xuanxin Hu, Nuohao Liu, Vrishank Jambur, Siamak Attarian, Ranran Su, Hongliang Zhang, Jianqi Xi, Hubin Luo, John Perepezko, Izabela Szlufarska

Abstract: Traditionally, the formation of amorphous shear bands (SBs) in crystalline materials has been undesirable, because SBs can nucleate voids and act as precursors to fracture. They also form as a final stage of accumulated damage. Only recently SBs were found to form in undefected crystals, where they serve as the primary driver of plasticity without nucleating voids. Here, we have discovered trends in materials properties that determine when amorphous shear bands will form and whether they will drive plasticity or lead to fracture. We have identified the materials systems that exhibit SB deformation, and by varying the composition, we were able to switch from ductile to brittle behavior. Our findings are based on a combination of experimental characterization and atomistic simulations, and they provide a potential strategy for increasing toughness of nominally brittle materials.

19.Atomistic theory of hot carrier relaxation in large plasmonic nanoparticles

Authors:S. M. João, Hanwen Jin, Johannes Lischner

Abstract: Recently, there has been significant interest in harnessing hot carriers generated from the decay of localized surface plasmons in metallic nanoparticles for applications in photocatalysis, photovoltaics and sensing. In this work, we present an atomistic approach to predict the population of hot carriers under continuous wave illumination in large nanoparticles. For this, we solve the equation of motion of the density matrix taking into account both excitation of hot carriers as well as subsequent relaxation effects. We present results for spherical Au and Ag nanoparticles with up to $250,000$ atoms. We find that the population of highly energetic carriers depends both on the material and the nanoparticle size. We also study the increase in the electronic temperature upon illumination and find that Ag nanoparticles exhibit a much larger temperature increase than Au nanoparticles. Finally, we investigate the effect of using different models for the relaxation matrix but find that qualitative features of the hot-carrier population are robust.

1.Using Targeted Phonon Excitation to Modulate Thermal Conductivity of Boron Nitride

Authors:Dongkai Pan, Xiao Wan, Zhicheng Zong, Yangjun Qin, Nuo Yang

Abstract: Modulation of thermal conductivity has become a hotspot in the field of heat conduction. A novel strategy based on targeted phonon excitation has been recently proposed for efficient and reversible modulation of thermal conductivity. In this article, the effectiveness of that strategy is further evaluated on hexagonal boron nitride through ab initio methods. Results indicate that thermal conductivity can be increased from 885 W m-1 K-1 to 1151 W m-1 K-1 or decreased to 356 W m-1 K-1, thereby broadening the scope of applicability of this strategy.

2.First-principle study of spin transport property in $L1_0$-FePd(001)/graphene heterojunction

Authors:Hayato Adachi, Ryuusuke Endo, Hikari Shinya, Hiroshi Naganuma, Mitsuharu Uemoto

Abstract: In our previous work, we synthesized a metal/2D material heterointerface consisting of $L1_0$-ordered iron-palladium (FePd) and graphene (Gr) called FePd(001)/Gr. This system has been explored by both experimental measurements and theoretical calculations. In this study, we focus on a heterojunction composed of FePd and multilayer graphene referred to as FePd(001)/$m$-Gr/FePd(001), where $m$ represents the number of graphene layers. We perform first-principles calculations to predict their spin-dependent transport properties. The quantitative calculations of spin-resolved conductance and magnetoresistance (MR) ratio (150-200%) suggest that the proposed structure can function as a magnetic tunnel junction in spintronics applications. We also find that an increase in $m$ not only reduces conductance but also changes transport properties from the tunneling behavior to the graphite $\pi$-band-like behavior. Furthermore, we examine the impact of lateral displacements (sliding) at the interface and find that the spin transport properties remain robust despite these changes; this is the advantage of two-dimensional material hetero-interfaces over traditional insulating barrier layers such as MgO.

3.Transport evidence of the three-dimensional Dirac semimetal phase in doped $α$-Sn grown by molecular beam epitaxy

Authors:Yuanfeng Ding, Bingxin Li, Chen Li, Yan-Bin Chen, Hong Lu, Yan-Feng Chen

Abstract: We report the quantum transport properties of the $\alpha$-Sn films grown on CdTe (001) substrates by molecular beam epitaxy. The $\alpha$-Sn films are doped with phosphorus to tune the Fermi level and access the bulk state. Clear Shubnikov-de Haas oscillations can be observed below 30 K and a nontrivial Berry phase has been confirmed. A nearly spherical Fermi surface has been demonstrated by angle-dependent oscillation frequencies. In addition, the sign of negative magnetoresistance which is attributed to the chiral anomaly has also been observed. These results provide strong evidence of the three-dimensional Dirac semimetal phase in $\alpha$-Sn.

4.Charge State-Dependent Symmetry Breaking of Atomic Defects in Transition Metal Dichalcogenides

Authors:Feifei Xiang, Lysander Huberich, Preston A. Vargas, Riccardo Torsi, Jonas Allerbeck, Anne Marie Z. Tan, Chengye Dong, Pascal Ruffieux, Roman Fasel, Oliver Gröning, Yu-Chuan Lin, Richard G. Hennig, Joshua A. Robinson, Bruno Schuler

Abstract: The functionality of atomic quantum emitters is intrinsically linked to their host lattice coordination. Structural distortions that spontaneously break the lattice symmetry strongly impact their optical emission properties and spin-photon interface. Here we report on the direct imaging of charge state-dependent symmetry breaking of two prototypical atomic quantum emitters in mono- and bilayer MoS$_2$ by scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM). By substrate chemical gating different charge states of sulfur vacancies (Vac$_\text{S}$) and substitutional rhenium dopants (Re$_\text{Mo}$) can be stabilized. Vac$_\text{S}^{-1}$ as well as Re$_\text{Mo}^{0}$ and Re$_\text{Mo}^{-1}$ exhibit local lattice distortions and symmetry-broken defect orbitals attributed to a Jahn-Teller effect (JTE) and pseudo-JTE, respectively. By mapping the electronic and geometric structure of single point defects, we disentangle the effects of spatial averaging, charge multistability, configurational dynamics, and external perturbations that often mask the presence of local symmetry breaking.

5.Ultrafast nonadiabatic phonon renormalization in photoexcited single-layer MoS$_2$

Authors:Nina Girotto, Fabio Caruso, Dino Novko

Abstract: Comprehending nonequilibrium electron-phonon dynamics at the microscopic level and at the short time scales is one of the main goals in condensed matter physics. Effective temperature models and time-dependent Boltzmann equations are standard techniques for exploring and understanding nonequilibrium state and the corresponding scattering channels. However, these methods consider only the time evolution of carrier occupation function, while the self-consistent phonon dressing in each time instant coming from the nonequilibrium population is ignored, which makes them less suitable for studying ultrafast phenomena where softening of the phonon modes plays an active role. Here, we combine ab-initio time-dependent Boltzmann equations and many-body phonon self-energy calculations to investigate the full momentum- and mode-resolved nonadiabatic phonon renormalization picture in the MoS$_2$ monolayer under nonequilibrium conditions. Our results show that the nonequilibrium state of photoexcited MoS$_2$ is governed by multi-valley topology of valence and conduction bands that brings about characteristic anisotropic electron-phonon thermalization paths and the corresponding phonon renormalization of strongly-coupled modes around high-symmetry points of the Brillouin zone. As the carrier population is thermalized towards its equilibrium state, we track in time the evolution of the remarkable phonon anomalies induced by nonequilibrium and the overall enhancement of the phonon relaxation rates. This work shows potential guidelines to tailor the electron-phonon relaxation channels and control the phonon dynamics under extreme photoexcited conditions.

6.Mechanisms and kinetics of C-S-H nucleation approaching the spinodal line: Insights into the role of organics additives

Authors:Christophe Labbez, Lina Bouzouaid, Alexander E. S. Van Driessche, Wai Li Ling, Juan Carlos Martinez, Barbara Lothenbach, Alejandro Fernandez-Martinez

Abstract: Wet chemistry C-S-H precipitation experiments were performed under controlled conditions of solution supersaturation in the presence and absence of gluconate and three hexitol molecules. Characterization of the precipitates with SAXS and cryo-TEM experiments confirmed the presence of a multi-step nucleation pathway. Induction times for the formation of the amorphous C-S-H spheroids were determined from light transmittance. Analysis of those data with the classical nucleation theory revealed a significant increase of the kinetic prefactor in the same order as the complexation constants of calcium and silicate with each of the organics. Finally, two distinct precipitation regimes of the C-S-H amorphous precursor were identified: i) a nucleation regime at low saturation indexes (SI) and ii) a spinodal nucleation regime at high SI where the free energy barrier to the phase transition is found to be of the order of the kinetic energy or less.

7.Strongly Anisotropic Spin and Orbital Rashba Effect at a Tellurium - Noble Metal Interface

Authors:B. Geldiyev, M. Ünzelmann, P. Eck, T. Kißlinger, J. Schusser, T. Figgemeier, P. Kagerer, N. Tezak, M. Krivenkov, A. Varykhalov, A. Fedorov, L. Nicolaï, J. Minár, K. Miyamoto, T. Okuda, K. Shimada, D. Di Sante, G. Sangiovanni, L. Hammer, M. A. Schneider, H. Bentmann, F. Reinert

Abstract: We study the interplay of lattice, spin and orbital degrees of freedom in a two-dimensional model system: a flat square lattice of Te atoms on a Au(100) surface. The atomic structure of the Te monolayer is determined by scanning tunneling microscopy (STM) and quantitative low-energy electron diffraction (LEED-IV). Using spin- and angle-resolved photoelectron spectroscopy (ARPES) and density functional theory (DFT), we observe a Te-Au interface state with highly anisotropic Rashba-type spin-orbit splitting at the X point of the Brillouin zone. Based on a profound symmetry and tight-binding analysis, we show how in-plane square lattice symmetry and broken inversion symmetry at the Te-Au interface together enforce a remarkably anisotropic orbital Rashba effect which strongly modulates the spin splitting.

8.Lone-Pair Stereochemistry Induces Ferroelectric Distortion and the Rashba Effect in Inorganic Halide Perovskites

Authors:Michael W. Swift, John L. Lyons

Abstract: The lone-pair s states of germanium, tin, and lead underlie many of the unconventional properties of the inorganic metal halide perovskites. Dynamic stereochemical expression of the lone pairs is well established for perovskites based on all three metals, but previously only the germanium perovskites were thought to express the lone pair crystallographically. In this work, we use advanced first-principles calculations with a hybrid functional and spin-orbit coupling to predict stable monoclinic polar phases of $\mathrm{CsSnI}_3$ and $\mathrm{CsSnBr}_3$, which exhibit a ferroelectric distortion driven by stereochemical expression of the tin lone pair. We also predict similar metastable ferroelectric phases of $\mathrm{CsPbI}_3$ and $\mathrm{CsPbBr}_3$. In addition to ferroelectricity, these phases exhibit the Rashba effect. Spin splitting in both the conduction and valence bands suggests that nanostructures based on these phases could host bright ground-state excitons. Finally, we discuss paths toward experimental realization of these phases via electric fields and tensile strain.

9.Surface Circular Photogalvanic Effect in Tl-Pb Monolayer Alloys on Si(111) with Giant Rashba Splitting

Authors:Ibuki Taniuchi, Ryota Akiyama, Rei Hobara, Shuji Hasegawa

Abstract: We have found that surface superstructures made of "monolayer alloys" of Tl and Pb on Si(111), having giant Rashba effect, produce non-reciprocal spin-polarized photocurrent via circular photogalvanic effect (CPGE) by obliquely shining circularly polarized near-infrared (IR) light. CPGE is here caused by injection of in-plane spin into spin-split surface-state bands, which is observed only on Tl-Pb alloy layers, but not on single-element Tl nor Pb layers. In the Tl-Pb monolayer alloys, despite their monatomic thickness, the magnitude of CPGE is comparable to or even larger than the cases of many other spin-split thin-film materials. The data analysis has provided the relative permittivity $\epsilon^{\ast}$ of the monolayer alloys to be $\sim$ 1.0, which is because the monolayer exists at a transition region between the vacuum and the substrate. The present result opens the possibility that we can optically manipulate spins of electrons even on monolayer materials.

1.High-throughput screening of Weyl semimetals

Authors:Davide Grassano, Davide Campi, Nicola Marzari

Abstract: Topological Weyl semimetals represent a novel class of non-trivial materials, where band crossings with linear dispersions take place at generic momenta across reciprocal space. These crossings give rise to low-energy properties akin to those of Weyl fermions, and are responsible for several exotic phenomena. Up to this day, only a handful of Weyl semimetals have been discovered, and the search for new ones remains a very active area. The main challenge on the computational side arises from the fact that many of the tools used to identify the topological class of a material do not provide a complete picture in the case of Weyl semimetals. In this work, we propose an alternative and inexpensive, criterion to screen for possible Weyl fermions, based on the analysis of the band structure along high-symmetry directions in the absence of spin-orbit coupling. We test the method by running a high-throughput screening on a set of 5455 inorganic bulk materials and identify 49 possible candidates for topological properties. A further analysis, carried out by identifying and characterizing the crossings in the Brillouin zone, shows us that 3 of these candidates are Weyl semimetals. Interestingly, while these 3 materials underwent other high-throughput screenings, none had revealed their topological behavior before.

2.First principles theory of the nitrogen interstitial in hBN: a plausible model for the blue emitter

Authors:Ádám Ganyecz, Rohit Babar, Zsolt Benedek, Igor Aharonovich, Gergely Barcza, Viktor Ivády

Abstract: Color centers in hexagonal boron nitride (hBN) have attracted considerable attention due to their remarkable optical properties enabling robust room temperature photonics and quantum optics applications in the visible spectral range. On the other hand, identification of the microscopic origin of color centers in hBN has turned out to be a great challenge that hinders in-depth theoretical characterization, on-demand fabrication, and development of integrated photonic devices. This is also true for the blue emitter, which is an irradiation damage in hBN emitting at 436 nm wavelengths with desirable properties. Here, we propose the negatively charged nitrogen split interstitial defect in hBN as a plausible microscopic model for the blue emitter. To this end, we carry out a comprehensive first principles theoretical study of the nitrogen interstitial. We carefully analyze the accuracy of first principles methods and show that the commonly used HSE hybrid exchange-correlation functional fails to describe the electronic structure of this defect. Using the generalized Koopman's theorem, we fine tune the functional and obtain a zero-phonon photoluminescence (ZPL) energy in the blue spectral range. We show that the defect exhibits high emission rate in the ZPL line and features a characteristic phonon side band that resembles the blue emitter's spectrum. Furthermore, we study the electric field dependence of the ZPL and numerically show that the defect exhibits a quadratic Stark shift for perpendicular to plane electric fields, making the emitter insensitive to electric field fluctuations in first order. Our work emphasize the need for assessing the accuracy of common first principles methods in hBN and exemplifies a workaround methodology. Furthermore, our work is a step towards understanding the structure of the blue emitter and utilizing it in photonics applications.

3.Brownian electric bubble quasiparticles

Authors:Hugo Aramberri, Jorge Íñiguez

Abstract: Recent works on electric bubbles (including the experimental demonstration of electric skyrmions) constitute a breakthrough akin to the discovery of magnetic skyrmions some 15 years ago. So far research has focused on obtaining and visualizing these objects, which often appear to be immobile (pinned) in experiments. Thus, critical aspects of magnetic skyrmions - e.g., their quasiparticle nature, Brownian motion - remain unexplored (unproven) for electric bubbles. Here we use predictive atomistic simulations to investigate the basic dynamical properties of these objects in pinning-free model systems. We show that it is possible to find regimes where the electric bubbles can present long lifetimes ($\sim$ ns) despite being relatively small ($\varnothing <$ 2 nm). Additionally, we find that they can display stochastic dynamics with large and highly tunable diffusion constants. We thus establish the quasiparticle nature of electric bubbles and put them forward for the physical effects and applications (e.g., in token-based Probabilistic Computing) considered for magnetic skyrmions.

4.Magnetic interactions in IV-VI diluted magnetic semiconductors

Authors:M. Górska, Ł. Kilański, A. Łusakowski

Abstract: Diluted magnetic semiconductors (DMS) are interesting because of the interplay between the electronic and magnetic subsystems. We describe selected magnetic properties of IV-VI diluted magnetic semiconductors, looking at the similarities and differences between magnetic properties of II-VI, IV-VI, and III-V DMS. We focus on the influence of the crystalline and electronic structure of the material on its magnetic properties, especially on the exchange interactions among magnetic ions. We describe methods of determination of the exchange parameters by using different experimental techniques, such as measurements of magnetic susceptibility, magnetization, and specific heat. We follow the development in the material technology from bulk crystals to thin films and nanostructures.

5.Unique properties of the optical activity in noncentrosymmetric superconductors: sum rule, missing area, and relation with the superconducting Edelstein effect

Authors:Koki Shinada, Robert Peters

Abstract: We present general properties of the optical activity in noncentrosymmetric materials, including superconductors. We derive a sum rule of the optical activity in general electric states and show that the summation of the spectrum is zero, which is independent of the details of electric states. The optical activity has a $\delta$-function singularity that vanishes in normal phases. However, the singularity emerges in superconducting phases, corresponding to the Meissner effect in the optical conductivity. The spectrum decreases by the superconducting gap and has a missing area compared to the normal phase. This area is exactly equivalent to the coefficient of the $\delta$-function singularity due to the universal sum rule. Furthermore, the coefficient is exactly equivalent to the superconducting Edelstein effect, which has not yet been observed in experiments. Thus, this measurement of the missing area offers an alternative way to observe the superconducting Edelstein effect.

1.Reduced-Order Model to Predict Thermal Conductivity of Dimensionally-Confined Materials

Authors:S. Aria Hosseini, Alex Greaney, Giuseppe Romano

Abstract: Predicting nanoscale thermal transport in dielectrics requires models, such as the Boltzmann transport equation (BTE), that account for phonon boundary scattering in structures with complex geometries. Although the BTE has been validated against several key experiments, its computational expense limits its applicability. Here, we demonstrate the use of an analytic reduced-order model for predicting the thermal conductivity in dimensionally confined materials, i.e., monolithic and porous thin films, and rectangular and cylindrical nanowires. The approach uses the recently developed "Ballistic Correction Model" (BCM) which accounts for materials' full distribution of phonon mean-free-paths. The model is validated against BTE simulations for a selection of base materials, obtaining excellent agreement. By furnishing a precise yet easy-to-use prediction of thermal transport in nanostructures, our work strives to accelerate the identification of materials for energy-conversion and thermal-management applications.

2.Broken Screw Rotational Symmetry in the Near-Surface Electronic Structure of $AB$-Stacked Crystals

Authors:Hiroaki Tanaka, Shota Okazaki, Masaru Kobayashi, Yuto Fukushima, Yosuke Arai, Takushi Iimori, Mikk Lippmaa, Kohei Yamagami, Yoshinori Kotani, Fumio Komori, Kenta Kuroda, Takao Sasagawa, Takeshi Kondo

Abstract: We investigate the electronic structure of $2H$-$\mathrm{Nb}\mathrm{S}_2$ and $h$$\mathrm{BN}$ by angle-resolved photoemission spectroscopy (ARPES) and photoemission intensity calculations. Although in bulk form, these materials are expected to exhibit band degeneracy in the $k_z=\pi/c$ plane due to screw rotation and time-reversal symmetries, we observe gapped band dispersion near the surface. We extract from first-principles calculations the near-surface electronic structure probed by ARPES and find that the calculated photoemission spectra from the near-surface region reproduce the gapped ARPES spectra. Our results show that the near-surface electronic structure can be qualitatively different from the bulk one due to partially broken nonsymmorphic symmetries.

3.Influence of band occupation on electron-phonon coupling in gold

Authors:Tobias Held, Sebastian T. Weber, Baerbel Rethfeld

Abstract: Electron-phonon coupling is a fundamental process that governs the energy relaxation dynamics of solids excited by ultrafast laser pulses. It has been found to strongly depend on electron temperature as well as on nonequilibrium effects. Recently, the effect of occupational nonequilibrium in noble metals, which outlasts the fully kinetic stage, has come into increased focus. In this work, we investigate the influence of nonequilibrium density distributions in gold on the electron-phonon coupling. We find a large effect on the coupling parameter which describes the energy exchange between the two subsystems. Our results challenge the conventional view that electron temperature alone is a sufficient predictor of electron-phonon coupling.

4.Optical, magneto-optical properties and fiber-drawing ability of tellurite glasses in the TeO2-ZnO-BaO ternary system

Authors:J. Hrabovsky, L. Strizik, F. Desevedavy, S. Tazlaru, M. Kucera, L. Nowak, R. Krystufek, J. Mistrik, V. Dedic, V. Kopecky Jr., G. Gadret, T. Wagner, F. Smektala, M. Veis

Abstract: The presented work is focused on the optical and magneto-optical characterization of TeO2-ZnO-BaO (TZB) tellurite glasses. We investigated the refractive index and extinction coefficient dispersion by spectroscopic ellipsometry from ultraviolet, 0.193 um, up to mid infrared, 25 um spectral region. Studied glasses exhibited large values of linear (n632 = 1.91-2.09) and non-linear refractive index (n2 = 1.20-2.67x10-11 esu), Verdet constant (V632 = 22-33 radT-1m-1) and optical band gap energy (Eg = 3.7-4.1 eV). The materials characterization revealed that BaO substitution by ZnO leads (at constant content of TeO2) to an increase in linear and nonlinear refractive index as well as Verdet constant while the optical band gap energy decreases. Fiber drawing ability of TeO2-ZnO-BaO glassy system has been demonstrated on 60TeO2-20ZnO-20BaO glass with presented mid infrared attenuation coefficient. Specific parameters such as dispersion and single oscillator energy, Abbe number, and first-/ third-order optical susceptibility are enclosed together with the values of magneto-optic anomaly derived from the calculation of measured dispersion of the refractive index.

5.Cruciform specimens biaxial extension performance relationship to constitutive identification

Authors:Gennaro Vitucci

Abstract: Main desired features of biaxial tests are: uniformity of stresses and strains; high strain levels in gauge areas; reliable constitutive parameters identification. Despite cruciform specimen suitability to modern tensile devices, standard testing techniques are still debated because of difficulties in matching these demands. This work aims at providing rational performance objectives and efficient cruciform specimens shapes in view of constitutive parameter fitting. Objective performance is evaluated along particular lines lying on principal directions in equibiaxial tensile tests. A rich specimen profile geometry is purposely optimized in silico by varying cost function and material compressibility. Experimental tests, monitored via digital image correlation, are carried out for validation. New shapes are designed and tested in a biaxial tensile apparatus and show to perform better than existing ones. Parameter fitting is efficiently performed by only exploiting full field strain measurements along lines. Small gauge areas and small fillet radii cruciform specimens get closer to the ideal behavior. For constitutive parameters identification in two-dimensional tensile experiments, data analysis on gauge lines deformation suffices.

6.Machine learned Force-Fields for an ab-initio Quality Description of Metal-Organic Frameworks

Authors:Sandro Wieser, Egbert Zojer

Abstract: Metal-organic frameworks (MOFs) are an incredibly diverse group of highly porous hybrid materials, which are interesting for a wide range of possible applications. For a reliable description of many of their properties accurate computationally highly efficient methods, like force-field potentials (FFPs), are required. With the advent of machine learning approaches, it is now possible to generate such potentials with relatively little human effort. Here, we present a recipe to parametrize two fundamentally different types of exceptionally accurate and computationally highly efficient machine learned potentials, which belong to the moment-tensor and kernel-based potential families. They are parametrized relying on reference configurations generated in the course of molecular dynamics based, active learning runs and their performance is benchmarked for a representative selection of commonly studied MOFs. For both potentials, comparison to a random set of validation structures reveals close to DFT precision in predicted forces and structural parameters of all MOFs. Essentially the same applies to elastic constants and phonon band structures. Additionally, for MOF-5 the thermal conductivity is obtained with full quantitative agreement to single-crystal experiments. All this is possible while maintaining a high degree of computational efficiency, with the obtained machine learned potentials being only moderately slower than the extremely simple UFF4MOF or Dreiding force fields. The exceptional accuracy of the presented FFPs combined with their computational efficiency has the potential of lifting the computational modelling of MOFs to the next level.

1.Crystallization Dynamics of Amorphous Yttrium Iron Garnet Thin Films

Authors:S. Sailler, G. Skobjin, H. Schlörb, B. Boehm, O. Hellwig, A. Thomas, S. T. B. Goennenwein, M. Lammel

Abstract: Yttrium iron garnet (YIG) is a prototypical material in spintronics due to its exceptional magnetic properties. To exploit these properties high quality thin films need to be manufactured. Deposition techniques like sputter deposition or pulsed laser deposition at ambient temperature produce amorphous films, which need a post annealing step to induce crystallization. However, not much is known about the exact dynamics of the formation of crystalline YIG out of the amorphous phase. Here, we conduct extensive time and temperature series to study the crystallization behavior of YIG on various substrates and extract the crystallization velocities as well as the activation energies needed to promote crystallization. We find that the type of crystallization as well as the crystallization velocity depend on the lattice mismatch to the substrate. We compare the crystallization parameters found in literature with our results and find an excellent agreement with our model. Our results allow us to determine the time needed for the formation of a fully crystalline film of arbitrary thickness for any temperature.

2.Density functional theory study on effect of NO annealing for SiC(0001) surface with atomic-scale steps

Authors:Mitsuharu Uemoto, Nahoto Funaki, Kazuma Yokota, Takuji Hosoi, Tomoya Ono

Abstract: Density functional theory calculations for the electronic structures of the 4H-SiC(0001)/SiO$_2$ interface with atomic-scale steps are carried out to investigate the effect of NO annealing. The characteristic behavior of the conduction band edge states of SiC is strongly affected over a wide area of the interface by the Coulomb interaction of the O atoms in the SiO$_2$ region as well as the step structure of the interface, resulting in the discontinuity of the inversion layers at the step edges under the gate bias. The spatially discontinued band only allows the very limited conduction paths in the inversion layer, leading to the significantly decreased mobile carrier density. It is found that the Coulomb interaction of the O atoms is screened and the inversion layers become continuous when the nitrided layers are inserted at the interface by NO annealing. This result is in good agreement with experimental findings that the improvement of the performance of SiC metal-oxide-semiconductor field-effect-transistors by NO annealing is attributed to an increase in the mobile electron density rather than an increase in the mobility of electrons in the inversion layer.

3.Ab-initio Study of Electronic and Lattice Dynamical Properties of monolayer ZnO under Strain

Authors:Saumen Chaudhuri, A. K. Das, G. P. Das, B. N. Dev

Abstract: First-principles density functional theory based calculations have been performed to investigate the strain-induced modifications in the electronic and vibrational properties of monolayer (ML) ZnO. Wide range of in-plane tensile and compressive strains along different directions are applied to analyse the modifications in detail. The electronic band gap reduces under both tensile and compressive strains and a direct to indirect band gap transition occurs for high values of biaxial tensile strain. The relatively low rate of decrease of band gap and large required strain for direct to indirect band gap transition compared to other $2$D materials are analysed. Systematic decrease in the frequency of the in-plane and increase in the out-of-plane optical phonon modes with increasing tensile strain are observed. The in-plane acoustic modes show linear dispersion for unstrained as well as strained cases. However, the out-of-plane acoustic mode (ZA), which shows quadratic dispersion in the unstrained condition, turns linear with strain. The dispersion of the ZA mode is analysed using the shell elasticity theory and the possibility of ripple formation with strain is analysed. The strain-induced linearity of the ZA mode indicates the absence of rippling under strain. Finally, the stability limit of ML-ZnO is investigated and found that for $18\%$ biaxial tensile strain the structure shows instability with the emergence of imaginary phonon modes. Furthermore, the potential of ML-ZnO to be a good thermoelectric material is analyzed in an intuitive way based on the calculated electronic and phononic properties. Our results, thus, not only highlight the significance of strain-engineering in tailoring the electronic and vibrational properties but also provide a thorough understanding of the lattice dynamics and mechanical strength of ML-ZnO.

4.Hydrostatic Pressure Induced Anomalous Enhancement in the Thermoelectric Performance of Monolayer MoS$_{2}$

Authors:Saumen Chaudhuri, Amrita Bhattacharya, A. K. Das, G. P. Das, B. N. Dev

Abstract: The hydrostatic pressure induced changes in the transport properties of monolayer (ML) MoS$_2$ have been investigated using first-principles density functional theory based calculations. The application of pressure induces shift in the conduction band minimum (CBM) from K to $\Lambda$, while retaining the band extrema at K in around the same energy at a pressure of 10 GPa. This increase in valley degeneracy is found to have a significant impact on the electronic transport properties of ML-MoS$_2$ via enhancement of the thermopower (S) by up to 140\% and power factor (S$^{2}$$\sigma$/$\tau$) by up to 310\% at 300 K. Besides, the very low deformation potential (E$_\text{DP}$) associated with the CB-$\Lambda$ valley results in a remarkably high electronic mobility ($\mu$) and relaxation time ($\tau$). Additionally, the application of pressure reduces the room temperature lattice thermal conductivity ($\kappa_\text{L}$) by 20\% of its unstrained value, owing to the increased anharmonicity and resulting increase in the intrinsic phonon scattering rates. The hydrostatic pressure induced increase in power factor (S$^{2}$$\sigma$) and the decrease in $\kappa_\text{L}$ act in unison to result in a substantial improvement in the overall thermoelectric performance (zT) of ML-MoS$_2$. At 900 K with an external pressure of 25 GPa, zT values of 1.63 and 1.21 are obtained for electron and hole doping, respectively, which are significantly higher compared to the zT values at zero pressure. For the implementation in a thermoelectric module where both n-type and p-type legs should be preferably made of the same material, the concomitant increase in zT of ML-MoS$_2$ for both types of doping with hydrostatic pressure can be highly beneficial.

5.Understanding the local structure, magnetism and optical properties in layered compounds with d9 ions: Insight into silver fluorides and K2CuF4

Authors:Inés Sánchez-Movellán, Guillermo Santamaría-Fernández, Pablo García-Fernández, José Antonio Aramburu, Miguel Moreno

Abstract: Using first-principles DFT calculations, we analyze the origin of the different crystal structures, optical and magnetic properties of two basic families of layered fluoride materials with formula A2MF4 (M = Ag, Cu, Ni, Mn; A = K, Cs, Rb). On one hand, Cs2AgF4 and K2CuF4 compounds (both with d9 metal cations) crystallize in an orthorhombic structure with Cmca space group and MA - F - MB bridge angle of 180, and they exhibit a weak ferromagnetism (FM) in the layer plane. On the other hand, K2NiF4 or K2MnF4 compounds (with d8 and d5 metal cations, respectively) have a tetragonal I4/mmm space group with 180 bridge angle and exhibit antiferromagnetism (AFM) in the layer plane. Firstly, we show that, contrary to what is claimed in the literature, the Cmca structure of Cs2AgF4 and K2CuF4 is not related to a cooperative Jahn-Teller effect among elongated MF64- units. Instead, first-principles calculations carried out in the I4/mmm parent phase of these two compounds show that MF64- units are axially compressed because the electrostatic potential from the rest of lattice ions force the hole to lie in the 3z2 - r2 molecular orbital (z being perpendicular to the layer plane). This fact increases the metal-ligand distance in the layer plane and makes that covalency in the bridging ligand has a residual character (clearly smaller than in K2NiF4 or KNiF3) stabilizing for only a few meV (7.9 meV for Cs2AgF4) an AFM order. However, this I4/mmm parent phase of Cs2AgF4 is unstable thus evolving towards the experimental Cmca structure with an energy gain of 140 meV, FM ordering and orthorhombic MF64- units.

6.Electrical detection and nucleation of a magnetic skyrmion in a magnetic tunnel junction observed via operando magnetic microscopy

Authors:by J. Urrestarazu Larrañaga, Naveen Sisodia, Van Tuong Pham, Ilaria Di Manici, Aurélien Masseboeuf, Kevin Garello, Florian Disdier, Bruno Fernandez, Sebastian Wintz, Markus Weigand, Mohamed Belmeguenai, Stefania Pizzini, Ricardo Sousa, Liliana Buda-Prejbeanu, Gilles Gaudin, Olivier Boulle

Abstract: Magnetic skyrmions are topological spin textures which are envisioned as nanometre scale information carriers in magnetic memory and logic devices. The recent demonstration of room temperature stabilization of skyrmions and their current induced manipulation in industry compatible ultrathin films were first steps towards the realisation of such devices. However, important challenges remain regarding the electrical detection and the low-power nucleation of skyrmions, which are required for the read and write operations. Here, we demonstrate, using operando magnetic microscopy experiments, the electrical detection of a single magnetic skyrmion in a magnetic tunnel junction (MTJ) and its nucleation and annihilation by gate voltage via voltage control of magnetic anisotropy. The nucleated skyrmion can be further manipulated by both gate voltage and external magnetic field, leading to tunable intermediate resistance states. Our results unambiguously demonstrate the readout and voltage controlled write operations in a single MTJ device, which is a major milestone for low power skyrmion based technologies.

7.Discovery of Stable Hybrid Organic-inorganic Double Perovskites for High-performance Solar Cells via Machine-learning Algorithms and Crystal Graph Convolution Neural Network Method

Authors:Linkang Zhan, Danfeng Ye, Xinjian Qiu, Yan Cen

Abstract: Hybrid peroskite solar cells are newly emergent high-performance photovoltaic devices, which suffer from disadvantages such as toxic elements, short-term stabilities, and so on. Searching for alternative perovskites with high photovoltaic performances and thermally stabilities is urgent in this field. In this work, stimulated by the recently proposed materials-genome initiative project, firstly we build classical machine-learning algorithms for the models of formation energies, bangdaps and Deybe temperatures for hybrid organic-inorganic double perovskites, then we choose the high-precision models to screen a large scale of double-perovskite chemical space, to filter out good pervoskite candidates for solar cells. We also analyze features of importances for the the three target properties to reveal the underlying mechanisms and discover the typical characteristics of high-performances double perovskites. Secondly we adopt the Crystal graph convolution neural network (CGCNN), to build precise model for bandgaps of perovskites for further filtering. Finally we use the ab-initio method to verify the results predicted by the CGCNN method, and find that, six out of twenty randomly chosen (CH3)2NH2-based HOIDP candidates possess finite bandgaps, and especially, (CH3)2NH2AuSbCl6 and (CH3)2NH2CsPdF6 possess the bandgaps of 0.633 eV and 0.504 eV, which are appropriate for photovoltaic applications. Our work not only provides a large scale of potential high-performance double-perovskite candidates for futural experimental or theoretical verification, but also showcases the effective and powerful prediction of the combined ML and CGCNN method proposed for the first time here.

8.Influence of Hydration and Dehydration on the Viscoelastic Properties of Snail Mucus by Brillouin Spectroscopy

Authors:Dillon F. Hanlon, Maynard J. Clouter, G. Todd Andrews

Abstract: Brillouin spectroscopy was used to probe the viscoelastic properties of diluted snail mucus at GHz frequencies over the range -11 $^\circ$C $\leq T \leq$ 52 $^\circ$C and of dehydrated mucus as a function of time. Two peaks were observed in the spectra for diluted mucus: the longitudinal acoustic mode of the liquid mucus peak varies with dilution but fluctuates around the typical value of 8.0 GHz. A second peak due to ice remained unchanged with varying dilution and was seen at 18.0 GHz and appeared below the dilutions "freezing" point depression. Only a single peak was found in all the dehydrated mucus spectra and was also attributed to the longitudinal acoustic mode of liquid mucus. Anomalous changes in the protein concentration dependence of the frequency shift, linewidth, and ``freezing" point depression and consequently, hypersound velocity, compressibility, and apparent viscosity suggest that the viscoelastic properties of this system is influenced by the presence of water. Furthermore, this research uncovered three unique transitions within the molecular structure. These transitions included the first stage of glycoprotein cross-linking, followed by the steady depletion of free water in the system, and eventually resulted in the creation of a gel-like state when all remaining free water was evaporated.

9.Machine learning density functionals from the random-phase approximation

Authors:Stefan Riemelmoser, Carla Verdi, Merzuk Kaltak, Georg Kresse

Abstract: Kohn-Sham density functional theory (DFT) is the standard method for first-principles calculations in computational chemistry and materials science. More accurate theories such as the random-phase approximation (RPA) are limited in application due to their large computational cost. Here, we construct a DFT substitute functional for the RPA using supervised and unsupervised machine learning (ML) techniques. Our ML-RPA model can be interpreted as a non-local extension to the standard gradient approximation. We train an ML-RPA functional for diamond surfaces and liquid water and show that ML-RPA can outperform the standard gradient functionals in terms of accuracy. Our work demonstrates how ML-RPA can extend the applicability of the RPA to larger system sizes, time scales and chemical spaces.

10.On the vibrational properties of transition metal doped ZnO: surface, defect, and bandgap engineering

Authors:Viviane M. A. Lage, Carlos Rodríguez-Fernández, Felipe S. Vieira, Rafael T. da Silva, Maria Inês B. Bernardi, Maurício M de Lima Jr., Andrés Cantarero, Hugo B. de Carvalho

Abstract: We present a comprehensive study on the structure and optical properties of Mn-and Co-doped ZnO samples prepared via solid-state reaction method with different dopant concentrations and atmospheres. The samples were structural and chemically characterized via X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray excited photoelectron spectroscopy. The optical characterization was performed via Raman, photoluminescence, and diffuse photoreflectance spectroscopies. Emphasis was done on the studies of their vibrational properties. The structural data confirm the incorporation of Mn and Co ions into the wurtzite ZnO lattice. It is demonstrated that the usual observed additional bands in the Raman spectrum of transitional metal (TM) doped ZnO are related to structural damage, deriving from the doping process, and surface effects. The promoted surface optical phonons (SOP) are of Fr\"ohlich character and, together with the longitudinal optical (LO) polar phonons, are directly dependent on the ZnO electronic structure. The enhancement of SOP and LO modes with TM-doping is explained in terms of nonhomogeneous doping, with the dopants concentrating mainly on the surface of grains, and a resonance effect due to the decrease of the ZnO bandgap promoted by the introduction of the 3d TM levels within the ZnO bandgap. We also discuss the origin of the controversial vibrational mode commonly observed in the Mn-doped ZnO system. It is stated that the observation of the analyzed vibrational properties is a signature of substitutional doping of the ZnO structure with tuning of ZnO optical absorption into the visible range of the electromagnetic spectrum.

1.Ballistic spin-transport properties of magnetic tunnel junctions with MnCr-based ferrimagnetic quaternary Heusler alloys

Authors:Tufan Roy, Masahito Tsujikawa, Masafumi Shirai

Abstract: We investigate the suitability of nearly half-metallic ferrimagnetic quaternary Heusler alloys, CoCrMnZ (Z=Al, Ga, Si, Ge) to assess the feasibility as electrode materials of MgO-based magnetic tunnel junctions (MTJ). Low magnetic moments of these alloys originated from the anti-ferromagnetic coupling between Mn and Cr spins ensure a negligible stray field in spintronics devices as well as a lower switching current required to flip their spin direction. We confirmed mechanical stability of these materials from the evaluated values of elastic constants, and the absence of any imaginary frequency in their phonon dispersion curves. The influence of swapping disorders on the electronic structures and their relative stability are also discussed. A high spin polarization of the conduction electrons are observed in case of CoCrMnZ/MgO hetrojunctions, independent of terminations at the interface. Based on our ballistic transport calculations, a large coherent tunnelling of the majority-spin $s$-like $\Delta_1$ states can be expected through MgO-barrier. The calculated tunnelling magnetoresistance (TMR) ratios are in the order of 1000\%. A very high Curie temperatures specifically for CoCrMnAl and CoCrMnGa, which are comparable to $bcc$ Co, could also yield a weaker temperature dependece of TMR ratios for CoCrMnAl/MgO/CoCrMnAl (001) and CoCrMnGa/MgO/CoCrMnGa (001) MTJ.

2.Erbium-based multifuncional compounds as molecular microkelvin-tunable driving-sensing units

Authors:Jarosław Rybusiński, Tomasz Fąs, Pablo Martin-Ramos, Victor Lavín, Jacek Szczytko, Jan Suffczyński, Inocencio R. Martín, Jesus Martin-Gil, Manuela Ramos Silva, Bruno Cury Camargo

Abstract: We demonstrate the selective control of the magnetic response and photoluminescence properties of Er3+ centers with light, by associating them with a highly conjugated beta-diketonate (1,3-di(2-naphthyl)-1,3-propanedione) ligand. We demonstrate this system to be an optically-pumped molecular compound emittingin infra-red, which can be employed as a precise heat-driving and detecting unit for low temperatures

3.Ferroelectricity in tetragonal ZrO$_2$ thin films

Authors:Ali El Boutaybi, Thomas Maroutian, Ludovic Largeau, Nathaniel Findling, Jean-Blaise Brubach, Rebecca Cervasio, Alban Degezelle, Sylvia Matzen, Laurent Vivien, Pascale Roy, Panagiotis Karamanis, Michel Rérat, Philippe Lecoeur

Abstract: We report on the crystal structure and ferroelectric properties of epitaxial ZrO$_2$ films ranging from 7 to 42 nm thickness grown on La$_{0.67}$Sr$_{0.33}$MnO$_3$-buffered (110)-oriented SrTiO$_3$ substrate. By employing X-ray diffraction, we confirm a tetragonal phase at all investigated thicknesses, with slight in-plane strain due to the substrate in the thinnest films. Further confirmation of the tetragonal phase was obtained through Infrared absorption spectroscopy with synchrotron light, performed on ZrO$_2$ membrane transferred onto a high resistive Silicon substrate. Up to a thickness of 31 nm, the ZrO$_2$ epitaxial films exhibit ferroelectric behavior, at variance with the antiferroelectric behavior reported previously for the tetragonal phase in polycrystalline films. However, the ferroelectricity is found here to diminish with increasing film thickness, with a polarization of about 13 $\mu$$^{-2}$ and down to 1 $\mu$$^{-2}$ for 7 nm and 31 nm-thick ZrO$_2$ films, respectively. This highlights the role of thickness reduction, substrate strain, and surface effects in promoting polarization in the tetragonal ZrO$_2$ thin films. These findings provide new insights into the ferroelectric properties and structure of ZrO$_2$ thin films, and open up new directions to investigate the origin of ferroelectricity in ZrO$_2$ and to optimize this material for future applications.

4.On-surface synthesis and characterization of Teranthene and Hexanthene: Ultrashort graphene nanoribbons with mixed armchair and zigzag edges

Authors:Gabriela Borin Barin, Marco Di Giovannantonio, Thorsten G. Lohr, Shantanu Mishra, Amogh Kinikar, Mickael L. Perrin, Jan Overbeck, Michel Calame, Xinliang Feng, Roman Fasel, Pascal Ruffieux

Abstract: Graphene nanoribbons (GNRs) exhibit a broad range of physicochemical properties that critically depend on their width and edge topology. While the chemically stable GNRs with armchair edges (AGNRs) are semiconductors with width-tunable band gap, GNRs with zigzag edges (ZGNRs) host spin-polarized edge states, which renders them interesting for applications in spintronic and quantum technologies. However, these states significantly increase their reactivity. For GNRs fabricated via on-surface synthesis under ultrahigh vacuum conditions on metal substrates, the expected reactivity of zigzag edges is a serious concern in view of substrate transfer and device integration under ambient conditions, but corresponding investigations are scarce. Using 10-bromo-9,9':10',9''-teranthracene as a precursor, we have thus synthesized hexanthene (HA) and teranthene (TA) as model compounds for ultrashort GNRs with mixed armchair and zigzag edges, characterized their chemical and electronic structure by means of scanning probe methods, and studied their chemical reactivity upon air exposure by Raman spectroscopy. We present a detailed identification of molecular orbitals and vibrational modes, assign their origin to armchair or zigzag edges, and discuss the chemical reactivity of these edges based on characteristic Raman spectral features.

5.Which Ion Dominates Temperature and Pressure Response of Halide Perovskites and Elpasolites?

Authors:Loreta A. Muscarella, Huygen J. Jöbsis, Bettina Baumgartner, P. Tim Prins, D. Nicolette Maaskant, Andrei V. Petukhov, Dmitry Chernyshov, Charles J. McMonagle, Eline M. Hutter

Abstract: Halide perovskite and elpasolite semiconductors are extensively studied for optoelectronic applications due to their excellent performance together with significant chemical and structural flexibility. However, there is still limited understanding of their basic elastic properties and how they vary with composition and temperature, which is relevant for synthesis and device operation. To address this, we performed temperature- and pressure-dependent synchrotron-based powder X-ray diffraction (XRD). In contrast to previous pressure-dependent XRD studies, our relatively low pressures (ambient to 0.06 GPa) enabled us to investigate the elastic properties of halide perovskites and elpasolites in their ambient crystal structure. We find that halide perovskites and elpasolites show common trends in the bulk modulus and thermal expansivity. Both materials become softer as the halide ionic radius increases from Cl to Br to I, exhibiting higher compressibility and larger thermal expansivity. The mixed-halide compositions show intermediate properties to the pure compounds. Contrary, cations show a minor effect on the elastic properties. Finally, we observe that thermal phase transitions in e.g., MAPbI3 and CsPbCl3 lead to a softening of the lattice, together with negative expansivity for certain crystal axes, already tens of degrees away from the transition temperature. Hence, the range in which the phase transition affects thermal and elastic properties is substantially broader than previously thought. These findings highlight the importance of considering the temperature-dependent elastic properties of these materials, since stress induced during manufacturing or temperature sweeps can significantly impact the stability and performance of the corresponding devices.

6.Reliable Synthesis of Large-Area Monolayer WS2 Single Crystals, Films, and Heterostructures with Extraordinary Photoluminescence Induced by Water Intercalation

Authors:Qianhui Zhang, Jianfeng Lu, Ziyu Wang, Zhigao Dai, Yupeng Zhang, Fuzhi Huang, Qiaoliang Bao, Wenhui Duan, Michael S. Fuhrer, Changxi Zheng

Abstract: Two-dimensional (2D) transition metal dichalcogenides (TMDs) hold great potential for future low-energy optoelectronics owing to their unique electronic, optical, and mechanical properties. Chemical vapor deposition (CVD) is the technique widely used for the synthesis of large-area TMDs. However, due to high sensitivity to the growth environment, reliable synthesis of monolayer TMDs via CVD remains challenging. Here we develop a controllable CVD process for large-area synthesis of monolayer WS2 crystals, films, and in-plane graphene-WS2 heterostructures by cleaning the reaction tube with hydrochloric acid, sulfuric acid and aqua regia. The concise cleaning process can remove the residual contaminates attached to the CVD reaction tube and crucibles, reducing the nucleation density but enhancing the diffusion length of WS2 species. The photoluminescence (PL) mappings of a WS2 single crystal and film reveal that the extraordinary PL around the edges of a triangular single crystal is induced by ambient water intercalation at the WS2-sapphire interface. The extraordinary PL can be controlled by the choice of substrates with different wettabilities.

7.A Continuum Theory of Elastic-Ferromagnetic Conductors

Authors:Jiashi Yang

Abstract: In this paper, a phenomenological theory of saturated ferromagnetoelastic conductors is established using a multi-continuum model and the classical laws of mechanics, thermodynamics and electromagnetics. The theory is nonlinear and is valid for large deformations and strong electromagnetic fields. The constitutive relations in the theory satisfy the saturation condition of the magnetization vector. The theory is with full electromagnetic couplings as governed by the equations of electrodynamics. It can describe the interactions of elastic, electromagnetic and spin waves. The theory can be reduced to various quasistatic theories with appropriate approximations of the electromagnetic fields. It is for anisotropic materials in general.

8.Femtomolar detection of the heart failure biomarker NT-proBNP in artificial saliva using an immersible liquid-gated aptasensor with reduced graphene oxide

Authors:Stefan Jaric, Anastasiia Kudriavtseva, Nikita Nekrasov, Alexey V. Orlov, Ivan A. Komarov, Leonty A. Barsukov, Ivana Gadjanski, Petr I. Nikitin, Ivan Bobrinetskiy

Abstract: Measuring NT-proBNP biomarker is recommended for preliminary diagnostics of the heart failure. Recent studies suggest a possibility of early screening of biomarkers in saliva for non-invasive identification of cardiac diseases at the point-of-care. However, NT-proBNP concentrations in saliva can be thousand times lower than in blood plasma, going down to pg/mL level. To reach this level, we developed a label-free aptasensor based on a liquid-gated field effect transistor using a film of reduced graphene oxide monolayer (rGO-FET) with immobilized NT-proBNP specific aptamer. We found that, depending on ionic strength of tested solutions, there were different levels of correlation in responses of electrical parameters of the rGO-FET aptasensor, namely, the Dirac point shift and transconductance change. The correlation in response to NT-proBNP was high for 1.6 mM phosphate-buffered saline (PBS) and zero for 16 mM PBS in a wide range of analyte concentrations, varied from 1 fg/mL to 10 ng/mL. The effect in transconductance and Dirac point shift in PBS solutions of different concentrations are discussed. The biosensor exhibited a high sensitivity for both transconductance (2*10E-6 S/decade) and Dirac point shift (2.3 mV/decade) in diluted PBS with the linear range from 10 fg/ml to 1 pg/ml. The aptasensor performance has been also demonstrated in undiluted artificial saliva with the achieved limit of detection down to 41 fg/mL (~4.6 fM).

9.Towards the mechanism and high performance of solid-state Li batteries

Authors:L. J. Zhang

Abstract: Recently some critical problems and challenges have been exposed, hindering the development and practical application of SSLBs, such as the low room temperature ionic conductivity of solid electrolyte, the risk of short circuit caused by lithium dendrite piercing the electrolyte, etc. In order to address these challenges, it's essential to obtain in-depth insights into mechanisms and systematic optimization of SSLBs, including interfaces, electrolytes, and battery structures. Here, this minireview provides a brief summary, including strategies for electrode and electrolyte preparation, advanced battery characterization techniques, and the latest computational and simulation methods to advance understanding of kinetic or atomic scale mechanisms. The above contents will play an active role in promoting the development and practical application of safer and higher performance SSLBs.

1.NMR study of Ni50+xTi50-x Strain-Glass

Authors:Rui Li, Jacob Santiago, Daniel Salas, Ibrahim Karaman, Joseph H. Ross Jr

Abstract: We studied Ni50+xTi50-x with compositions up to x = 2, performing 47Ti and 49Ti nuclear magnetic resonance (NMR) measurements from 4 K to 400 K. For large x in this system, a strain-glass appears in which frozen ferroelastic nano-domains replace the displacive martensite structural transition. Here we demonstrate that NMR can provide an extremely effective probe of the strain glass freezing process, with large changes in NMR line-shape due to the effects of random strains which become motionally narrowed at high temperatures. At the same time with high-resolution x-ray diffraction we confirm the lack of structural changes in x >= 1.2 samples, while we show that there is little change in the electronic behavior across the strain glass freezing temperature. NMR spin-lattice relaxation time (T1) measurements provide a further measure of the dynamics of the freezing process, and indicate a predominantly thermally activated behavior both above and below the strain-glass freezing temperature. We show that the strain glass results are consistent with a very small density of critically divergent domains undergoing a Vogel-Fulcher-type freezing process, coexisting with domains exhibiting faster dynamics and stronger pinning.

2.Electron-induced non-monotonic pressure dependence of the lattice thermal conductivity of θ-TaN

Authors:Ashis Kundu, Yani Chen, Xiaolong Yang, Fanchen Meng, Jesús Carrete, Mukul Kabir, Georg K. H. Madsen, Wu Li

Abstract: Recent theoretical and experimental research suggests that $\theta$-TaN is a semimetal with high thermal conductivity ($\kappa$), primarily due to the contribution of phonons ($\kappa_\texttt{ph}$). By using first-principles calculations, we show a non-monotonic pressure-dependence of the $\kappa$ of $\theta$-TaN. $\kappa_\texttt{ph}$ first increases until it reaches a maximum at around 60 GPa, and then decreases. This anomalous behaviour is a consequence of the competing pressure responses of phonon-phonon and phonon-electron interactions, in contrast to the other known materials BAs and BP, where the non-monotonic pressure dependence is caused by the interplay between different phonon-phonon scattering channels. Although TaN has similar phonon dispersion features to BAs at ambient pressure, its response to pressure is different and an overall stiffening of the phonon branches takes place. Consequently, the relevant phonon-phonon scattering weakens as pressure increases. However, the increased electronic density of states around the Fermi level significantly enhances phonon-electron scattering at high pressures, driving a decrease in $\kappa_{\mathrm{ph}}$. At intermediate pressures ($\sim$20$-$70 GPa), the $\kappa$ of TaN surpasses that of BAs. Our work provides deeper insight into phonon transport in semimetals and metals where phonon-electron scattering is relevant.

3.Revisiting Néel 60 years on: the magnetic anisotropy of $\mathrm{L}1_0$ FeNi (tetrataenite)

Authors:Christopher D. Woodgate, Christopher E. Patrick, Laura H. Lewis, Julie B. Staunton

Abstract: The magnetocrystalline anisotropy energy of atomically ordered $\mathrm{L}1_0$ FeNi (the meteoritic mineral tetrataenite) is studied within a first-principles electronic structure framework. Two compositions are examined: equiatomic Fe$_{0.5}$Ni$_{0.5}$ and an Fe-rich composition, Fe$_{0.56}$Ni$_{0.44}$. It is confirmed that, for the single crystals modelled in this work, the leading-order anisotropy coefficient $K_1$ dominates the higher-order coefficients $K_2$ and $K_3$. To enable comparison with experiment, the effects of both imperfect atomic long-range order and finite temperature are included. While our computational results initially appear to undershoot the measured experimental values for this system, careful scrutiny of the original analysis due to N\'{e}el et al. [J. Appl. Phys. 35, 873 (1964)] suggests that our computed value of $K_1$ is, in fact, consistent with experimental values, and that the noted discrepancy has its origins in the nanoscale polycrystalline, multivariant nature of experimental samples, that yields much larger values of $K_2$ and $K_3$ than expected a priori. These results provide fresh insight into the existing discrepancies in the literature regarding the value of tetrataenite's uniaxial magnetocrystalline anisotropy in both natural and synthetic samples.

4.Raman Spectroscopy of Monolayer to Bulk PtSe2 Exfoliated Crystals

Authors:Marin Tharrault, Eva Desgué, Dominique Carisetti, Bernard Plaçais, Christophe Voisin, Pierre Legagneux, Emmanuel Baudin

Abstract: Raman spectroscopy is widely used to assess the quality of 2D materials thin films. This report focuses on $\rm{PtSe_2}$, a noble transition metal dichalcogenide which has the remarkable property to transit from a semi-conductor to a semi-metal with increasing layer number. While polycrystalline $\rm{PtSe_2}$ can be grown with various cristalline qualities, getting insight into the monocrystalline intrinsic properties remains challenging. We report on the study of exfoliated 1 to 10 layers $\rm{PtSe_2}$ by Raman spectroscopy, featuring record linewidth. The clear Raman signatures allow layer-thickness identification and provides a reference metrics to assess crystal quality of grown films.

5.Machine Learning Potential for Modelling H$_2$ Adsorption/Diffusion in MOF with Open Metal Sites

Authors:Shanping Liu, Romain Dupuis, Dong Fan, Salma Benzaria, Michael Bonneau, Prashant Bhatt, Mohamed Eddaoudi, Guillaume Maurin

Abstract: Metal-organic frameworks (MOFs) incorporating open metal sites (OMS) have been identified as promising sorbents for many societally relevant-adsorption applications including CO$_2$ capture, natural gas purification and H$_2$ storage. It is critical to derive generic interatomic potential to achieve accurate and effective evaluation of MOFs for H$_2$ adsorption. On this path, as a proof-of-concept, the Al-soc-MOF containing Al-OMS, previously envisaged as a potential candidate for H$_2$ adsorption, was selected and a machine learning potential (MLP) was derived from a dataset initially generated by ab-initio molecular dynamics (AIMD) simulations. This MLP was further implemented in MD simulations to explore the binding modes of H$_2$ as well as its temperature dependence distribution in the MOFs pores from 10K to 90K. MLP-Grand Canonical Monte Carlo (GCMC) simulations were further performed to predict the H$_2$ sorption isotherm of Al-soc-MOF at 77K that was further confirmed by gravimetric sorption measurements. As a further step, MLP-based MD simulations were conducted to anticipate the kinetics of H$_2$ in this MOF. This work delivers the first MLP able to describe accurately the interactions between the challenging H$_2$ guest molecule and MOFs containing OMS. This innovative strategy applied to one of the most complex molecules owing to its highly polarizable nature alongside its quantum-mechanical effects that are only accurately described by quantum calculations, paves the way towards a more systematic accurate and efficient in silico assessment of the MOFs containing OMS for H$_2$ adsorption and beyond to the low-pressure capture/sensing of diverse molecules.

6.A new approach to analyzing the spinor wave functions: Effect of strain on the electronic structure and optical transitions in bulk CdSe

Authors:A. I. Lebedev

Abstract: An approach to analyzing the spinor wave functions that appear in the electronic structure calculations when taking the spin-orbit interaction into account is developed. It is based on the projection analysis of angular parts of wave functions onto irreducible representations of the point group and analysis of the evolution of the energy levels upon the adiabatic turning on the spin-orbit interaction. The technique is illustrated by an example of the changes in the valence band structure in strained bulk CdSe with zinc-blende structure. An analysis of the character of mixing of various branches of the valence band supports the Luttinger-Kohn model of the valence band. It is shown that the above calculations complemented by the Zeeman splitting in a magnetic field make it possible to unambiguously determine the polarization of all optical transitions. Using the spinor wave functions, matrix elements of optical transitions between the valence subbands and the conduction band are calculated.

7.A quantitative phase-field model for void evolution in defect supersaturated environments: a novel introduction of defect reaction asymmetry

Authors:Sreekar Rayaprolu, Kyle Starkey, Anter El-Azab

Abstract: Voids develop in crystalline materials under energetic particle irradiation, as in nuclear reactors. Understanding the underlying mechanisms of void nucleation and growth is of utmost importance as it leads to dimensional instability of the metallic materials. In the past two decades, researchers have adopted the phase-field approach to study the phenomena of void evolution under irradiation. The approach involves modeling the boundary between the void and matrix with a diffused interface. However, none of the existing models are quantitative in nature. This work introduces a thermodynamically consistent, quantitative diffuse interface model based on KKS formalism to describe the void evolution under irradiation. The model concurrently considers both vacancies and self-interstitials in the description of void evolution. Unique to our model is the presence of two mobility parameters in the equation of motion of the phase-field variable. The two mobility parameters relate the driving force for vacancy and self-interstitial interaction to the interface motion, analogous to dislocation motion through climb and glide processes. The asymptotic matching of the phase-field model with the sharp-interface theory fixes the two mobility parameters in terms of the material parameters in the sharp-interface model. The Landau coefficient, which controls the height of the double-well function in the phase field variable, and the gradient coefficient of the phase field variable are fixed based on the interfacial energy and interface width of the boundary. With all the parameters in the model determined in terms of the material parameters, we thus have a new phase field model for void evolution. Simple test cases will show the void evolution under various defect supersaturation to validate our new phase-field model.

8.Theory of reactions between hydrogen and group-III acceptors in silicon

Authors:José Coutinho, Diana Gomes, Vitor J. B. Torres, Tarek O. Abdul Fattah, Vladimir P. Markevich, Anthony R. Peaker

Abstract: The thermodynamics of several reactions involving atomic and molecular hydrogen with group-III acceptors is investigated. The results provide a first-principles-level account of thermally- and carrier-activated processes involving these species. Acceptor-hydrogen pairing is revisited as well. We present a refined physicochemical picture of long-range migration, compensation effects, and short-range reactions, leading to fully passivated $\equiv\textrm{Si-H}\cdots X\equiv$ structures, where $X$ is a group-III acceptor element. The formation and dissociation of acceptor-H and acceptor-H$_{2}$ complexes is considered in the context of Light and elevated Temperature Induced Degradation (LeTID) of silicon-based solar cells. Besides explaining observed trends and answering several fundamental questions regarding the properties of acceptor-hydrogen pairing, we find that the BH$_{2}$ complex is a by-product along the reaction of H$_{2}$ molecules with boron toward the formation of BH pairs (along with subtraction of free holes). The calculated changes in Helmholtz free energies upon the considered defect reactions, as well as activation barriers for BH$_{2}$ formation/dissociation (close to $\sim1$ eV) are compatible with the experimentally determined activation energies of degradation/recovery rates of Si:B-based cells during LeTID. Dihydrogenated acceptors heavier than boron are anticipated to be effective-mass-like shallow donors, and therefore, unlikely to show similar non-radiative recombination activity.

9.Premature jump-down mimicks nonlinear damping in nanoresonators

Authors:Safvan Palathingal, Dominic Vella

Abstract: Recent experiments on nano-resonators in a bistable regime use the `jump-down' point between states to infer mechanical properties of the membrane or a load, but often suggest the presence of some nonlinear damping. Motivated by such experiments, we develop a mechanical model of a membrane subject to a uniform, oscillatory load and linear damping. We solve this model numerically and compare its jump-down behaviour with standard asymptotic predictions for a one-dimensional Duffing oscillator with strain stiffening. We show that the axisymmetric, but spatially-varying, problem can be mapped to the Duffing problem with coefficients determined rationally from the model's Partial Differential Equations. However, we also show that jump-down happens earlier than expected (i.e.~at lower frequency, and with a smaller oscillation amplitude). Although this premature jump-down is often interpreted as the signature of a nonlinear damping in experiments, its appearance in numerical simulations with only linear damping suggests instead that indicate that the limitations of asymptotic results may, at least sometimes, be the cause. We therefore suggest that care should be exercised in interpreting the results of nano-resonator experiments.

1.Influence of cation vacancy concentrations on ultra-low thermal conductivity in $(1-x)$BiVO$_4$-$x$Bi$_{2/3}$MoO$_4$ scheelite solid solutions

Authors:Guillaume F. Nataf GREMAN UMR7347, CNRS, University of Tours, INSA Centre Val de Loire, 37000 Tours, France, Hicham Ait Laasri GREMAN UMR7347, CNRS, University of Tours, INSA Centre Val de Loire, 37000 Tours, France, Damien Brault GREMAN UMR7347, CNRS, University of Tours, INSA Centre Val de Loire, 37000 Tours, France, Tatiana Chartier GREMAN UMR7347, CNRS, University of Tours, INSA Centre Val de Loire, 37000 Tours, France, Chalit Ya GREMAN UMR7347, CNRS, University of Tours, INSA Centre Val de Loire, 37000 Tours, France, Fabian Delorme GREMAN UMR7347, CNRS, University of Tours, INSA Centre Val de Loire, 37000 Tours, France, Isabelle Monot-Laffez GREMAN UMR7347, CNRS, University of Tours, INSA Centre Val de Loire, 37000 Tours, France, Fabien Giovannelli GREMAN UMR7347, CNRS, University of Tours, INSA Centre Val de Loire, 37000 Tours, France

Abstract: Bismuth vanadate - bismuth molybdate solid-solution was prepared to elaborate ceramics with different amounts of cation vacancies. Dense ceramics with similar microstructures were obtained and the evolution of their melting point, specific heat, thermal diffusivity, and conductivity as a function of the amount of vacancy was evaluated. At room temperature, the thermal conductivity decreases from 1.74 W m$^{-1}$ K$^{-1}$ for BiVO$_{4}$ (x=0) to 1.12 W m$^{-1}$ K$^{-1}$ for Bi$_{0.867}$$\square$$_{0.133}$Mo$_{0.4}$V$_{0.6}$O$_{4}$ (x=0.4). Moreover, we show that a very small amount of vacancy (1.7%, x=0.05) is enough to provide a large decrease in thermal conductivity by more than 15%, in agreement with a mass fluctuation scattering model. However, the temperature of the melting point also decreases with increasing amount of vacancy. Our results suggest adding only a very small amount of vacancy as the best strategy to obtain superior materials for thermal barriers and thermoelectric devices, with ultra-low thermal conductivity and high-temperature stability.

2.High-harmonic spectroscopy of strongly bound excitons in solids

Authors:Simon Vendelbo Bylling Jensen, Lars Bojer Madsen, Angel Rubio, Nicolas Tancogne-Dejean

Abstract: We explore the nonlinear response of ultrafast strong-field driven excitons in a one-dimensional solid with ab initio simulations. We demonstrate from our simulations and analytical model that a finite population of excitons imprints unique signatures to the high-harmonic spectra of materials. We show the exciton population can be retrieved from the spectra. We further demonstrate signatures of exciton recombination and that a shift of the exciton level is imprinted into the harmonic signal. The results open the door to high-harmonic spectroscopy of excitons in condensed-matter systems.

3.The rule of four: anomalous stoichiometries of inorganic compounds

Authors:Elena Gazzarrini, Rose K. Cersonsky, Marnik Bercx, Carl S. Adorf, Nicola Marzari

Abstract: Why are materials with specific characteristics more abundant than others? This is a fundamental question in materials science and one that is traditionally difficult to tackle, given the vastness of compositional and configurational space. We highlight here the anomalous abundance of inorganic compounds whose primitive unit cell contains a number of atoms that is a multiple of four. This occurrence - named here the 'rule of four' - has to our knowledge not previously been reported or studied. Here, we first highlight the rule's existence, especially notable when restricting oneself to experimentally known compounds, and explore its possible relationship with established descriptors of crystal structures, from symmetries to energies. We then investigate this relative abundance by looking at structural descriptors, both of global (packing configurations) and local (the smooth overlap of atomic positions) nature. Contrary to intuition, the overabundance does not correlate with low-energy or high-symmetry structures; in fact, structures which obey the 'rule of four' are characterized by low symmetries and loosely packed arrangements maximizing the free volume. We are able to correlate this abundance with local structural symmetries, and visualize the results using a hybrid supervised-unsupervised machine learning method.

4.Understanding magnetoelectric switching in BiFeO$_3$ thin films

Authors:Natalya S. Fedorova, Dmitri E. Nikonov, John M. Mangeri, Hai Li, Ian A. Young, Jorge Íñiguez

Abstract: In this work we use a phenomenological theory of ferroelectric switching in BiFeO$_3$ thin films to uncover the mechanism of the two-step process that leads to the reversal of the weak magnetization of these materials. First, we introduce a realistic model of a BiFeO$_3$ film, including the Landau energy of isolated domains as well as the constraints that account for the presence of the substrate and the multidomain configuration found experimentally. We use this model to obtain statistical information about the switching behavior - by running dynamical simulations based on the Landau-Khalatnikov time-evolution equation, including thermal fluctuations - and we thus identify the factors that drive the two-step polarization reversal observed in the experiments. Additionally, we apply our model to test potential strategies for optimizing the switching characteristics.

5.Super-tetragonal Sr4Al2O7: a versatile sacrificial layer for high-integrity freestanding oxide membranes

Authors:Jinfeng Zhang, Ting Lin, Liang Si, Ao Wang, Qingyu He, Huan Ye, Jingdi Lu, Qing Wang, Zhengguo Liang, Feng Jin, Shengru Chen, Minghui Fan, Er-Jia Guo, Qinghua Zhang, Lin Gu, Zhenlin Luo, Wenbin Wu, Lingfei Wang

Abstract: Identifying a suitable water-soluble sacrificial layer is crucial to fabricating large-scale freestanding oxide membranes, which stimulates intriguing functionalities and enables novel integrations with semiconductor technologies. In this work, we introduce a new water-soluble sacrificial layer, "super-tetragonal" Sr4Al2O7 (SAOT). Its unique atomic structure ensures a coherent growth of perovskite ABO3/SAOT heterostructures, effectively inhibiting crack formation in the water-released membranes. For various non-ferroelectric oxide membranes with lattice constants ranging from 3.85 to 4.04 A, the crack-free areas can span up to millimeter-scale. The high water-solubility of SAOT shortens the exfoliation duration to a few minutes only. Our findings highlight the SAOT as an effective and versatile sacrificial layer for freestanding oxide membranes with superior integrity, crystallinity, and functionalities, further promoting their potential for innovative device applications.

6.Unpinned Dirac-Fermions in Carbon-Phosphorous-Arsenic Based Ternary Monolayer

Authors:Amrendra Kumar, C. Kamal

Abstract: We predict energetically and dynamically stable ternary Carbon-Phosphorous-Arsenic (CPAs2) monolayers in buckled geometric structure by employing density functional theory based calculations. We consider three different symmetric configurations, namely, inversion (i), mirror (m) and rotational (r). The low-energy dispersions in electronic band structure and density of states (DOS) around the Fermi level contain two contrasting features: (a) parabolic dispersion around highly symmetric Gamma point with a step function in DOS due to nearly-free-particle-like Schroedinger-Fermions and (b) linear dispersion around highly symmetric K point with linear DOS due to massless Dirac-Fermions for i-CPAs2 monolayer. The step function in DOS is a consequence of two-dimensionality of the system in which the motion of nearly-free-particles is confined. However, a closer look at (b) reveals that the ternary monolayers possess distinct characters, namely (i) massless-gapless, (ii) slightly massive-gapped and (iii) unpinned massless-gapless Dirac-Fermions for i, m and r-CPAs2 configurations respectively. Thus, the nature of states around the Fermi level depends crucially on the symmetry of systems. In addition, we probe the influence of mechanical strain on the properties of CPAs2 monolayer. The results indicate that the characteristic dispersions of (a) and (b) move in opposite directions in energy which leads to a metal-to-semimetal transition in i and r-CPAs2 configurations, for a few percentages of tensile strain. On the other hand, a strain induced metal-to-semiconductor transition is observed in m-CPAs2 configuration with a tunable energy band gap. Interestingly, unlike graphene, the Dirac cones can be unpinned from highly symmetric K (and K') point, but they are restricted to move along the edges (K-M'-K') of first Brillouin zone due to C2 symmetry in i and r-CPAs2 configurations.

1.Advances of Machine Learning in Materials Science: Ideas and Techniques

Authors:Sue Sin Chong, Yi Sheng Ng, Hui-Qiong Wang, Jin-Cheng Zheng

Abstract: In this big data era, the use of large dataset in conjunction with machine learning (ML) has been increasingly popular in both industry and academia. In recent times, the field of materials science is also undergoing a big data revolution, with large database and repositories appearing everywhere. Traditionally, materials science is a trial-and-error field, in both the computational and experimental departments. With the advent of machine learning-based techniques, there has been a paradigm shift: materials can now be screened quickly using ML models and even generated based on materials with similar properties; ML has also quietly infiltrated many sub-disciplinary under materials science. However, ML remains relatively new to the field and is expanding its wing quickly. There are a plethora of readily-available big data architectures and abundance of ML models and software; The call to integrate all these elements in a comprehensive research procedure is becoming an important direction of material science research. In this review, we attempt to provide an introduction and reference of ML to materials scientists, covering as much as possible the commonly used methods and applications, and discussing the future possibilities.

2.Computational prediction of high thermoelectric performance in As$_{2}$Se$_{3}$ by engineering out-of-equilibrium defects

Authors:Anderson S. Chaves, Murilo Aguiar Silva, Alex Antonelli

Abstract: We employed first-principles calculations to investigate the thermoelectric transport properties of the compound As$_2$Se$_3$. Early experiments and calculations have indicated that these properties are controlled by a kind of native defect called antisites. Our calculations using the linearized Boltzmann transport equation within the relaxation time approximation show good agreement with the experiments for defect concentrations of the order of 10$^{19}$ cm$^{-3}$. Based on our total energy calculations, we estimated the equilibrium concentration of antisite defects to be about 10$^{14}$ cm$^{-3}$. These results suggest that the large concentration of defects in the experiments is due to kinetic and/or off-stoichiometry effects and in principle it could be lowered, yielding relaxation times similar to those found in other chalcogenide compounds. In this case, for relaxation time higher than 10 fs, we obtained high thermoelectric figures of merit of 3 for the p-type material and 2 for the n-type one.

3.Establishing Magnetic Coupling in Spin-crossover-2D Hybrid Nanostructures via Interfacial Charge-transfer Interaction

Authors:Shatabda Bhattacharya, Shubhadip Moulick, Chinmoy Das, Shiladitya Karmakar, Hirokazu Tada, Tanusri Saha-Dasgupta, Pradip Chakraborty, Atindra Nath Pal

Abstract: Despite a clear demonstration of bistability in spin-crossover (SCO) materials, the absence of long-range magnetic order and poor electrical conductivity limit their prospect in spintronic and nanoelectronic applications. Intending to create hybrid devices made of spin-crossover (SCO)-2D architecture, here, we report an easily processable Fe-based SCO nanostructures grown on 2D reduced graphene oxide (rGO). The heterostructure shows enhanced cooperativity due to formation of interfacial charge transfer induced inter-molecular interaction. The spin transition temperature is controlled by tuning the coverage area of SCO nanostructured networks over the 2D surfaces, thus manipulating hysteresis (aka memory) of the heterostructure. The enhanced magnetic coupling of the heterostructure leads to the spontaneous magnetization states with a large coercive field of $\sim$ 3000 Oe. Additionally, the low conductivity of the pristine SCO nanostructures is addressed by encapsulating them on suitable 2D rGO template, enabling detection of magnetic bistable spin states during high-spin/low-spin conductance change. This adds spin functionality in conductance switching for realizing hybrid 2D spintronic devices. Ab-inito calculations, on the experimentally proposed nanostructures, corroborate the enhanced magnetic interaction in the proposed architecture facilitated by interfacial charge transfer and provide insights on the microscopic mechanism.

4.Affordable inline structuration measurements of printable mortar with a pocket shear vane

Authors:Léo Demont, Romain Mesnil, Nicolas Ducoulombier, Jean-François Caron

Abstract: The control of mortar rheology is of paramount importance in the design of systems and structures in 3D printing concrete by extrusion. This is particularly sensitive for two-component (2K) processes that use an accelerator to switch the printed mortar very quickly from a liquid behavior to a sufficiently solid behavior to be able to be printed. It is necessary to set up simple and effective tests within a precise methodological framework to qualify materials evolving so quickly in an industrial context. It is obvious that inline solutions, that is to say, post-printing solutions, will be more desirable than benchtop-type solutions reproducing the printing conditions as well as possible, but imperfectly. After some main key points about measuring the structuration of mortars, we propose an original inline test using a pocket shear vane tester. The protocols are precisely described and the simplicity and quality of the results are demonstrated.

5.Reliable phase quantification in focused probe electron ptychography of thin materials

Authors:Christoph Hofer, Timothy J. Pennycook

Abstract: Electron ptychography provides highly sensitive, dose efficient phase images which can be corrected for aberrations after the data has been acquired. This is crucial when very precise quantification is required, such as with sensitivity to charge transfer due to bonding. Drift can now be essentially eliminated as a major impediment to focused probe ptychography, which benefits from the availability of easily interpretable simultaneous Z-contrast imaging. However challenges have remained when quantifying the ptychographic phases of atomic sites. The phase response of a single atom has a negative halo which can cause atoms to reduce in phase when brought closer together. When unaccounted for, as in integrating methods of quantification, this effect can completely obscure the effects of charge transfer. Here we provide a new method of quantification that overcomes this challenge, at least for 2D materials, and is robust to experimental parameters such as noise, sample tilt.

6.Nuclear quantum effect on the elasticity of ice VII under pressure: A path-integral molecular dynamics study

Authors:Jun Tsuchiya, Motoyuki Shiga, Shinji Tsuneyuki, Elizabeth C. Thompson

Abstract: We investigate the effect of nuclear quantum effects (NQEs) of hydrogen atoms on the elasticity of ice VII at high pressure and ambient temperature conditions using ab initio path-integral molecular dynamics (PIMD) calculations. We find that the NQEs of hydrogen contributes to the transition of ice VII from a static disordered structure to a dynamically disordered structure at pressures exceeding 40 GPa. This transition is marked by a discontinuous increase of the elastic constants. Comparison of ab initio molecular dynamics and PIMD calculations reveal that NQEs increase the elastic constants of ice by about 20% at 70 GPa and 300 K.

7.High-Throughput Density Functional Theory Screening of Double Transition Metal MXene Precursors

Authors:Kat Nykiel, Alejandro Strachan

Abstract: MXenes are an emerging class of 2D materials of interest in applications ranging from energy storage to electromagnetic shielding. MXenes are synthesized by selective etching of layered bulk MAX phases into sheets of 2D MXenes. Their chemical tunability has been significantly expanded with the successful synthesis of double transition metal MXenes. While knowledge of the structure and energetics of double transition metal MAX phases is critical to designing and optimizing new MXenes, only a small subset of these materials been explored. We present a comprehensive dataset of key properties of MAX phases obtained using density functional theory within the generalized gradient approximation exchange-correlation functionals. Energetics and structure of 8,712 MAX phases have been calculated and stored in a queryable, open database hosted at nanoHUB.

1.Layer number and stacking order-dependent thermal transport in molybdenum disulfide with sulfur vacancies

Authors:Ranjuna M K, Jayakumar Balakrishnan

Abstract: Recent theoretical works on two-dimensional molybdenum disulfide, MoS$_2$, with sulfur vacancies predict that the suppression of thermal transport in MoS$_2$ by point defects is more prominent in monolayers and becomes negligible as layer number increases. Here, we investigate experimentally the thermal transport properties of two-dimensional molybdenum disulfide crystals with inherent sulfur vacancies. We study the first-order temperature coefficients of interlayer and intralayer Raman modes of MoS$_2$ crystals with different layer numbers and stacking orders. The in-plane thermal conductivity ($\kappa$) and total interface conductance per unit area ($ g $) across the 2D material-substrate interface of mono-, bi- and tri-layer MoS$_2$ samples are measured using the micro-Raman thermometry. Our results clearly demonstrate that the thermal conductivity is significantly suppressed by sulfur vacancies in monolayer MoS$_2$. However, this reduction in $\kappa$ becomes less evident as the layer number increases, confirming the theoretical predictions. No significant variation is observed in the $\kappa$ and $ g $ values of 2H and 3R stacked bilayer MoS$_2$ samples.

2.Unexpected magnetism explained in Cu/Cu2O-rGO nanocomposite

Authors:Rajarshi Roy, Kaustav Bhattacharjee, Satya Prakash Pati, Korak Biswas, Kalyan Kumar Chattopadhyay

Abstract: The observation of room temperature ferromagnetism along with a low temperature paramagnetic counterpart in undoped Cu-Cu2O-rGO nanocomposite was demonstrated. A phenomenological approach was taken to explain the observations based on 3D Ising model for arbitrary spins generated due to Cu vacancy in the Cu2O system preferably at the interface.

3.Weyl phonons in chiral crystals

Authors:Tiantian Zhang, Zhiheng Huang, Zitian Pan, Luojun Du, Guangyu Zhang, Shuichi Murakami

Abstract: Chirality is an indispensable concept that pervades fundamental science and nature, manifesting itself in diverse forms such as chiral quasiparticles and chiral structures. Of particular interest are Weyl phonons carrying specific Chern numbers and chiral phonons doing circular motions in crystals. Up to now, Weyl and chiral phonons have been studied independently and the interpretations of chirality seem to be different in these two concepts, impeding our understanding. Here, we demonstrate that Weyl and chiral phonons are entangled in chiral crystals. Employing a typical chiral crystal of elementary tellurium (Te) as a case study, we expound on the intrinsic relationship between Chern number of Weyl phonons and pseudo-angular momentum (PAM) of chiral phonons. In light of the mutual coupling, we propose Raman scattering as a new technique to demonstrate the existence of Weyl phonons in Te, by detecting the chirality-induced energy splitting between the two constituent chiral phonon branches for Weyl phonons. By using the same experimental approach, we also observe the obstructed phonon surface states for the first time.

4.The Emerging Weak Antilocalization Effect in Semimetal Ta$_{0.7}$Nb$_{0.3}$Sb$_2$ Single Crystal

Authors:Lei Guo, Meng Xu, Lei Chen, Ting Wei Chen, Weiyao Zhao, Xiaoling Wang, Shuai Dong, Ren-Kui Zheng

Abstract: Weak antilocalization (WAL) effect is commonly observed in 2D systems, or 3D topological insulators, topological semimetal systems. Here we report the clear sign of WAL effect in high quality Ta$_{0.7}$Nb$_{0.3}$Sb$_2$ single crystals, in below 50$^\circ$ K region. The chemical vapor transport method was employed to grow the single crystal samples, the high crystallization quality and uniform element distribution are verified by X-ray diffractions and electron microscopy techniques. Employing the Hall effect and two-band model fitting, the high carrier mobility (> 1000 cm$^2$V$^{-1}$s$^{-1}$ in 2 to 300$^\circ$ K region) and off-compensation electron/hole ratio are obtained. Due to the different angular dependence of WAL effect and the fermiology of Ta$_{0.7}$Nb$_{0.3}$Sb$_2$ single crystal, interesting magnetic-field-induced symmetry change is observed in angular magnetoresistance. These interesting transport properties will lead to more theoretical and applicational exploration in Ta$_{0.7}$Nb$_{0.3}$Sb$_2$ and related semimetal materials.

5.Reversible and nonvolatile manipulation of the spin-orbit interaction in ferroelectric field-effect transistors based on a two-dimensional bismuth oxychalcogenide

Authors:Ming-Yuan Yan, Shuang-Shuang Li, Jian-Min Yan, Li Xie, Meng Xu, Lei Guo, Shu-Juan Zhang, Guan-Yin Gao, Fei-Fei Wang, Shan-Tao Zhang, Xiaolin Wang, Yang Chai, Weiyao Zhao, Ren-Kui Zheng

Abstract: Spin-orbit interaction (SOI) offers a nonferromagnetic scheme to realize spin polarization through utilizing an electric field. Electrically tunable SOI through electrostatic gates have been investigated, however, the relatively weak and volatile tunability limit its practical applications in spintronics. Here, we demonstrate the nonvolatile electric-field control of SOI via constructing ferroelectric Rashba architectures, i.e., 2D Bi2O2Se/PMN-PT ferroelectric field effect transistors. The experimentally observed weak antilocalization (WAL) cusp in Bi2O2Se films implies the Rashba-type SOI that arises from asymmetric confinement potential. Significantly, taking advantage of the switchable ferroelectric polarization, the WAL-to-weak localization (WL) transition trend reveals the competition between spin relaxation and dephasing process, and the variation of carrier density leads to a reversible and nonvolatile modulation of spin relaxation time and spin splitting energy of Bi2O2Se films by this ferroelectric gating. Our work provides a scheme to achieve nonvolatile control of Rashba SOI with the utilization of ferroelectric remanent polarization.

6.Topological Insulator VxBi1.08-xSn0.02Sb0.9Te2S as a Promising n-type Thermoelectric Material

Authors:Lei Chen, Weiyao Zhaoa, Meng Li, Guangsai Yang, Lei Guo, Abudulhakim Bake, Peng Liu, David Cortie, Ren-Kui Zheng, Zhenxiang Cheng, Xiaolin Wang

Abstract: As one of the most important n-type thermoelectric (TE) materials, Bi2Te3 has been studied for decades, with efforts to enhance the thermoelectric performance based on element doping, band engineering, etc. In this study, we report a novel bulk-insulating topological material system as a replacement for n-type Bi2Te3 materials: V doped Bi1.08Sn0.02Sb0.9Te2S (V:BSSTS) . The V:BSSTS is a bulk insulator with robust metallic topological surface states. Furthermore, the bulk band gap can be tuned by the doping level of V, which is verified by magnetotransport measurements. Large linear magnetoresistance is observed in all samples. Excellent thermoelectric performance is obtained in the V:BSSTS samples, e.g., the highest figure of merit ZT of ~ 0.8 is achieved in the 2% V doped sample (denoted as V0.02) at 550 K. The high thermoelectric performance of V:BSSTS can be attributed to two synergistic effects: (1) the low conductive secondary phases Sb2S3, and V2S3 are believed to be important scattering centers for phonons, leading to lower lattice thermal conductivity; and (2) the electrical conductivity is increased due to the high-mobility topological surface states at the boundaries. In addition, by replacing one third of costly tellurium with abundant, low-cost, and less-toxic sulfur element, the newly produced BSSTS material is inexpensive but still has comparable TE performance to the traditional Bi2Te3-based materials, which offers a cheaper plan for the electronics and thermoelectric industries. Our results demonstrate that topological materials with unique band structures can provide a new platform in the search for new high performance TE materials.

7.A critical perspective for emerging ultra-thin solar cells with ultra-high power-per-weight outputs

Authors:Apostolos Panagiotopoulos, Temur Maksudov, George Kakavelakis, George Perrakis, Essa A. Alharbi, Dimitar Kutsarov, Furkan H. Isikgor, Salman Alfihed, Konstantinos Petridis, Maria Kafesaki, S. Ravi P. Silva, Thomas D. Anthopoulos, Michael Graetzel

Abstract: Ultrathin, solution-processed emerging solar cells with high power-per-weight (PPW) outputs demonstrate unique potential for applications where low weight, high power output, and flexibility are indispensable. The following perspective explores the literature of emerging PVs and highlights the maximum reported PPW values of Perovskite Solar Cells (PSCs) 29.4 W/g, Organic Solar Cells (OSCs) 32.07 W/g and Quantum Dot Solar Cells (QDSC) 15.02 W/g, respectively. The record PPW values of OSCs and PSCs are approximately one order of magnitude higher compared to their inorganic ultrathin solar cells counterparts (approx. 3.2 W/g for CIGS and a-Si). This consists emerging PVs, very attractive for a variety of applications where the PPW is the key parameter. In particular, both OSCs and PSCs can be implemented in different scenarios of applications (indoor and biocompatible applications for OSCs and outdoor and high-energy radiation conversion conditions for the PSCs) due to their unique optoelectronic and physiochemical properties. Finally, our theoretical optical and electrical simulation and optimization study for the most promising and well-suited PV technologies, showed an impressive maximum realistic theoretical PPW limit of 74.3 and 93.7 W/g for PSCs and OSCs, respectively. Our finding shows that the literature PSCs and OSCs towards high PPW outputs, is not quite close to the theoretical maximum and thus more work needs to be done to further increase the PPW output of these promising PV technologies.

8.Emergent magnetism with continuous control in the ultrahigh conductivity layered oxide PdCoO2

Authors:Matthew Brahlek, Alessandro R. Mazza, Abdulgani Annaberdiyev, Michael Chilcote, Gaurab Rimal, Gábor B. Halász, Anh Pham, Yun-Yi Pai, Jaron T. Krogel, Jason Lapano, Benjamin J. Lawrie, Gyula Eres, Jessica McChesney, Thomas Prokscha, Andreas Suter, Seongshik Oh, John W. Freeland, Yue Cao, Jason S. Gardner, Zaher Salman, Robert G. Moore, Panchapakesan Ganesh, T. Zac Ward

Abstract: The current challenge to realizing continuously tunable magnetism lies in our inability to systematically change properties such as valence, spin, and orbital degrees of freedom as well as crystallographic geometry. Here, we demonstrate that ferromagnetism can be externally turned on with the application of low-energy helium implantation and subsequently erased and returned to the pristine state via annealing. This high level of continuous control is made possible by targeting magnetic metastability in the ultra-high conductivity, non-magnetic layered oxide PdCoO2 where local lattice distortions generated by helium implantation induce emergence of a net moment on the surrounding transition metal octahedral sites. These highly-localized moments communicate through the itinerant metal states which triggers the onset of percolated long-range ferromagnetism. The ability to continuously tune competing interactions enables tailoring precise magnetic and magnetotransport responses in an ultra-high conductivity film and will be critical to applications across spintronics.

9.Lattice structure dependence of laser-induced ultrafast magnetization switching in ferrimagnets

Authors:J. A. Vélez, R. M. Otxoa, U. Atxitia

Abstract: The experimental discovery of single-pulse ultrafast magnetization switching in ferrimagnetic alloys, such as GdFeCo and MnRuGa, opened the door to a promising route toward faster and more energy efficient data storage. A recent semi-phenomenological theory has proposed that a fast, laser-induced demagnetization below a threshold value puts the system into a dynamical regime where angular momentum transfer between sublattices dominates. Notably, this threshold scales inversely proportional to the number of exchange-coupled nearest neighbours considered in the model, which in the simplest case is directly linked to the underlying lattice structure. In this work, we study the role of the lattice structure on the laser-induced ultrafast magnetization switching in ferrimagnets by complementing the phenomenological theory with atomistic spin dynamics computer simulations. We consider a spin model of the ferrimagnetic GdFeCo alloy with increasing number of exchange-coupled neighbours. Within this model, we demonstrate that the laser-induced magnetization dynamics and switching depends on the lattice structure. Further, we determine that the critical laser energy for switching reduces for decreasing number of exchange-coupled neighbours.

10.Electron-phonon coupling in semiconductors at high electronic temperatures

Authors:Nikita Medvedev

Abstract: A nonperturbative dynamical coupling approach based on tight-binding molecular dynamics is used to evaluate the electron-ion (electron-phonon) coupling parameter in irradiated semiconductors as a function of the electronic temperature up to ~25,000 K. The method accounts for arbitrary electronic distribution function via the Boltzmann equation, enabling a comparative analysis of various models: fully equilibrium electronic distribution, band-resolved local equilibria (distinct temperatures and chemical potential of electrons in the valence and the conduction band), and a full nonequilibrium distribution. It is demonstrated that the nonequilibrium produces the electron-phonon coupling parameter different by at most ~35% from its equilibrium counterpart for identical deposited energy density, allowing to use the coupling parameter as a function of the single electronic equivalent (or kinetic) temperature. The following 14 semiconductors are studied here - group IV: Si, Ge, SiC; group III-V: AlAs, AlP, GaP, GaAs, GaSb; oxides: ZnO, TiO2, Cu2O; layered PbI2; ZnS and B4C.

11.Comparing Forward and Inverse Design Paradigms: A Case Study on Refractory High-Entropy Alloys

Authors:Arindam Debnath, Lavanya Raman, Wenjie Li, Adam M. Krajewski, Marcia Ahn, Shuang Lin, Shunli Shang, Allison M. Beese, Zi-Kui Liu, Wesley F. Reinhart

Abstract: The rapid design of advanced materials is a topic of great scientific interest. The conventional, ``forward'' paradigm of materials design involves evaluating multiple candidates to determine the best candidate that matches the target properties. However, recent advances in the field of deep learning have given rise to the possibility of an ``inverse'' design paradigm for advanced materials, wherein a model provided with the target properties is able to find the best candidate. Being a relatively new concept, there remains a need to systematically evaluate how these two paradigms perform in practical applications. Therefore, the objective of this study is to directly, quantitatively compare the forward and inverse design modeling paradigms. We do so by considering two case studies of refractory high-entropy alloy design with different objectives and constraints and comparing the inverse design method to other forward schemes like localized forward search, high throughput screening, and multi objective optimization.

1.Combined theoretical and experimental study of the Moiré dislocation network at the SrTiO$_3$-(La,Sr)(Al,Ta)O$_3$ interface

Authors:Chiara Ricca, Elizabeth Skoropata, Marta D. Rossell, Rolf Erni, Urs Staub, Ulrich Aschauer

Abstract: Recently a highly ordered Moir\'e dislocation lattice was identified at the interface between a \ce{SrTiO3} (STO) thin film and the (LaAlO$_3$)$_{0.3}$(Sr$_2$TaAlO$_6$)$_{0.7}$ (LSAT) substrate. A fundamental understanding of the local ionic and electronic structure around the dislocation cores is crucial to further engineer the properties of these complex multifunctional heterostructures. Here we combine experimental characterization via analytical scanning transmission electron microscopy with results of molecular dynamics and density functional theory calculations to gain insights into the structure and defect chemistry of these dislocation arrays. Our results show that these dislocations lead to undercoordinated Ta/Al cations at the dislocation core, where oxygen vacancies can easily be formed, further facilitated by the presence of cation vacancies. The reduced Ti$^{3+}$ observed experimentally at the dislocations by electron energy-loss spectroscopy are a consequence of both the structure of the dislocation itself, as well as of the electron-doping due to oxygen vacancy formation. Finally, the experimentally observed Ti diffusion into LSAT around the dislocation core occurs only together with cation-vacancy formation in LSAT or Ta diffusion into STO.

2.Vibrational Entropic Stabilization of Layered Chalcogenides: From Ordered Vacancy Compounds to 2D Layers

Authors:Roberto Prado-Rivera, Daniela Radu, Vincent H. Crespi, Yuanxi Wang

Abstract: Despite the rapid pace of computationally and experimentally discovering new two-dimensional layered materials, a general criteria for a given compound to prefer a layered structure over a non-layered one remains unclear. Articulating such criteria would allow one to identify materials at the verge of an inter-dimensional structural phase transition between a 2D layered phase and 3D bulk one, with potential applications in phase change memory devices. Here we identify a general stabilization effect driven by vibrational entropy that can favor 2D layered structures over 3D bulk structures at higher temperatures, which can manifest in ordered vacancy compounds where phase competition is tight. We demonstrate this vibrational-entropy stabilization effect for three prototypical ordered vacancy chalcogenides, ZnIn2S4 and In2S3, and Cu3VSe4, either by vacancy rearrangement or by cleaving through existing vacancies. The relative vibrational entropy advantage of the 2D layered phase originates mainly from softened out-of-plane dilation phonon modes.

3.Correlations, disorder, and multi-magnon processes in terahertz spin dynamics of magnetic nanostructures: A first-principles investigation

Authors:S. Paischer, D. Eilmsteiner, I. Maznichenko, N. Buczek, Kh. Zakeri, A. Ernst, P. Buczek

Abstract: Understanding the profound impact of correlation effects and crystal imperfections is essential for an accurate description of solids. Here we study the role of correlation, disorder, and multi-magnon processes in THz magnons. Our findings reveal that a significant part of the electron self-energy, which goes beyond the adiabatic local spin density approximation, arises from the interaction between electrons and a virtual magnon gas. This interaction leads to a substantial modification of the exchange splitting and a renormalization of magnon energies, in agreement with the experimental data. We establish a quantitative hierarchy of magnon relaxation processes based on first principles.

4.Nanoscale domain engineering in SrRuO$_3$ thin films

Authors:Céline Lichtensteiger, Chia-Ping Su, Iaroslav Gaponenko, Marios Hadjimichael, Ludovica Tovaglieri, Patrycja Paruch, Alexandre Gloter, Jean-Marc Triscone

Abstract: We investigate nanoscale domain engineering via epitaxial coupling in a set of SrRuO$_3$/PbTiO$_3$/SrRuO$_3$ heterostructures epitaxially grown on (110)$_o$-oriented DyScO$_3$ substrates. The SrRuO$_3$ layer thickness is kept at 55 unit cells, whereas the PbTiO$_3$ layer is grown to thicknesses of 23, 45 and 90 unit cells. Through a combination of atomic force microscopy, x-ray diffraction and high resolution scanning transmission electron microscopy studies, we find that above a certain critical thickness of the ferroelectric layer, the large structural distortions associated with the ferroelastic domains propagate through the top SrRuO$_3$ layer, locally modifying the orientation of the orthorhombic SrRuO$_3$ and creating a modulated structure that extends beyond the ferroelectric layer boundaries.

5.Biaxial strain tuning of exciton energy and polarization in monolayer WS2

Authors:G. Kourmoulakis, A. Michail, I. Paradisanos, X. Marie, M. M. Glazov, B. Jorissen, L. Covaci, E. Stratakis, K. Papagelis, J. Parthenios, G. Kioseoglou

Abstract: We perform micro-photoluminescence and Raman experiments to examine the impact of biaxial tensile strain on the optical properties of WS2 monolayers. A strong shift on the order of -130 meV per % of strain is observed in the neutral exciton emission at room temperature. Under near-resonant excitation we measure a monotonic decrease in the circular polarization degree under applied strain. We experimentally separate the effect of the strain-induced energy detuning and evaluate the pure effect coming from biaxial strain. The analysis shows that the suppression of the circular polarization degree under biaxial strain is related to an interplay of energy and polarization relaxation channels as well as to variations in the exciton oscillator strength affecting the long-range exchange interaction.

6.In-plane magnetocrystalline anisotropy in the van der Waals antiferromagnet FePSe$_3$ probed by magneto-Raman scattering

Authors:Dipankar Jana, Piotr Kapuscinski, Amit Pawbake, Anastasios Papavasileiou, Zdenek Sofer, Ivan Breslavetz, Milan Orlita, Marek Potemski, Clement Faugeras

Abstract: Magnon gap excitations selectively coupled to phonon modes have been studied in FePSe$_3$ layered antiferromagnet with magneto-Raman scattering experiments performed at different temperatures. The bare magnon excitation in this material has been found to be split (by $\approx~1.2$ cm$^{-1}$) into two components each being selectively coupled to one of the two degenerated, nearby phonon modes. Lifting the degeneracy of the fundamental magnon mode points out toward the biaxial character of the FePS$_3$ antiferromagnet, with an additional in-plane anisotropy complementing much stronger, out-of-plane anisotropy. Moreover, the tunability, with temperature, of the phonon- versus the magnon-like character of the observed coupled modes has been demonstrated.

7.Gas flow-directed growth of aligned carbon nanotubes from nonmetallic seeds

Authors:Yuanjia Liu, Taiki Inoue, Mengyue Wang, Michiharu Arifuku, Noriko Kiyoyanagi, Yoshihiro Kobayashi

Abstract: Kite growth is a process that utilizes laminar gas flow in chemical vapor deposition to grow long, well-aligned carbon nanotubes (CNTs) that are suitable for electronic application. This process uses metal nanoparticles as catalytic seeds for CNT growth. However, these nanoparticles remain as impurities in the grown CNT. In this study, nanodiamonds (NDs) with negligible catalytic activity were utilized as nonmetallic seeds instead of metal catalysts because they are stable at high temperatures and facilitate the growth of low-defect CNTs without residual metal impurities. Results demonstrate the successful growth of over 100-$\mu$m-long CNTs by carefully controlling the growth conditions. Secondary electron (SE) yield and atomic force microscopy analyses revealed that most of the aligned CNTs were grown from ND, and not the metal impurities, via the tip-growth mode. Structural characterizations revealed the high crystallinity of CNTs, with relatively small diameters. This study presents the first successful use of nonmetallic seeds for kite growth and provides a convincing alternative for starting materials to prepare long, aligned CNTs without metal impurities. The findings of this study pave the way for more convenient fabrication of aligned CNT-based devices, potentially simplifying the production process by avoiding the need for the removal of metal impurities.

8.Conduction band tuning by controlled alloying of Fe into Cs2AgBiBr6 double perovskite powders

Authors:Huygen J. Jobsis, Kostas Fykouras, Joost W. C. Reinders, Jacco van Katwijk, Joren M. Dorresteijn, Tjom Arens, Ina Vollmer, Loreta A. Muscarella, Linn Leppert, Eline M. Hutter

Abstract: Halide double perovskite semiconductors such as Cs2AgBiBr6 are widely investigated as a more stable, less toxic alternative to lead-halide perovskites in light conversion applications including photovoltaics and photoredox catalysis. However, the relatively large and indirect bandgap of Cs2AgBiBr6 limits efficient sunlight absorption. Here, we show that controlled replacement of Bi3+ with Fe3+ via mechanochemical synthesis results in a remarkable tunable absorption onset between 2.1 and ~1 eV. Our first-principles density functional theory (DFT) calculations suggest that this bandgap reduction originates primarily from a lowering of the conduction band upon introduction of Fe3+. Furthermore, we find that the tunability of the conduction band energy is reflected in the photoredox activity of these semiconductors. Finally, our DFT calculations predict a direct bandgap when >50% of Bi3+ is replaced with Fe3+. Our findings open new avenues for enhancing the sunlight absorption of double perovskite semiconductors and for harnessing their full potential in sustainable energy applications.

9.Ni-O-Ag catalyst enables 103-m2 artificial photosynthesis with >16% solar-to-chemical energy conversion efficiency

Authors:Yaguang Li, Fanqi Meng, Qixuan Wu, Dachao Yuan, Haixiao Wang, Bang Liu, Junwei Wang, Xingyuan San, Lin Gu, Shufang Wang, Qingbo Meng

Abstract: Herein, NiO nanosheets supported with Ag single atoms are synthesized for photothermal CO2 hydrogenation to achieve 1065 mmol g-1 h-1 of CO production rate under 1 sun irradiation, revealing the unparalleled weak sunlight driven reverse water-gas shift reaction (RWGS) activity. This performance is attributed to the coupling effect of Ag-O-Ni sites to enhance the hydrogenation of CO2 and weaken the CO adsorption, resulting in 1434 mmol g-1 h-1 of CO yield at 300 degree, surpassing any low-temperature RWGS performances ever reported. Building on this, we integrated the 2D Ni1Ag0.02O1 supported photothermal RWGS with commercial photovoltaic electrolytic water splitting, leading to the realization of 103 m2 scale artificial photosynthesis system with a daily CO yield of 18.70 m3, a photochemical energy conversion efficiency of >16%, over 90% H2 ultilazation efficiency, outperforming other types of artificial photosynthesis. The results of this research chart a promising course for designing practical, natural sunlight-driven artificial photosynthesis systems and highly efficient platinum-free CO2 hydrogenation catalysts. This work is a significant step towards harnessing solar energy more efficiently and sustainably, opening exciting possibilities for future research and development in this area.

10.Coherent Dynamics of Charge Carriers in γ-InSe Revealed by Ultrafast Spectroscopy

Authors:Jianwei Shen, Jiayu Liang, Qixu Zhao, Menghui Jia, Jinquan Chen, Haitao Sun, Qinghong Yuan, Hong-Guang Duan, Ajay Jha, Yan Yang, Zhenrong Sun

Abstract: For highly efficient ultrathin solar cells, layered indium selenide (InSe), a van der Waals solid, has shown a great promise. In this paper, we study the coherent dynamics of charge carriers generation in {\gamma}-InSe single crystals. We employ ultrafast transient absorption spectroscopy to examine the dynamics of hot electrons after resonant photoexcitation. To study the effect of excess kinetic energy of electrons after creating A exciton (VB1 to CB transition), we excite the sample with broadband pulses centered at 600, 650, 700 and 750 nm, respectively. We analyze the relaxation and recombination dynamics in {\gamma}-InSe by global fitting approach. Five decay associated spectra with their associated lifetimes are obtained, which have been assigned to intraband vibrational relaxation and interband recombination processes. We extract characteristic carrier thermalization times from 1 to 10 ps. To examine the coherent vibrations accompanying intraband relaxation dynamics, we analyze the kinetics by fitting to exponential functions and the obtained residuals are further processed for vibrational analysis. A few key phonon coherences are resolved and ab-initio quantum calculations reveal the nature of the associated phonons. The wavelet analysis is employed to study the time evolution of the observed coherences, which show that the low-frequency coherences last for more than 5 ps. Associated calculations reveal that the contribution of the intralayer phonon modes is the key determining factor for the scattering between free electrons and lattice. Our results provide fundamental insights into the photophysics in InSe and help to unravel their potential for high-performance optoelectronic devices.

11.Temperature and thickness dependence of the thermal conductivity in 2D ferromagnet Fe$_3$GeTe$_2$

Authors:Marcel S. Claro, Javier Corral-Sertal, Adolfo O. Fumega, Santiago Blanco-Canosa, Manuel Suárez-Rodríguez, Luis E. Hueso, Victor Pardo, Francisco Rivadulla

Abstract: The emergence of symmetry-breaking orders such as ferromagnetism and the weak interlayer bonding in van der Waals materials, offers a unique platform to engineer novel heterostructures and tune transport properties like thermal conductivity. Here, we report the experimental and theoretical study of the cross-plane thermal conductivity, $\kappa_\perp$, of the van der Waals 2D ferromagnet Fe$_3$GeTe$_2$. We observe a non-monotonic increase of $\kappa_\perp$ with the thickness and a large suppression in artificially-stacked layers, indicating a diffusive transport regime with ballistic contributions. These results are supported by the theoretical analyses of the accumulated thermal conductivity, which show an important contribution of phonons with mean free paths between 10 and 200 nm. Moreover, our experiments show a reduction of the $\kappa_\perp$ in the low-temperature ferromagnetic phase occurring at the magnetic transition. The calculations show that this reduction in $\kappa_\perp$ is associated with a decrease in the group velocities of the acoustic phonons and an increase in the phonon-phonon scattering of the Raman modes that couple to the magnetic phase. These results demonstrate the potential of van der Waals ferromagnets for thermal transport engineering.

12.On the use of SRIM for calculating arc-dpa exposure

Authors:E. Mitsi, K. Koutsomitis, G. Apostolopoulos

Abstract: We propose two methods for evaluating athermal recombination corrected (arc) displacement damage parameters in ion irradiations employing the computer code SRIM (Stopping and Range of Ions in Matter). The first method consists of post-processing the detailed SRIM output for all simulated damage events and re-calculating according to the arc damage model. In the second method, an approximate empirical formula is devised which gives the average displacements in the arc damage model as a function of the corresponding quantity according to the standard Norgett-Robinson-Torrens model, which is readily obtained from SRIM.

13.Competing mechanisms govern the thermal rectification behavior in semi-stochastic polycrystalline graphene with graded grain-density distribution

Authors:Simanta Lahkar, Raghavan Ranganathan

Abstract: Thermal rectifiers are devices that have different thermal conductivities in opposing directions of heat flow. The realization of practical thermal rectifiers relies significantly on a sound understanding of the underlying mechanisms of asymmetric heat transport, and two-dimensional materials offer a promising opportunity in this regard owing to their simplistic structures together with a vast possibility of tunable imperfections. However, the in-plane thermal rectification mechanisms in 2D materials like graphene having directional gradients of grain sizes have remained elusive. In fact, understanding the heat transport mechanisms in polycrystalline graphene, which are more practical to synthesize than large-scale single-crystal graphene, could potentially allow a unique opportunity to combine with other defects and designs for effective optimization of the thermal rectification property. In this work, we investigated the thermal rectification behavior in periodic atomistic models of polycrystalline graphene whose grain arrangements were generated semi-stochastically in order to have different gradient grain-density distributions along the in-plane heat flow direction. We employed the centroid Voronoi tessellation technique to generate realistic grain boundary structures for graphene, and the non-equilibrium molecular dynamics simulations method was used to calculate the thermal conductivities and thermal rectification values. Additionally, detailed phonon characteristics and propagating phonon spatial energy densities were analyzed based on the fluctuation-dissipation theory to elucidate the competitive interplay between two underlying mechanisms that determine the degree of asymmetric heat flow in graded polycrystalline graphene.

1.Gigantic Anisotropy of Self-Induced Spin-Orbit Torque in Weyl Ferromagnet Co2MnGa

Authors:Motomi Aoki Kyoto Univ . CSRN, Kyoto Univ, Yuefeng Yin . Monash Univ . ARC, Simon Granville . Robinson Research Institute . The MacDiamid Institute, Yao Zhang . Robinson Research Institute . The MacDiamid Institute, Nikhil V. Medhekar . Monash Univ . ARC, Livio Leiva Kyoto Univ, Ryo Ohshima Kyoto Univ . CSRN, Kyoto Univ, Yuichiro Ando Kyoto Univ . CSRN, Kyoto Univ . PRESTO-JST, Masashi Shiraishi Kyoto Univ . CSRN, Kyoto Univ

Abstract: Spin-orbit torque (SOT) is receiving tremendous attention from both fundamental and application-oriented aspects. Co2MnGa, a Weyl ferromagnet that is in a class of topological quantum materials, possesses cubic-based high structural symmetry, the L21 crystal ordering, which should be incapable of hosting anisotropic SOT in conventional understanding. Here we show the discovery of a gigantic anisotropy of self-induced SOT in Co2MnGa. The magnitude of the SOT is comparable to that of heavy metal/ferromagnet bilayer systems despite the high inversion symmetry of the Co2MnGa structure. More surprisingly, a sign inversion of the self-induced SOT is observed for different crystal axes. This finding stems from the interplay of the topological nature of the electronic states and their strong modulation by external strain. Our research enriches the understanding of the physics of self-induced SOT and demonstrates a versatile method for tuning SOT efficiencies in a wide range of materials for topological and spintronic devices.

2.Plasmon excitations across the charge-density-wave transition in single layer TiSe$_2$

Authors:Zahra Torbatian, Dino Novko

Abstract: $1T$-TiSe$_2$ is believed to posses a soft electronic mode, i.e., plasmon or exciton, that might be responsible for the exciton condensation and charge-density-wave (CDW) transition. Here, we explore collective electronic excitations in single-layer $1T$-TiSe$_2$ by using the ab-initio electromagnetic linear response and unveil intricate scattering pathways of two-dimensional (2D) plasmon mode. We found the dominant role of plasmon-phonon scattering, which in combination with the CDW gap excitations leads to the anomalous temperature dependence of the plasmon linewidth across the CDW transition. Below the transition temperature $T_{\rm CDW}$ a strong hybridization between 2D plasmon and CDW excitations is obtained. These optical features are highly tunable due to temperature-dependent CDW gap modifications and are argued to be universal for the CDW-bearing 2D materials.

3.Magnetic Proximity induced efficient charge-to-spin conversion in large area PtSe$_{2}$/Ni$_{80}$Fe$_{20}$ heterostructures

Authors:Richa Mudgal, Alka Jakhar, Pankhuri Gupta, Ram Singh Yadav, B. Biswal, P. Sahu, Himanshu Bangar, Akash Kumar, Niru Chowdhury, Biswarup Satpati, B. R. K. Nanda, S. Satpathy, Samaresh Das, P. K. Muduli

Abstract: As a topological Dirac semimetal with controllable spin-orbit coupling and conductivity, PtSe$_2$, a transition-metal dichalcogenide, is a promising material for several applications from optoelectric to sensors. However, its potential for spintronics applications is yet to be explored. In this work, we demonstrate that PtSe$_{2}$/Ni$_{80}$Fe$_{20}$ heterostructure can generate a large damping-like current-induced spin-orbit torques (SOT), despite the absence of spin-splitting in bulk PtSe$_{2}$. The efficiency of charge-to-spin conversion is found to be $(-0.1 \pm 0.02)$~nm$^{-1}$ in PtSe$_{2}$/Ni$_{80}$Fe$_{20}$, which is three times that of the control sample, Ni$_{80}$Fe$_{20}$/Pt. Our band structure calculations show that the SOT due to the PtSe$_2$ arises from an unexpectedly large spin splitting in the interfacial region of PtSe$_2$ introduced by the proximity magnetic field of the Ni$_{80}$Fe$_{20}$ layer. Our results open up the possibilities of using large-area PtSe$_{2}$ for energy-efficient nanoscale devices by utilizing the proximity-induced SOT.

4.Double glass transition in polyethylene naphthalate structural relaxation by MDSC, BDS and TSDC

Authors:J. C. Cañadas, J. A. Diego, S. Diez-Berart, D. O. López, M. Mudarra, J. Salud, J. Sellarès

Abstract: We present the experimental study of the primary, $\alpha$, and secondary, $\beta^*$, relaxations of the glassy polymer polyethylene naphthalate (PEN), by Modulated Differential Scanning Calorimetry (MDSC), Thermally Stimulated Discharge Currents (TSDC) and Broadband Dielectric Spectroscopy (BDS). Results show how the $\alpha$ and $\beta^*$ relaxations can be considered part of a very broad and distributed relaxation. The $\beta^*$ relaxation is composed of a main contribution ($\beta_3^*$) and two additional ones ($\beta_1^*$ and $\beta_2^*$) and each elementary mode of the relaxation has its own glass transition temperature. This scenario gives rise to an extended glass transition mainly centered in $T_{g\beta^*} \sim 305$ K and $T_{g\alpha} \sim 387$ K.

5.Symmetry Analysis with Spin Crystallographic Groups: Disentangling Spin-Orbit-Free Effects in Emergent Electromagnetism

Authors:Hikaru Watanabe, Kohei Shinohara, Takuya Nomoto, Atsushi Togo, Ryotaro Arita

Abstract: Recent studies identified spin-order-driven phenomena such as spin-charge interconversion without relying on the relativistic spin-orbit interaction. Those physical properties can be prominent in systems containing light magnetic atoms due to sizable exchange splitting and may pave the way for realizations of giant responses correlated with the spin degree of freedom. In this paper, we present a systematic symmetry analysis based on the spin crystallographic groups and identify physical property of a vast number of magnetic materials up to 1500 in total. Absence of spin-orbital entanglement leads to the spin crystallographic symmetry having richer property compared to the well-known magnetic space group symmetry. By decoupling the spin and orbital degrees of freedom, our analysis enables us to take a closer look into the relation between the dimensionality of spin structures and the resultant physical properties and to identify the spin and orbital contributions separately. In stark contrast to the established analysis with magnetic space groups, the spin crystallographic group manifests richer symmetry including spin translation symmetry and leads to nontrivial emergent responses. For representative examples, we discuss geometrical nature of the anomalous Hall effect and magnetoelectric effect, and classify the spin Hall effect arising from the spontaneous spin-charge coupling. Using the power of computational analysis, we apply our symmetry analysis to a wide range of magnets, encompassing complex magnets such as those with noncoplanar spin structures as well as collinear and coplanar magnets. We identify emergent multipoles relevant to physical responses and argue that our method provides a systematic tool for exploring sizable electromagnetic responses driven by spin ordering.

6.Optically Induced Avoided Crossing in Graphene

Authors:Sören Buchenau, Benjamin Grimm-Lebsanft, Florian Biebl, Tomke Glier, Lea Westphal, Janika Reichstetter, Dirk Manske, Michael Fechner, Andrea Cavalleri, Sonja Herres-Pawlis, Michael Rübhausen

Abstract: Degenerate states in condensed matter are frequently the cause of unwanted fluctuations, which prevent the formation of ordered phases and reduce their functionalities. Removing these degeneracies has been a common theme in materials design, pursued for example by strain engineering at interfaces. Here, we explore a non-equilibrium approach to lift degeneracies in solids. We show that coherent driving of the crystal lattice in bi- and multilayer graphene, boosts the coupling between two doubly-degenerate modes of E1u and E2g symmetry, which are virtually uncoupled at equilibrium. New vibronic states result from anharmonic driving of the E1u mode to large amplitdues, boosting its coupling to the E2g mode. The vibrational structure of the driven state is probed with time-resolved Raman scattering, which reveals laser-field dependent mode splitting and enhanced lifetimes. We expect this phenomenon to be generally observable in many materials systems, affecting the non-equilibrium emergent phases in matter.

7.Spin-Flop Ordering from Frustrated Ferro- and Antiferromagnetic Interactions: A Combined Theoretical and Experimental Study of a $\mathrm{Mn}/\mathrm{Fe}(100)$ Monolayer

Authors:C. Grazioli, Dario Alfè, S. R. Krishnakumar, Subhra Sen Gupta, M. Veronese, S. Turchini, Nicola Bonini, Andrea Dal Corso, D. D. Sarma, Stefano Baroni, C. Carbone

Abstract: The occurrence of a noncollinear magnetic structure at a Mn monolayer grown epitaxially on Fe(100) is predicted theoretically, using spinor density-functional theory, and observed experimentally, using x-ray magnetic circular dichroism (XMCD) and linear dichroism (XMLD) spectroscopies. The combined use of XMCD and XMLD at the Mn-absorption edge allows us to assess the existence of ferromagnetic and antiferromagnetic order at the interface, and also to determine the moment orientations with element specificity. The experimental results thus obtained are in excellent agreement with the magnetic structure determined theoretically.

8.Study of the electronic structure of short chain oligothiophenes

Authors:Cesare Grazioli, Oscar Baseggio, Mauro Stener, Giovanna Fronzoni, Monica de Simone, Marcello Coreno, Ambra Guarnaccio, Antonio Aantagata, Maurizio D'Auria

Abstract: The electronic structure of short-chain thiophenes (thiophene, 2,2'-bithiophene and 2,2':5',2'-terthiophene) in the gas phase has been investigated by combining the outcomes of Near-Edge X-ray-Absorption Fine-Structure (NEXAFS) and X-ray Photoemission Spectroscopy (XPS) at the C K-edge with those of density functional theory (DFT) calculations. The calculated NEXAFS spectra provide a comprehensive description of the main experimental features and allow their attribution. The evolution of the C1s NEXAFS spectral features is analyzed as a function of the number of thiophene rings; a tendency to a stabilization for increasing chain length is found. The computation of the binding energy allows to assign the experimental XPS peaks to the different carbon sites on the basis of both the inductive effects generated by the presence of the S atom as well as of the differential aromaticity effects.

9.Ab initio investigation of laser-induced ultrafast demagnetization of L1$_0$ FePt: Intensity dependence and importance of electron coherence

Authors:M. S. Mrudul, Peter M. Oppeneer

Abstract: We theoretically investigate the optically-induced demagnetization of ferromagnetic FePt using the time-dependent density functional theory (TDDFT). We compare the demagnetization mechanism in the perturbative and nonperturbative limits of light-matter interaction and show how the underlying mechanism of the ultrafast demagnetization depends on the driving laser intensity. Our calculations show that the femtosecond demagnetization in TDDFT is a longitudinal magnetization reduction and results from a nonlinear optomagnetic effect, akin to the inverse Faraday effect. The demagnetization scales quadratically with the electric field $E$ in the perturbative limit, i.e., $\Delta M_z \propto E^{2}$. Moreover, the magnetization dynamics happens dominantly at even multiples $n\omega_0$, ($n = 0, 2, \cdots$) of the pump-laser frequency $\omega_0$, whereas odd multiples of $\omega_0$ do not contribute. We further investigate the demagnetization in conjunction to the optically-induced change of electron occupations and electron correlations. Correlations within the Kohn-Sham local-density framework are shown to have an appreciable yet distinct effect on the amount of demagnetization depending on the laser intensity. Comparing the ${ab~initio}$ computed demagnetizations with those calculated from spin occupations, we show that electronic coherence plays a dominant role in the demagnetization process, whereas interpretations based on the time-dependent occupation numbers poorly describe the ultrafast demagnetization.

1.Superconductivity in a van der Waals layered quasicrystal

Authors:Yuki Tokumoto, Kotaro Hamano, Sunao Nakagawa, Yasushi Kamimura, Shintaro Suzuki, Ryuji Tamura, Keiichi Edagawa

Abstract: van der Waals (vdW) layered transition-metal chalcogenides are attracting significant attention owing to their fascinating physical properties. This group of materials consists of abundant members with various elements, having a variety of different structures. However, all vdW layered materials studied to date have been limited to crystalline materials, and the physical properties of vdW layered quasicrystals have not yet been reported. Here, we report on the discovery of superconductivity in a vdW layered quasicrystal of Ta1.6Te. The electrical resistivity, magnetic susceptibility, and specific heat of the Ta1.6Te quasicrystal fabricated by reaction sintering, unambiguously validated the occurrence of bulk superconductivity at a transition temperature of ~1 K. This discovery can pioneer new research on assessing the physical properties of vdW layered quasicrystals as well as two-dimensional quasicrystals; moreover, it paves the way toward new frontiers of superconductivity in thermodynamically stable quasicrystals, which has been the predominant challenge facing condensed matter physics since the discovery of quasicrystals almost four decades ago.

2.Layer thickness crossover of type-II multiferroic magnetism in NiI2

Authors:Shuang Wu, Xinyu Chen, Canyu Hong, Xiaofei Hou, Zhanshan Wang, Zhiyuan Sheng, Zeyuan Sun, Yanfeng Guo, Shiwei Wu

Abstract: The discovery of atomically thin van der Waals ferroelectric and magnetic materials encourages the exploration of 2D multiferroics, which holds the promise to understand fascinating magnetoelectric interactions and fabricate advanced spintronic devices. In addition to building a heterostructure consisting of ferroelectric and magnetic ingredients, thinning down layered multiferroics of spin origin such as NiI2 becomes a natural route to realize 2D multiferroicity. However, the layer-dependent behavior, widely known in the community of 2D materials, necessitates a rigorous scrutiny of the multiferroic order in the few-layer limit. Here, we interrogate the layer thickness crossover of helimagnetism in NiI2 that drives the ferroelectricity and thereby type-II multiferroicity. By using wavelength-dependent polarization-resolved optical second harmonic generation (SHG) to probe the ferroic symmetry, we find that the SHG arises from the inversion-symmetry-breaking magnetic order, not previously assumed ferroelectricity. This magnetism-induced SHG is only observed in bilayer or thicker layers, and vanishes in monolayer, suggesting the critical role of interlayer exchange interaction in breaking the degeneracy of geometrically frustrated spin structures in triangular lattice and stabilizing the type-II multiferroic magnetism in few-layers. While the helimagnetic transition temperature is layer dependent, the few-layer NiI2 exhibits another thickness evolution and reaches the bulk-like behavior in trilayer, indicated by the intermediate centrosymmetric antiferromagnetic state as revealed in Raman spectroscopy. Our work therefore highlights the magnetic contribution to SHG and Raman spectroscopy in reduced dimension and guides the optical study of 2D multiferroics.

3.Lattice dynamics and spin excitations in the metal-organic framework [CH$_3$NH$_3$][Co(HCOO)$_3$]

Authors:Lei Ding, Claire V. Colin, Virginie Simonet, Chris Stock, Jean-Blaise Brubach, Marine Verseils, Pascale Roy, Victoria Garcia Sakai, Michael M. Koza, Andrea Piovano, Alexandre Ivanov, Jose A. Rodriguez-Rivera, Sophie de Brion, Manila Songvilay

Abstract: In metal-organic-framework (MOF) perovskites, both magnetic and ferroelectric orderings can be readily realized by compounding spin and charge degrees of freedom. The hydrogen bonds that bridge the magnetic framework and organic molecules have long been thought of as a key in generating multiferroic properties. However, the underlying physical mechanisms remain unclear. Here, we combine neutron diffraction, quasielastic and inelastic neutron scattering, and THz spectroscopy techniques to thoroughly investigate the dynamical properties of the multiferroic MOF candidate [CH$_3$NH$_3$][Co(HCOO)$_3$] through its multiple phase transitions. The wide range of energy resolutions reachable by these techniques enables us to scrutinize the coupling between the molecules and the framework throughout the phase transitions and interrogate a possible magnetoelectric coupling. Our results also reveal a structural change around 220 K which may be associated with the activation of a nodding donkey mode of the methylammonium molecule due to the ordering of the CH$_3$ groups. Upon the occurrence of the modulated phase transition around 130 K, the methylammonium molecules undergo a freezing of its reorientational motions which is concomitant with a change of the lattice parameters and anomalies of collective lattice vibrations. No significant change has been however observed in the lattice dynamics around the magnetic ordering, which therefore indicates the absence of a substantial magneto-electric coupling in zero-field.

4.Two-Dimensional Platinum Telluride with Ordered Te Vacancy Superlattice for Efficient and Robust Hydrogen Evolution

Authors:Xin Xu, Xuechun Wang, Shuming Yu, Guowei Liu, Yaping Ma, Hao Li, Jiangang Yang, Chenhui Wang, Jing Li, Tao Sun, Weifeng Zhang, Kedong Wang, Nan Xu, Fangfei Ming, Ping Cui, Zhenyu Zhang, Xudong Xiao

Abstract: Defect engineering to activate the basal planes of transition metal dichalcogenides (TMDs) is critical for the development of TMD-based electrocatalysts as the chemical inertness of basal planes restrict their potential applications in hydrogen evolution reaction (HER). Here, we report the synthesis and evaluation of few-layer (7x7)-PtTe2-x with an ordered, well-defined and high-density Te vacancy superlattice. Compared with pristine PtTe2, (2x2)-PtTe2-x and Pt(111), (7x7)-PtTe2-x exhibits superior HER activities in both acidic and alkaline electrolytes due to its rich structures of undercoordinated Pt sites. Furthermore, the (7x7)-PtTe2-x sample features outstanding catalytic stability even compared to the state-of-the-art Pt/C catalyst. Theoretical calculations reveal that the interactions between various undercoordinated Pt sites due to proximity effect can provide superior undercoordinated Pt sites for hydrogen adsorption and water dissociation. This work will enrich the understanding of the relationship between defect structures and electrocatalytic activities and provide a promising route to develop efficient Pt-based TMD electrocatalysts.

5.Inorganic synthesis-structure maps in zeolites with machine learning and crystallographic distances

Authors:Daniel Schwalbe-Koda, Daniel E. Widdowson, Tuan Anh Pham, Vitaliy A. Kurlin

Abstract: Zeolites are inorganic materials known for their diversity of applications, synthesis conditions, and resulting polymorphs. Although their synthesis is controlled both by inorganic and organic synthesis conditions, computational studies of zeolite synthesis have focused mostly on organic template design. In this work, we use a strong distance metric between crystal structures and machine learning (ML) to create inorganic synthesis maps in zeolites. Starting with 253 known zeolites, we show how the continuous distances between frameworks reproduce inorganic synthesis conditions from the literature without using labels such as building units. An unsupervised learning analysis shows that neighboring zeolites according to our metric often share similar inorganic synthesis conditions, even in template-based routes. In combination with ML classifiers, we find synthesis-structure relationships for 14 common inorganic conditions in zeolites, namely Al, B, Be, Ca, Co, F, Ga, Ge, K, Mg, Na, P, Si, and Zn. By explaining the model predictions, we demonstrate how (dis)similarities towards known structures can be used as features for the synthesis space. Finally, we show how these methods can be used to predict inorganic synthesis conditions for unrealized frameworks in hypothetical databases and interpret the outcomes by extracting local structural patterns from zeolites. In combination with template design, this work can accelerate the exploration of the space of synthesis conditions for zeolites.

6.Breakdown of phonon band theory in MgO

Authors:Gabriele Coiana, Johannes Lischner, Paul Tangney

Abstract: We present a series of detailed images of the distribution of kinetic energy among frequencies and wavevectors in the bulk of an MgO crystal as it is heated slowly until it melts. These spectra, which are Fourier transforms of velocity-velocity correlation functions calculated from accurate molecular dynamics (MD) simulations, provide a valuable perspective on the growth of thermal disorder in ionic crystals. We use them to explain why the most striking and rapidly-progressing departures from a band structure occur among longitudinal optical (LO) modes, which would be the least active modes at low temperature ($T$) if phonons did not interact. The degradation of the LO band begins, at low $T$, as an anomalously-large broadening of modes near the center of the Brillouin zone (BZ), which gradually spreads towards the BZ boundary. The LO band all but vanishes before the crystal melts, and transverse optical (TO) modes' spectral peaks become so broad that the TO branches no longer appear band-like. Acoustic bands remain relatively well defined until melting of the crystal manifests in the spectra as their sudden disappearance. We argue that, even at high $T$, the long wavelength acoustic (LWA) phonons of an ionic crystal can remain partially immune to disorder generated by its LO phonons; whereas, even at low $T$, its LO phonons can be strongly affected by LWA phonons. This is because LO displacements average out in much less than the period of an LWA phonon; whereas during each period of an LO phonon an LWA phonon appears as a quasistatic perturbation of the crystal, which warps the LO mode's intrinsic electric field. LO phonons are highly sensitive to acoustic warping of their intrinsic fields because their frequencies depend strongly on them: They cause the large frequency difference between LO and TO bands known as {\em LO-TO splitting}.

7.Critical Analysis of Skyrmionic Material Co$_{6.5}$Ru$_{1.5}$Zn$_8$Mn$_4$: a complex interplay of short and long-range interactions around the transition temperature

Authors:Afsar Ahmed, Arnab Bhattacharya, Samik DuttaGupta, I. Das

Abstract: Critical behaviour study in magnetism is important owing to its application for understanding the nature of underlying spin-spin interactions by determining the critical parameters in the vicinity of a phase transition. In this article, we report the novel manifestation of crossover behaviour between two universality classes governing spin interaction across the ferromagnetic Curie temperature $T_C$ in critical scaling of anomalous hall conductivity isotherms for a skyrmion-hosting itinerant ferromagnet Co$_{6.5}$Ru$_{1.5}$Zn$_{8}$Mn$_4$. Along with the magnetotransport scaling, the traditional critical behaviour of magnetic isotherms yields $\beta$ = 0.423 $\pm$ 0.004, $\gamma$ = 1.08 $\pm$ 0.016, and $\delta$ = 3.553 $\pm$ 0.009 suggesting the 3D Heisenberg and Mean field type of spin interactions below and above $T_C$, respectively. The isotropic magnetic exchange strength decays as $J(r) \approx r^{ -4.617}$, implying the prevalence of crossover from long-range ordering to short-range type interaction. In addition, the existence of a fluctuation-disordered magnetic phase immediately below $T_C$ has been observed in the magnetocaloric effect. The novel approach of generating a low-field phase diagram employing the quantitative criterion of phase transition from the scaling of isothermal magneto-entropic change shows an excellent convergence with the phase boundaries obtained from conventional magnetic and anomalous Hall conductivity scaling. This simultaneous scaling of magnetization and AHC isotherms for systems with crossover behaviour establishes the universality of the magnetotransport-based critical scaling approach which still remains in its infancy.

1.Coupling of the triple-Q state to the atomic lattice by anisotropic symmetric exchange

Authors:Felix Nickel, André Kubetzka, Soumyajyoti Haldar, Roland Wiesendanger, Stefan Heinze, Kirsten von Bergmann

Abstract: We identify the triple-Q (3Q) state as magnetic ground state in Pd/Mn and Rh/Mn bilayers on Re(0001) using spin-polarized scanning tunneling microscopy and density functional theory. An atomistic model reveals that in general the 3Q state with tetrahedral magnetic order and zero net spin moment is coupled to a hexagonal atomic lattice in a highly symmetric orientation via the anisotropic symmetric exchange interaction, whereas other spin-orbit coupling terms cancel due to symmetry. Our experiments are in agreement with the predicted orientation of the 3Q state. A distortion from the ideal tetrahedral angles leads to other orientations of the 3Q state which, however, results in a reduced topological orbital magnetization compared to the ideal 3Q state.

2.Magneto-transport and electronic structures in MoSi2 bulks and thin films with different orientations

Authors:W. Afzal, F. Yun, Z. Li, Z. Yue, W. Zhao, L. Sang, G. Yang, Y. He, G. Peleckis, M. Fuhrer, X. Wang

Abstract: We report a comprehensive study of magneto-transport properties in MoSi2 bulk and thin films. Textured MoSi2 thin films of around 70 nm were deposited on silicon substrates with different orientations. Giant magnetoresistance of 1000% was observed in sintered bulk samples while MoSi2 single crystals exhibit a magnetoresistance (MR) value of 800% at low temperatures. At the low temperatures, the MR of the textured thin films show weak anti-localization behaviour owing to the spin orbit coupling effects. Our first principle calculation show the presence of surface states in this material. The resistivity of all the MoSi2 thin films is significantly low and nearly independent of the temperature, which is important for electronic devices.

3.Oxide layer dependent orbital torque efficiency in ferromagnet/Cu/Oxide heterostructures

Authors:Junyeon Kim, Jun Uzuhashi, Masafumi Horio, Tomoaki Senoo, Dongwook Go, Daegeun Jo, Toshihide Sumi, Tetsuya Wada, Iwao Matsuda, Tadakatsu Ohkubo, Seiji Mitani, Hyun-Woo Lee, YoshiChika Otani

Abstract: The utilization of orbital transport provides a versatile and efficient spin manipulation mechanism. As interest in orbital-mediated spin manipulation grows, we face a new issue to identify the underlying physics that determines the efficiency of orbital torque (OT). In this study, we systematically investigate the variation of OT governed by orbital Rashba-Edelstein effect at the Cu/Oxide interface, as we change the Oxide material. We find that OT varies by a factor of ~2, depending on the Oxide. Our results suggest that the active electronic interatomic interaction (hopping) between Cu and oxygen atom is critical in determining OT. This also gives us an idea of what type of material factors is critical in forming a chiral orbital Rashba texture at the Cu/Oxide interface.

4.High pressure-temperature phase diagram of ammonia hemihydrate

Authors:L. Andriambariarijaona, F. Datchi H. Zhang, K. Béneut, B. Baptiste, N. Guignot, S. Ninet

Abstract: We report a comprehensive experimental investigation of the phase diagram of ammonia hemihydrate (AHH) in the range of 2-30 GPa and 300-700 K, based on Raman spectroscopy and x-ray diffraction experiments and visual observations. Four solid phases, denoted AHH-II, DIMA, pbcc and qbcc, are present in this domain, one of which, AHH-qbcc was discovered in this work. We show that, unlike previously thought, the body-centered cubic (bcc) phase obtained on heating AHH-II below 10 GPa, denoted here as AHH-pbcc, is distinct from the DIMA phase, although both present the same bcc structure and O/N positional disorder. Our results actually indicates that AHH-pbcc is a plastic form of DIMA, characterized by free molecular rotations. AHH-qbcc is observed in the intermediate P-T range between AHH-II and DIMA. It presents a complex x-ray pattern reminiscent of the "quasi-bcc" structures that have been theoretically predicted, although none of these structures is consistent with our data. The transition lines between all solid phases as well as the melting curve have been mapped in detail, showing that: (1) the new qbcc phase is the stable one in the intermediate P-T range 10-19 GPa, 300-450 K, although the II-qbcc transition is kinetically hindered for T < 450 K, and II directly transits to DIMA in a gradual fashion from 25 to 35 GPa at 300 K. (2) The stability domain of qbcc shrinks above 450 K and eventually terminates at a pbcc-qbcc-DIMA triple point at 21.5 GPa-630 K. (3) A direct and reversible transition occurs between AHH-pbcc and DIMA above 630 K. (4) The pbcc solid stability domain extends up to the melting line above 3 GPa, and a II-pbcc-liquid triple point is identified at 3 GPa-320 K.

5.Electrons in helical magnetic field: a new class of topological metals

Authors:Yu. B. Kudasov

Abstract: Two theorems on electron states in helimagnets are proved. They reveal a Kramers-like degeneracy in helical magnetic field. Since a commensurate helical magnetic system is transitionally invariant with two multiple periods (ordinary translations and generalized ones with rotations), the band structure turns out to be topologically nontrivial. Together with the degeneracy, this gives an unusual spin structure of electron bands. A 2D model of nearly free electrons is proposed to describe conductive hexagonal palladium layers under an effective field of magnetically ordered CrO$_2$ spacers in PdCrO$_2$. The spin texture of the Fermi surface leads to abnormal conductivity.

6.Dynamic Formation of Preferentially Lattice Oriented, Self Trapped Hydrogen Clusters

Authors:M. A. Cusentino, E. L. Sikorski, M. J. McCarthy, A. P. Thompson, M. A. Wood

Abstract: A series of MD and DFT simulations were performed to investigate hydrogen self-clustering and retention in tungsten. Using a newly develop machine learned interatomic potential, spontaneous formation of hydrogen platelets was observed after implanting low-energy hydrogen into tungsten at high fluxes and temperatures. The platelets formed along low miller index orientations and neighboring tetrahedral and octahedral sites and could grow to over 50 atoms in size. High temperatures above 600 K and high hydrogen concentrations were needed to observe significant platelet formation. A critical platelet size of six hydrogen atoms was needed for long term stability. Platelets smaller than this were found to be thermally unstable within a few nanoseconds. To verify these observations, characteristic platelets from the MD simulations were simulated using large-scale DFT. DFT corroborated the MD results in that large platelets were also found to be dynamically stable for five or more hydrogen atoms. The LDOS from the DFT simulated platelets indicated that hydrogen atoms, particularly at the periphery of the platelet, were found to be at least as stable as hydrogen atoms in bulk tungsten. In addition, electrons were found to be localized around hydrogen atoms in the platelet itself and that hydrogen atoms up to 4.2 Angstrom away within the platelet were found to be bonded suggesting that the hydrogen atoms are interacting across longer distances than previously suggested. These results reveal a self-clustering mechanisms for hydrogen within tungsten in the absence of radiation induced or microstructural defects that could be a precursor to blistering and potentially explain the experimentally observed high hydrogen retention particularly in the near surface region.

7.Cubic silicon carbide under tensile pressure: Spinodal instability

Authors:Carlos P. Herrero, Rafael Ramirez, Gabriela Herrero-Saboya

Abstract: Silicon carbide is a hard, semiconducting material presenting many polytypes, whose behavior under extreme conditions of pressure and temperature has attracted large interest. Here we study the mechanical properties of 3C-SiC over a wide range of pressures (compressive and tensile) by means of molecular dynamics simulations, using an effective tight-binding Hamiltonian to describe the interatomic interactions. The accuracy of this procedure has been checked by comparing results at T = 0 with those derived from ab-initio density-functional-theory calculations. This has allowed us to determine the metastability limits of this material and in particular the spinodal point (where the bulk modulus vanishes) as a function of temperature. At T = 300 K, the spinodal instability appears for a lattice parameter about 20% larger than that corresponding to ambient pressure. At this temperature, we find a spinodal pressure P_s = -43 GPa, which becomes less negative as temperature is raised (P_s = -37.9 GPa at 1500 K). These results pave the way for a deeper understanding of the behavior of crystalline semiconductors in a poorly known region of their phase diagrams.

8.Efficient, Accurate, and Transferable Machine Learning Potentials: Application to Dislocations and Cracks in Iron

Authors:Lei Zhang, Gábor Csányi, Erik van der Giessen, Francesco Maresca

Abstract: Machine learning interatomic potentials (ML-IAPs) enable quantum-accurate classical molecular dynamics (MD) simulations of large systems, including defects like dislocations and cracks. While various ML-IAPs are able to replicate DFT per-atom energies with root-mean-square error (RMSE) ~1 meV, the ability to accurately predict systems larger than density functional theory (DFT) supercells is unclear to date. Based on two independent DFT databases, we optimise a variety of ML-IAPs based on four state-of-the-art packages and show the Pareto front of the computational speed versus testing energy and force RMSE. We then perform extensive validation on a broad range of properties that are crucial to simulate plasticity and fracture of metals. The core structures and Peierls barriers of screw, M111 and three edge dislocations are compared with DFT/MD results from published literature. We find that these properties can be sensitive to the database and the ML scheme. Next, we compute the traction-separation curve and critical stress intensity factor based on K-test, in which the effects of the database and cutoff radius are visible. Cleavage on the pre-existing crack plane, without dislocation emission, is found to be the atomistic fracture mechanism under pure mode-I loading, independent of the ML packages and the training DFT database. Our findings not only reveal the correlation between RMSE and the average error of predicted physical properties, the dislocation properties, and fracture mechanism in bcc iron but also highlight the importance of validating ML-IAPs by using indicators beyond RMSE, including model uncertainty quantification.

9.DFT+μ: Density Functional Theory for Muon Site Determination

Authors:S. J. Blundell, T. Lancaster

Abstract: The technique of muon spin rotation ({\mu}SR) has emerged in the last few decades as one of the most powerful methods of obtaining local magnetic information. To make the technique fully quantitative, it is necessary to have an accurate estimate of where inside the crystal structure the muon implants. This can be provided by density functional theory calculations using an approach that is termed DFT+{\mu}, density functional theory with the implanted muon included. This article reviews this approach, describes some recent successes in particular {\mu}SR experiments, and suggests some avenues for future exploration.

10.Altermagnetic surface states: towards the observation and utilization of altermagnetism in thin films, interfaces and topological materials

Authors:Raghottam M Sattigeri, Giuseppe Cuono, Carmine Autieri

Abstract: The altermagnetism influences the electronic states allowing the presence of non-relativistic spinsplittings. Since altermagnetic spin-splitting is present along specific k-paths of the 3D Brillouin zone, we expect that the altermagnetic surface states will be present on specific surface orientations. We unveil the properties of the altermagnetic surface states considering three representative space groups: tetragonal, orthorhombic and hexagonal. We calculate the 2D projected Brillouin zone from the 3D Brillouin zone. We study the surfaces with their respective 2D Brillouin zones establishing where the spin-splittings with opposite sign merge annihilating the altermagnetic properties and on which surfaces the altermagnetism is preserved. Looking at the three principal surface orientations, we find that for several cases two surfaces are blind to the altermagnetism, while the altermagnetism survives for one surface orientation. Which surface preserves the altermagnetism depends also on the magnetic order. We show that an electric field orthogonal to the blind surface can activate the altermagnetism. Our results predict which surfaces to cleave in order to preserve altermagnetism in surfaces or interfaces and this paves the way to observe non-relativistic altermagnetic spin-splitting in thin films via spin-resolved ARPES and to interface the altermagnetism with other collective modes. We open future perspectives for the study of altermagnetic effects on the trivial and topological surface states.

1.Large scale synthesis of 2D graphene oxide by mechanical milling of 3D carbon nanoparticles in air

Authors:Sandip Das, Subhamay Pramanik, Sumit Mukherjee, Tatan Ghosh, Rajib Nath, Probodh K. Kuiri

Abstract: Graphene oxide (GO) is one of the important functional materials. Large-scale synthesis of it is very challenging. Following a simple cost-effective route, large-scale GO was produced by mechanical (ball) milling, in air, of carbon nanoparticles (CNPs) present in carbon soot in the present study. The thickness of the GO layer was seen to decrease with an increase in milling time. Ball milling provided the required energy to acquire the in-plane graphitic order in the CNPs reducing the disorders in it. As the surface area of the layered structure became more and more with the increase in milling time, more and more oxygen of air got attached to the carbon in graphene leading to the formation of GO. An increase in the time of the ball mill up to 5 hours leads to a significant increase in the content of GO. Thus ball milling can be useful to produce large-scale two-dimensional GO for a short time.

2.Defects, band bending and ionization rings in MoS2

Authors:Iolanda Di Bernardo, James Blyth, Liam Watson, Kaijian Xing, Yi-Hsun Chen, Shao-Yu Chen, Mark T. Edmonds, Michael S. Fuhrer

Abstract: Chalcogen vacancies in transition metal dichalcogenides are widely acknowledged as both donor dopants and as a source of disorder. The electronic structure of sulphur vacancies in MoS2 however is still controversial, with discrepancies in the literature pertaining to the origin of the in-gap features observed via scanning tunneling spectroscopy (STS) on single sulphur vacancies. Here we use a combination of scanning tunnelling microscopy (STM) and STS to study embedded sulphur vacancies in bulk MoS2 crystals. We observe spectroscopic features dispersing in real space and in energy, which we interpret as tip position- and bias-dependent ionization of the sulphur vacancy donor due to tip induced band bending (TIBB). The observations indicate that care must be taken in interpreting defect spectra as reflecting in-gap density of states, and may explain discrepancies in the literature.

3.Antiferromagnetic topological insulating state in Tb$_{0.02}$Bi$_{1.08}$Sb$_{0.9}$Te$_2$S single crystals

Authors:Lei Guo, Weiyao Zhao, Qile Li, Meng Xu, Lei Chen, Abdulhakim Bake, Thi-Hai-Yen Vu, Yahua He, Yong Fang, David Cortie, Sung-Kwan Mo, Mark Edmonds, Xiaolin Wang, Shuai Dong, Julie Karel, Ren-Kui Zheng

Abstract: Topological insulators are emerging materials with insulating bulk and symmetry protected nontrivial surface states. One of the most fascinating transport behaviors in a topological insulator is the quantized anomalous Hall insulator, which has been observed inmagnetic-topological-insulator-based devices. In this work, we report a successful doping of rare earth element Tb into Bi$_{1.08}$Sb$_{0.9}$Te$_2$S topological insulator single crystals, in which the Tb moments are antiferromagnetically ordered below ~10 K. Benefiting from the in-bulk-gap Fermi level, transport behavior dominant by the topological surface states is observed below ~ 150 K. At low temperatures, strong Shubnikov-de Haas oscillations are observed, which exhibit 2D-like behavior. The topological insulator with long range magnetic ordering in rare earth doped Bi$_{1.08}$Sb$_{0.9}$Te$_2$S single crystal provides an ideal platform for quantum transport studies and potential applications.

4.Trions, Exciton Dynamics and Spectral Modifications in Doped Carbon Nanotubes: A Singular Defect-Driven Mechanism

Authors:Klaus H. Eckstein, Pascal Kunkel, Markus Voelckel, Friedrich Schöppler, Tobias Hertel

Abstract: Doping substantially influences the electronic and photophysical properties of semiconducting single-wall carbon nanotubes (s-SWNTs). Although prior studies have noted that surplus charge carriers modify optical spectra and accelerate non-radiative exciton decay in doped s-SWNTs, a direct mechanistic correlation of trion formation, exciton dynamics and energetics remains elusive. This work examines the influence of doping-induced non-radiative decay and exciton confinement on s-SWNT photophysics. Using photoluminescence, continuous-wave absorption, and pump-probe spectroscopy, we show that localization of and barrier formation by trapped charges can be jointly quantified using diffusive exciton transport- and particle-in-the-box models, yielding a one-to-one correlation between charge carrier concentrations derived from these models. The study highlights the multifaceted role of exohedral counterions, which trap charges to create quenching sites, form barriers to exciton movement, and host trion states. This contributes significantly to understanding and optimizing the photophysical properties of doped SWNTs.

5.Structure maps for MAX phases formability revisited

Authors:Yiming Zhang, Yongjia Xu, Qing Huang, Shiyu Du, Mian Li, Youbing Li, Zeyu Mao, Qi Han

Abstract: The extraordinary chemical diversity of MAX phases raises the question of how many and which novel ones are yet to be discovered. The conventional schemes rely either on executions of well designed experiments or elaborately crafted calculations; both of which have been key tactics within the past several decades that have yielded many of important new materials we are studying and using today. However, these approaches are expensive despite the emergence of high throughput automations or evolution of high speed computers. In this work, we have revisited the in prior proposed light duty strategy, i.e. structure mapping, for describing the genomic conditions under which one MAX phase could form; that allow us to make successful formability and non formability separation of MAX phases with a fidelity of 95.5%. Our results suggest that the proposed coordinates, and further the developed structure maps, are able to offer a useful initial guiding principles for systematic screenings of potential MAX phases and provide untapped opportunities for their structure prediction and materials design.

6.Coexistence of Logarithmic and SdH Quantum Oscillations in Ferromagnetic Cr-doped Tellurium Single Crystals

Authors:Shu-Juan Zhang, Lei Chen, Shuang-Shuang Li, Ying Zhang, Jian-Min Yan, Fang Tang, Yong Fang, Lin-Feng Fei, Weiyao Zhao, Julie Karel, Yang Chai, Ren-Kui Zheng

Abstract: We report the synthesis of transition-metal-doped ferromagnetic elemental single-crystal semiconductors with quantum oscillations using the physical vapor transport method. The 7.7 atom% Cr-doped Te crystals (Cr_Te) show ferromagnetism, butterfly-like negative magnetoresistance in the low temperature (< 3.8 K) and low field (< 0.15 T) region, and high Hall mobility, e.g., 1320 cm2 V-1 s-1 at 30 K and 350 cm2 V-1 s-1 at 300 K, implying that Cr_Te crystals are ferromagnetic elemental semiconductors. When B // c // I, the maximum negative MR is -27% at T = 20 K and B = 8 T. In the low temperature semiconducting region, Cr_Te crystals show strong discrete scale invariance dominated logarithmic quantum oscillations when the direction of the magnetic field B is parallel to the [100] crystallographic direction and show Landau quantization dominated Shubnikov-de Haas (SdH) oscillations for B // [210] direction, which suggests the broken rotation symmetry of the Fermi pockets in the Cr_Te crystals. The findings of coexistence of multiple quantum oscillations and ferromagnetism in such an elemental quantum material may inspire more study of narrow bandgap semiconductors with ferromagnetism and quantum phenomena.

7.Abnormal CO2 and H2O Diffusion in CALF-20(Zn) Metal-Organic Framework Angstropores

Authors:Magnin Yann, Dirand Estelle, Maurin Guillaume, Llewellyn Philip

Abstract: Carbon mitigation is one challenging issue that the world is facing. To tackle deleterious impacts of CO2, processes emerged, including chemisorption from amine based solvents, and more recently physisorption in porous solids. While CO2 capture from amine is more mature, this process is corrosive and detrimental for environment. Physisorption in Metal-Organic Frameworks (MOFs) is currently attracting a considerable attention, however the selection of the optimum sorbent is still challenging. While CO2 adsorption by MOFs have been widely explored from a thermodynamics standpoint, dynamical aspects remain less explored. CALF-20(Zn) MOF was recently proposed as a promising alternative to the commercially used CO2 13X zeolite sorbents, however, in-depth understanding of microscopic mechanisms originating its good performance still have to be achieved. In this report, we deliver a microscopic insight of CO2 and H2O in CALF-20(Zn) by atomistic simulations. CALF-20(Zn) revealed to exhibit unconventional guest-host behaviors that give rise to abnormal thermodynamic and diffusion. The hydrophobic nature of the solid leads to a low water adsorption enthalpy at low loading followed by a gradual increase, driven by strong water hydrogen bonds, found to arrange as quasi 1D water wires in MOF porosity, recalling water behavior in carbon nanotubes and aquaporins. While no super-diffusion found, this behavior was shown to impact diffusion along with guests loading, with a minimum correlated with inflection point of adsorption isotherm corresponding to wires formation. Interestingly, diffusion of both CO2 and H2O were also found to be of the same order of magnitude with similar non-linear behaviors.

8.Intrinsic ferroelectric switching in two dimensions

Authors:Liyi Bai, Changming Ke, Tianyuan Zhu, Shi Liu

Abstract: Two-dimensional (2D) ferroelectric semiconductors with electrically addressable polarization present opportunities for integrating ferroelectrics into high-density ultrathin nanoelectronics. However, efforts to improve critical characteristics such as switching speed and endurance of 2D ferroelectric-based devices have been hampered by the limited microscopic understanding of ferroelectric switching in 2D. Taking 2D $\alpha$-In$_2$Se$_3$ with out-of-plane polarization as a model, we employ deep-learning-assisted large-scale molecular dynamics simulations to analyze the switching processes of 2D domains and 1D domain walls, revealing mechanisms fundamentally different from those of bulk ferroelectrics. We discover that a single domain is unswitchable by an out-of-plane electric field due to forbidden splitting of Wyckoff orbits. This "splitting restriction principle" also explains the robust POP presented in sliding ferroelectricity and moir\'e ferroelectricity. Counterintuitively, 1D domain walls are easily moved by in-plane fields despite lacking in-plane effective polarization. The field-driven 1D walls exhibit unusual avalanche dynamics characterized by abrupt, intermittent moving patterns. The propagating velocity at various temperatures, field orientations, and strengths can be statistically described with a single creep equation, featuring a dynamical exponent of 2 that is distinct from all known values for elastic interfaces moving in disordered media. We demonstrate a tunable onset field for the intrinsic creep-depinning transition, suggesting a simple route for on-demand configuration of switching speed.

9.Towards understanding the electronic structure of the simpler members of two-dimensional halide-perovskites

Authors:Efstratios Manousakis

Abstract: In this paper we analyze the band-structure of two-dimensional (2D) halide perovskites by considering structures related to the simpler case of the series, (BA)$_2$PbI$_4$, in which PbI$_4$ layers are intercalated with butylammonium (BA=CH$_3$(CH$_2$)$_3$NH$_3$) organic ligands. We use density-functional-theory (DFT) based calculations and tight-binding (TB) models aiming to discover a simple description of the bands in the vicinity of the valence-band maximum and the conduction-band minimum. We find that the atomic orbitals of the butylammonium chains have negligible contribution to the Bloch states which form the conduction and valence bands in near the Fermi energy. Our calculations reveal a rather universal, i.e., independent of the intercalating BA, rigid-band picture characteristic of the layered perovskite ``matrix''. Besides demonstrating the above conclusion, the main goal of this paper is to find accurate TB models which capture the essential features of the DFT bands near the Fermi energy. First, we ignore electron hopping along the $c$-axis and the octahedral distortions and this increased symmetry halves the Bravais-lattice unit-cell size and the Brillouin zone unfolds to a 45$^{\circ}$ rotated square and this allows some analytical handling of the 2D TB-Hamiltonian. The Pb $6s$ and I $5s$ orbitals are far away from the Fermi level and, thus, we integrate them out to obtain an effective model which only includes hybridized Pb $6p$ and I $5p$ states. Our TB-based treatment a) provides a good quantitative description of the DFT band-structure, b) helps us conceptualize the complex electronic structure in the family of these materials in a simple way and c) yields the one-body part to be combined with appropriately screened electron interaction to describe many-body effects, such as excitonic bound-states.

1.Titanium and titanium oxides at the K- and L-edges: validating theoretical calculations of X-ray absorption and X-ray emission spectra with measurements

Authors:Karina Bzheumikhova, John Vinson, Rainer Unterumsberger, Malte Wansleben, Claudia Zech, Kai Schüler, Philipp Hönicke, Burkhard Beckhoff

Abstract: Using well-calibrated experimental data we validate theoretical X-ray absorption spectroscopy (XAS) as well as X-ray emission spectroscopy (XES) calculations for titanium (Ti), titanium oxide (TiO), and titanium dioxide (TiO$_2$) at the Ti K- and L-edges as well as O K-edge. XAS and XES in combination with a multi-edge approach offer a detailed insight into the electronic structure of materials since both the occupied and unoccupied states, are probed. The experimental results are compared with ab initio calculations from the OCEAN package which uses the Bethe-Salpeter equation (BSE) approach. Using the same set of input parameters for each compound for calculations at different edges, the transferability of the OCEAN calculations across different spectroscopy methods and energy ranges is validated. Thus, the broad applicability for analysing and interpreting the electronic structure of materials with the OCEAN package is shown.

2.Visualization of out-of-plane spin generation in mirror symmetry broken Co

Authors:Yakun Liu, Fanrui Hu, Guoyi Shi, Hyunsoo Yang

Abstract: Generating out-of-plane spins in sputtered materials holds immense potential for achieving field-free spin-orbit torque switching in practical applications and mass production. In this work, we present the detection of out-of-plane spins from single-layer ferromagnetic Co layers, which are visualized through helicity-dependent photomapping techniques. Our experiments have shown that out-of-plane spin generation is dependent on the magnetization direction, current density, and Co thickness. Our findings indicate that amorphous sputtered Co can be a promising candidate as an out-of-plane spin source material for industrial massive production.

3.Temperature dependence of photo-induced phase segregation in bromide-rich mixed halide perovskites

Authors:Grigorii Verkhogliadov, Ross Haroldson, Dmitry Gets, Anvar A. Zakhidov, Sergey V. Makarov

Abstract: Mixed halide perovskites undergo phase segregation, manifested as spectral red-shifting of photoluminescence spectra under illumination. In the iodine-bromide mixed perovskites, the origin of the low-energy luminescence is related to iodine-enriched domains formation. Such domains create favorable bands for the induced carrier funneling into them. Despite the phase segregation process is crucial for mixed halide perovskite-based optoelectronics, numerous gaps exist within the understanding of this phenomenon. One such gap pertains to the emergence of temporary and intermediate photoluminescence peaks during the initial stages of phase segregation. However, these peaks appear only within the first few seconds of illumination. Nevertheless, the decreasing temperature may prolong these initial stages. In this work, we carry out a detailed study of the temperature dependence of anion segregation in MAPbBr_2I and MAPbBr2.5I0.5 halide perovskites, to obtain a deeper comprehension of segregation processes, particularly during their initial stages. The temporal evolution of low-temperature photoluminescence reveals the undergoing of the intermediate stage during the segregation process and temperature-related phase transition from orthorhombic to tetragonal phase. To complement the phase segregation study, the temperature dependence of time-resolved photoluminescence spectroscopy is provided, allowing us to estimate the change in the photoluminescence lifetimes for the initial and segregated peaks with temperature.

4.Dissipation in solids under oscillatory shear: Role of damping scheme and sample thickness

Authors:R. L. C. Vink

Abstract: We study dissipation as a function of sample thickness in solids under global oscillatory shear applied to the top layer of the sample. Two types of damping mechanism are considered: Langevin and Dissipative Particle Dynamics (DPD). In the regime of low driving frequency, and under strain-controlled conditions, we observe that for Langevin damping, dissipation increases with sample thickness, while for DPD damping, it decreases. Under force-controlled conditions, dissipation increases with sample thickness for both damping schemes. These results can be physically understood by treating the solid as a one-dimensional harmonic chain in the quasi-static limit, for which explicit equations (scaling relations) describing dissipation as a function of chain length (sample thickness) are provided. The consequences of these results, in particular regarding the choice of damping scheme in computer simulations, are discussed.

5.Evidence for a conical spin spiral state in the Mn triple-layer on W(001): spin-polarized scanning tunneling microscopy and first-principles calculations

Authors:Paula M. Weber, Tim Drevelow, Jing Qi, Matthias Bode, Stefan Heinze

Abstract: The spin structure of a Mn triple layer grown pseudomorphically on surfaces is studied using spin-polarized scanning tunneling microscopy (SP-STM) and density functional theory (DFT). In SP-STM images a c$(4 \times 2)$ super structure is found. The magnetic origin of this contrast is verified by contrast reversal and using the c$(2 \times 2)$ AFM state of the Mn double layer as a reference. SP-STM simulations show that this contrast can be explained by a spin spiral propagating along the [110] direction with an angle close to $90^\circ$ between magnetic moments of adjacent Mn rows. To understand the origin of this spin structure, DFT calculations have been performed for a large number of competing collinear and non-collinear magnetic states including the effect of spin-orbit oupling (SOC). Surprisingly, a collinear state in which the magnetic moments of top and central Mn layer are aligned antiparallel and those of the bottom Mn layer are aligned parallel to the central layer is the energetically lowest state. We show that in this so-called "up-down-down" ($\uparrow \downarrow \downarrow$) state the magnetic moments in the Mn bottom layer are only induced by those of the central Mn layer. Flat spin spirals propagating either in one, two, or all Mn layers are shown to be energetically unfavorable to the collinear $\uparrow \downarrow \downarrow$ state even upon including the Dzyaloshinskii-Moriya interaction (DMI). However, conical spin spirals with a small opening angle of about $10^\circ$ are only slightly energetically unfavorable within DFT and could explain the experimental observations. Surprisingly, the DFT energy dispersion of conical spin spirals including SOC cannot be explained if only the DMI is taken into account. Therefore, higher-order interactions such as chiral biquadratic terms need to be considered which could explain the stabilization of a conical spin spiral state.

6.Synthesis of single-crystalline LuN films

Authors:Guanhua Su, Shuling Xiang, Jiachang Bi, Fugang Qi, Peiyi Li, Shunda Zhang, Shaozhu Xiao, Ruyi Zhang, Zhiyang Wei, Yanwei Cao

Abstract: In the nitrogen-doped lutetium hydride (Lu-H-N) system, the presence of Lu-N chemical bonds plays a key role in the emergence of possible room-temperature superconductivity at near ambient pressure. However, due to the synthesis of single-crystalline LuN being a big challenge, the understanding of LuN is insufficient thus far. Here, we report on the epitaxial growth of single-crystalline LuN films. The crystal structures of LuN films were characterized by high-resolution X-ray diffraction. The measurement of low-temperature electrical transport indicates the LuN film is semiconducting from 300 to 2 K, yielding an activation gap of $\sim$ 0.02 eV. Interestingly, negative magnetoresistances can be observed below 12 K, which can result from the defects and magnetic impurities in LuN films. Our results uncover the electronic and magnetic properties of single-crystalline LuN films.

7.Fractional Skyrme lines in ferroelectric barium titanate

Authors:Chris Halcrow, Egor Babaev

Abstract: We predict a new kind of topological defect in ferroelectric barium titanate which we call a skyrme line. These are line-like objects characterized by skyrmionic topological charge. As well as configurations with integer charge, the charge density can split into well-localized fractional parts. We show that under certain conditions the fractional skyrme lines are stable. We discuss a mechanism to create fractional topological charge objects and investigate their stability.

8.Ultrafast Orbital Hall Effect in Metallic Nanoribbons

Authors:Oliver Busch, Franziska Ziolkowski, Börge Göbel, Ingrid Mertig, Jürgen Henk

Abstract: The orbital Hall effect can generate currents of angular momentum more efficiently than the spin Hall effect in most metals. However, so far, it has only been understood as a steady state phenomenon. In this theoretical study, the orbital Hall effect is extended into the time domain. We investigate the orbital angular momenta and their currents induced by a femtosecond laser pulse in a Cu nanoribbon. Our numerical simulations provide detailed insights into the laser-driven electron dynamics on ultrashort timescales with atomic resolution. The ultrafast orbital Hall effect described in this work is consistent with the familiar pictorial representation of the static orbital Hall effect, but we also find pronounced differences between physical quantities that carry orbital angular momentum and those that carry charge. For example, there are deviations in the time series of the respective currents. This study lays the foundations for investigating ultrafast Hall effects in confined metallic systems.

9.Quantum-mechanical effects in photoluminescence from thin crystalline gold films

Authors:Alan R. Bowman, Álvaro Rodríguez Echarri, Fatemeh Kiani, Fadil Iyikanat, Ted V. Tsoulos, Joel D. Cox, Ravishankar Sundararaman, F. Javier García de Abajo, Giulia Tagliabue

Abstract: Luminescence constitutes a unique source of insight into hot carrier processes in metals, including those in plasmonic nanostructures, for sensing and energy applications. However, being weak in nature, metal luminescence remains poorly understood, its microscopic origin strongly debated, and its potential for understanding nanoscale carrier dynamics largely unexploited. Here we reveal quantum-mechanical effects emanating in the luminescence from thin monocrystalline gold flakes. Specifically, we present experimental evidence and develop a first-principles parameterized model of bulk gold luminescence to demonstrate luminescence is photoluminescence when exciting in the interband regime. Our model allows us to identify changes to gold luminescence due to quantum-mechanical effects as gold film thickness is reduced. Excitingly, we observe quantum mechanical effects in the luminescence signal for flakes thinner than 40 nm, due to changes in the band structure near the Fermi level. We qualitatively reproduce these effects with first-principles modelling. Thus, we present a unified description of luminescence in gold, enabling its widespread application as a probe of carrier dynamics and light-matter interactions in this material and paving the way for future explorations of hot carriers and charge transfer dynamics in a multitude of systems.

1.Giant geometry modulation on magnetic proximity effect observed in isomeric oxide heterostructures

Authors:Meng Wang, Shunsuke Mori, Xiuzhen Yu, Masahiro Sawada, Ryutaro Yoshimi, Naoya Kanazawa, Fumitaka Kagawa

Abstract: Magnetic proximity effect (MPE) is generally considered to occur at the magnetic-nonmagnetic material interface within a short-range space domain, while the structural geometry modulation on such an interface effect has not been explored. Here, we fabricate isomeric paramagnetic metallic IrO2 with rutile and anatase structures, respectively, on a ferrimagnetic insulating CoFe2O4, and study the MPE-induced magnetism by anomalous Hall effect (AHE) measurements. The rutile phase with layered structure shows a conventional AHE and identical coercive-field with CoFe2O4, indicating a concomitant magnetic switching as a result of a strong magnetic coupling at the interface. In contrast, the anatase phase with tetrahedral structure exhibits an unconventional AHE with negative coercive-field at low temperatures. Further analyses indicate that in anatase, the contribution that strongly couples with CoFe2O4 is dramatically suppressed while a giant frustration-like response emerges. Our findings reveal that the MPE-induced spin orders can be pronouncedly modulated by structural geometry.

2.Electrical polarization switching in bulk single crystal GaFeO$_{3}$

Authors:Maria Biernacka, Paweł Butkiewicz, Konrad J. Kapcia, Wojciech Olszewski, Dariusz Satuła, Marek Szafrański, Marcin Wojtyniak, Krzysztof Szymański

Abstract: The electrical polarization switching on stoichiometric GaFeO$_{3}$ single crystal was measured, and a new model of atomic displacements responsible for the polarization reverse was proposed. The widely adapted mechanism of polarization switching in GaFeO$_{3}$ can be applied to stoichiometric, perfectly ordered crystals. However, the grown single crystals, as well as thin films of Ga-Fe-O, show pronounced atomic disorder. By piezoresponse force microscopy, the electrical polarization switching on a crystal surface perpendicular to the electrical polarization direction was demonstrated. Atomic disorder in the crystal was measured by X-ray diffraction and M\"ossbauer spectroscopy. These measurements were supported by ab initio calculations. By analysis of atomic disorder and electronic structure calculations, the energies of defects of cations in foreign cationic sites were estimated. The energies of the polarization switch were estimated, confirming the proposed mechanism of polarization switching in GaFeO$_{3}$ single crystals.

3.Frustration-induced magnetic bimerons in transition metal halide CoX2 (X = Cl, Br) monolayers

Authors:Yu Wang, Shuai Dong, Xiaoyan Yao

Abstract: With the field of two-dimensional (2D) magnetic materials expanding rapidly, noncollinear topological magnetic textures in 2D materials are attracting growing interest recently. As the in-plane counterpart of magnetic skyrmions, magnetic bimerons have the same topological advantages, but are rarely observed in experiments. Employing first-principles calculations and Monte Carlo simulations, we predict that the centrosymmetric transition metal halide CoX2 (X = Cl, Br) monolayers can be promising candidates for observing the frustration-induced bimerons. These bimerons crystallize into stable triangular lattice under an appropriate magnetic field. Compared to the skyrmions driven by the Dzyaloshinskii-Moriya interaction or the long-ranged magnetic dipole-dipole interactions, these frustration-induced bimerons have much smaller size and flexible tunability. Furthermore, the biaxial strain provides an effective method to tune the frustration and thereby to tune the bimeron lattice. In detail, for CoCl2 monolayer, tensile strain can be applied to generate bimeron lattice, further shrink bimeron size and increase the density of bimerons. For CoBr2 monolayer with inherent bimeron lattice state, a unique orientation rotation of bimeron lattice controlled by compressive strain is predicted.

1.Mapping Orthorhombic Domains with Geometrical Phase Analysis in Rare-Earth Nickelate Heterostructures

Authors:Bernat Mundet, Marios Hadjimichael, Jennifer Fowlie, Lukas Korosec, Lucia Varbaro, Claribel Dominguez, Jean-Marc Triscone, Duncan T. L. Alexander

Abstract: Most perovskite oxides belong to the Pbnm space group, composed by an anisotropic unit cell, A-site antipolar displacements and oxygen octahedral tilts. Mapping the orientation of the orthorhombic unit cell in epitaxial heterostructures that consist of at least one Pbnm compound is often required to understand and control the different degrees of coupling established at their coherent interfaces and, therefore, their resulting physical properties. However, retrieving this information from the strain maps generated with high-resolution scanning transmission electron microscopy can be challenging, because the three pseudocubic lattice parameters are very similar in these systems. Here, we present a novel methodology for mapping the crystallographic orientation in Pbnm systems. It makes use of the geometrical phase analysis algorithm, as applied to aberration-corrected scanning transition electron microscopy images, but in an unconventional way. The method is fast and robust, giving real-space maps of the lattice orientations in Pbnm systems, from both cross-sectional and plan-view geometries and across large fields of view. As an example, we apply our methodology to rare-earth nickelate heterostructures, in order to investigate how the crystallographic orientation of these films depends on various structural constraints that are imposed by the underlying single crystal substrates. We observe that the resulting domain distributions and associated defect landscapes mainly depend on a competition between the epitaxial compressive/tensile and shear strains, together with the matching of atomic displacements at the substrate/film interface. The results point towards strategies for controlling these characteristics by appropriate substrate choice.

2.Structural pathway for nucleation and growth of topologically close-packed phase from parent hexagonal crystal

Authors:Junyuan Bai, Hongbo Xie, Xueyong Pang, Min Jiang, Gaowu Qin

Abstract: The solid diffusive phase transformation involving the nucleation and growth of one nucleus is universal and frequently employed but has not yet been fully understood at the atomic level. Here, our first-principles calculations reveal a structural formation pathway of a series of topologically close-packed (TCP) phases within the hexagonally close-packed (hcp) matrix. The results show that the nucleation follows a nonclassical nucleation process, and the whole structural transformation is completely accomplished by the shuffle-based displacements, with a specific 3-layer hcp-ordering as the basic structural transformation unit. The thickening of plate-like TCP phases relies on forming these hcp-orderings at their coherent TCP/matrix interface to nucleate ledge, but the ledge lacks the dislocation characteristics considered in the conventional view. Furthermore, the atomic structure of the critical nucleus for the Mg2Ca and MgZn2 Laves phases was predicted in terms of Classical Nucleation Theory (CNT), and the formation of polytypes and off-stoichiometry in TCP precipitates is found to be related to the nonclassical nucleation behavior. Based on the insights gained, we also employed high-throughput screening to explore several common hcp-metallic (including hcp-Mg, Ti, Zr, and Zn) systems that may undergo hcp-to-TCP phase transformations. These insights can deepen our understanding of solid diffusive transformations at the atomic level, and constitute a foundation for exploring other technologically important solid diffusive transformations.

3.Manifestation of chiral magnetic current in Floquet-Weyl semimetals

Authors:Tsung-Yu Chen, Po-Hao Chou, Chung-Yu Mou

Abstract: Materials that can host macroscopic persistent current are important because they are useful for energy storage. However, there are very few examples of such materials in nature. Superconductors are known as an example in which flow of supercurrent can persist up to 100,000 years. The chiral magnetic current is possibly the second example predicted by the chiral magnetic effect. It was proposed to be realized in recently discovered Weyl semimetals. However, a no-go theorem negates the chiral magnetic effect and shows that the chiral magnetic current is generally absent in any equilibrium condensed-matter system. Here we show how to break the no-go theorem by resorting to dynamical transitions in time-frequency space. By driving an insulator using a time-periodic potential and coupling it to a phonon heat bath that provides suitable dissipation, we show that a Floquet-Weyl semi-metallic phase with Fermi-Dirac-like distribution emerges. Furthermore, we show that even in the presence of a static magnetic field, the resulting steady Floquet-Weyl semimetal supports non-vanishing chiral magnetic current. Our dynamical model provides a systematic way to fully realize the chiral magnetic effect in condensed matter systems.

4.Temperature-driven confinements of surface electrons and adatoms in a weakly interacting 2D organic porous network

Authors:Lu Lyu, Jin Xiao, Zakaria M. Abd El-Fattah, Tobias Eul, Mostafa Ashoush, Jun He, Wei Yao, Ignacio Piquero-Zulaica, Sina Mousavion, Benito Arnoldi, Sebastian Becker, Johannes V. Barth, Martin Aeschlimann, Benjamin Stadtmüller

Abstract: Two-dimensional organic porous networks (2DOPNs) have opened new vistas for tailoring the physicochemical characteristics of metallic surfaces. These typically chemically bound nanoporous structures act as periodical quantum wells leading to the 2D confinements of surface electron gases, adatoms and molecular guests. Here we propose a new type of porous network with weakly interacting 2,4,6-triphenyl-1,3,5-triazine (TPT) molecules on a Cu(111) surface, in which a temperature-driven (T-driven) phase transition can reversibly alter the supramolecular structures from a close-packed (CP-TPT) phase to a porous-network (PN-TPT) phase. Crucially, only the low-temperature PN-TPT exhibits subnano-scale cavities that can confine the surface state electrons and metal adatoms. The confined surface electrons undergo a significant electronic band renormalization. To activate the spin degree of freedom, the T-driven PN-TPT structure can additionally trap Co atoms within the cavities, forming highly ordered quantum dots. Our theoretical simulation reveals a complex spin carrier transfer from the confined Co cluster to the neighbouring TPT molecules via the underlying substrate. Our results demonstrate that weakly interacting 2DOPN offers a unique quantum switch capable of steering and controlling electrons and spin at surfaces via tailored quantum confinements.

5.Giant confinement of excited surface electrons in a two-dimensional metal-organic porous network

Authors:Lu Lyu, Tobias Eul, Wei Yao, Jin Xiao, Zakaria M. Abd El-Fattah, Mostafa Ashoush, Ignacio Piquero-Zulaica, Johannes V. Barth, Martin Aeschlimann, Benjamin Stadtmüller

Abstract: Two-dimensional metal-organic porous networks (2D-MOPNs) are highly ordered quantum boxes for exploring surface confinements. In this context, the electron confinement from occupied Shockley-type surface states (SS) has been vigorously studied in 2D-MOPNs. In contrast, the confinement of excited surface states, such as image potential states (IPSs), remains elusive. In this work, we apply two-photon photoemission to investigate the confinement exemplarily for the first image state in a Cu-coordinated T4PT porous network (Cu-T4PT). Due to the lateral potential confinement in the Cu-T4PT, periodic replicas of the IPS as well as the SS are present in a momentum map. Surprisingly, the first IPS transforms into a nearly flat band with a substantial increase of the effective mass (> 150 %), while the band dispersion of the SS is almost unchanged. The giant confinement effect of the excited electrons can be attributed to the wavefunction location of the first IPS perpendicular to the surface, where the majority probability density mainly resides at the same height as repulsive potentials formed by the Cu-T4PT network. This coincidence leads to a more effective scattering barrier to the IPS electrons, which is not observed in the SS. Our findings demonstrate that the vertical potential landscape in a porous architecture also plays a crucial role in surface electron confinement.

6.Tailoring the ferromagnetic surface potential landscape by a templating two-dimensional metal-organic porous network

Authors:Lu Lyu, Martin Anstett, Ka Man Yu, Azadeh Kadkhodazadeh, Martin Aeschlimann, Benjamin Stadtmüller

Abstract: Two-dimensional metal-organic porous networks (2D-MOPNs) have been identified as versatile nanoarchitectures to tailor surface electronic and magnetic properties on noble metals. In this context, we propose a protocol to redecorate a ferromagnetic surface potential landscape using a 2D-MOPN. Ultrathin cobalt (Co) films grown on Au(111) exhibit a well-ordered surface triangular reconstruction. On the ferromagnetic surface, the adsorbed 2,4,6-tris(4-pyridyl)-1,3,5triazine (T4PT) molecules can coordinate with the native Co atoms to form a large-scale Co-T4PT porous network. The Co-T4PT network with periodic nanocavities serves as a templating layer to reshape the ferromagnetic surface potential. The subsequently deposited C60 molecules are steered by the network porous potential and the neighboring C60 interactions. The prototype of the ferromagnetic-supported 2D-MOPN is a promising template for the tailoring of molecular electronic and spin properties.

7.Machine Learning Predictions of High-Curie-Temperature Materials

Authors:Joshua F. Belot, Valentin Taufour, Stefano Sanvito, Gus L. W. Hart

Abstract: Technologies that function at room temperature often require magnets with a high Curie temperature, $T_\mathrm{C}$, and can be improved with better materials. Discovering magnetic materials with a substantial $T_\mathrm{C}$ is challenging because of the large number of candidates and the cost of fabricating and testing them. Using the two largest known data sets of experimental Curie temperatures, we develop machine-learning models to make rapid $T_\mathrm{C}$ predictions solely based on the chemical composition of a material. We train a random forest model and a $k$-NN one and predict on an initial dataset of over 2,500 materials and then validate the model on a new dataset containing over 3,000 entries. The accuracy is compared for multiple compounds' representations ("descriptors") and regression approaches. A random forest model provides the most accurate predictions and is not improved by dimensionality reduction or by using more complex descriptors based on atomic properties. A random forest model trained on a combination of both datasets shows that cobalt-rich and iron-rich materials have the highest Curie temperatures for all binary and ternary compounds. An analysis of the model reveals systematic error that causes the model to over-predict low-$T_\mathrm{C}$ materials and under-predict high-$T_\mathrm{C}$ materials. For exhaustive searches to find new high-$T_\mathrm{C}$ materials, analysis of the learning rate suggests either that much more data is needed or that more efficient descriptors are necessary.

8.Magnon-magnon coupling in synthetic ferrimagnets

Authors:A. Sud, K. Yamamoto, K. Z. Suzuki, S. Mizukami, H. Kurebayashi

Abstract: Magnetic multilayers with interlayer exchange coupling have been widely studied for both static and dynamic regimes. Their dynamical responses depend on the exchange coupling strength and magnetic properties of individual layers. Magnetic resonance spectra in such systems are conveniently discussed in terms of coupling of acoustic and optical modes. At a certain value of applied magnetic field, the two modes come close to being degenerate and the spectral gap indicates the strength of mode hybridisation. In this work, we theoretically and experimentally study the mode hybridisation of interlayer-exchange-coupled moments with dissimilar magnetisation and thickness of two ferromagnetic layers. In agreement with symmetry analysis for eigenmodes, our low-symmetry multilayers exhibit sizable spectral gaps for all experimental conditions. The spectra agree well with the predictions from the Landau-Lifshitz-Gilbert equation at the macrospin limit whose parameters are independently fixed by static measurements.

9.Second-order Band Topology in Antiferromagnetic (MnBi$_2$Te$_4$)(Bi$_2$Te$_3$)$_{m}$ Films

Authors:Fangyang Zhan, Zheng Qin, Dong-Hui Xu, Xiaoyuan Zhou, Da-Shuai Ma, Rui Wang

Abstract: The existence of fractionally quantized topological corner states serves as a key indicator for two-dimensional second-order topological insulators (SOTIs), yet has not been experimentally observed in realistic materials. Here, based on first-principles calculations and symmetry arguments, we propose a strategy for achieving SOTI phases with in-gap corner states in (MnBi$_2$Te$_4$)(Bi$_2$Te$_3$)$_{m}$ films with antiferromagnetic (AFM) order. Starting from the prototypical AFM MnBi$_2$Te$_4$ bilayer, we show by an effective lattice model that such SOTI phase originate from the interplay between intrinsic spin-orbital coupling and interlayer AFM exchange interactions. Furthermore, we demonstrate that the nontrivial corner states are linked to rotation topological invariants under three-fold rotation symmetry $C_3$, resulting in $C_3$-symmetric SOTIs with corner charges fractionally quantized to $\frac{n}{3} \lvert e \rvert $ (mod $e$). Due to the great recent achievements in (MnBi$_2$Te$_4$)(Bi$_2$Te$_3$)$_{m}$ systems, our results providing reliable material candidates for experimentally accessible AFM higher-order band topology would draw intense attentions.

10.Layer-dependent electronic structures and magnetic ground states of polar-polar $\rm{LaVO_3/KTaO_3}$ (001) interfaces

Authors:Shubham Patel, Narayan Mohanta, Snehasish Nandy, Subhendra D. Mahanti, A Taraphder

Abstract: Using first-principles and model Hamiltonian approach, we explore the electronic properties of polar-polar LaVO$_3$/KTaO$_3$ (LVO/KTO, 001) hetero-interfaces of up to six and five layers of KTO and LVO, respectively. Our calculations suggest the presence of multiple Lifshitz transitions (LT) in the $t_{2g}$ bands which may show up in high thermal conductivity and Seebeck coefficient. The LT can be tuned by the number of LaVO$_3$ layers or gate voltage. The spin-orbit coupling is found to be negligible, coming only from the Ta $5d_{xy}$-derived band, 5$d_{xz}$ and 5$d_{yz}$ bands being far away from the Fermi level. The magnetic properties of the interfaces, due to Vanadium ions, turn out to be intriguing. The magnetic states are highly sensitive to the number of layers of LaVO$_3$ and KTaO$_3$: the interfaces with equal number of LVO and KTO layers always favor an antiferromagnetic (AFM) ordering. Moreover, the combination of even-even and odd-odd layers shows an AFM order for more than two LaVO$_3$ layers. The spin-polarized density of states reveals that all the interfaces with ferromagnetic (FM) ground states are \textit{half-metallic}. The small energy differences between AFM and FM configurations indicate a possible coexistence of competing AFM and FM ground states in these interfaces. In addition, the interface requires different number of LVO layers for it to be metallic: half-metallic FM for three and above, and metallic AFM for four and above.

11.Synergistic Niobium Doped Two-Dimensional Zirconium Diselenide: An Efficient Electrocatalyst for O$_2$ Reduction Reaction

Authors:Ashok Singh, Srimanta Pakhira

Abstract: The development of high-activity and low-price cathodic catalysts to facilitate the electrochemical sluggish O$_2$ reduction reaction (ORR) is very important to achieve the commercial application of fuel cells. Here, we have investigated the electrocatalytic activity of two-dimensional single-layer Nb-doped zirconium diselenide (2D Nb-ZrSe$_2$) towards ORR by employing the dispersion corrected Density Functional Theory (DFT-D) method. Through our study, we computed structural properties, electronic properties, and energetics of the 2D Nb-ZrSe$_2$ and ORR intermediates to analyze the electrocatalytic performance of the 2D Nb-ZrSe$_2$. The electronic properties calculations depict that the 2D monolayer ZrSe$_2$ has a large band gap of 1.48 eV, which is not favorable for the ORR mechanism. After the doping of Nb, the electronic band gap vanishes and 2D Nb-ZrSe$_2$ acts as a conductor. We studied both the dissociative and associative pathways through which the ORR can proceed to reduce the oxygen molecule (O$_2$). Our results show that the more favorable path for O$_2$ reduction on the surface of the 2D Nb-ZrSe$_2$ is the 4e$^-$ associative path. The detailed ORR mechanisms (both associated and dissociative) have been explored by computing the changes of Gibbs free energy ({\Delta}G). All the ORR reaction intermediate steps are thermodynamically stable and energetically favorable. The free energy profile for the associative path shows the downhill behavior of the free energy vs. the reaction steps, suggesting that all ORR intermediate structures are catalytically active for the 4e$^-$ associative path and a high 4e$^-$ reduction pathway selectivity. Therefore, 2D Nb-ZrSe$_2$ is a promising catalyst for the ORR which can be used as an alternative ORR catalyst compared with expensive platinum (Pt).

1.Observation of nonvolatile magneto-thermal switching in superconductors

Authors:Hiroto Arima, Md. Riad Kasem, Hossein Sepehri-Amin, Fuyuki Ando, Ken-ichi Uchida, Yoshikazu Mizuguchi

Abstract: Applying a magnetic field to a solid changes its thermal-transport properties. Although such magneto-thermal-transport phenomena are usually small effects, giant magneto-thermal resistance has recently been observed in spintronic materials1,2 and superconductors3,4, opening up new possibilities in thermal management technologies. However, the thermal conductivity conventionally changes only when a magnetic field is applied due to the absence of nonvolatility, which limits potential applications of thermal switching devices5,6. Here, we report the observation of nonvolatile thermal switching that changes the thermal conductivity when a magnetic field is applied and retains the value even when the field is turned off. This unconventional magneto-thermal switching, surprisingly, arises in commercial Sn-Pb solders and is realized by phase-separated superconducting states and resultant nonuniform magnetic flux distributions. This result confirms the versatility of the observed phenomenon and aids the development of active solid-state thermal management devices.

2.Emergent zero-field anomalous Hall effect in a reconstructedrutileantiferromagnetic metal

Authors:Meng Wang, Katsuhiro Tanaka, Shiro Sakai, Ziqian Wang, Ke Deng, Yingjie Lyu, Cong Li, Di Tian, Shengchun Shen, Naoki Ogawa, Naoya Kanazawa, Pu Yu, Ryotaro Arita, Fumitaka Kagawa

Abstract: Anomalous Hall effect (AHE) emerged in antiferromagnetic metals shows intriguing physics and application potential. In contrast to certain noncollinear antiferromagnets, rutile RuO$_2$ has been proposed recently to exhibit a crystal-assisted AHE with collinear antiferromagnetism. However, in RuO$_2$, the on-site magnetic moment accompanying itinerant 4d electrons is quite small, and more importantly, the AHE at zero external field is prohibited by symmetry because of the high-symmetry [001] direction of the N\'eel vector. Here, we show the AHE at zero field in the collinear antiferromagnet, Cr-doped RuO$_2$. The appropriate doping of Cr at Ru sites results in a rotation of the N\'eel vector from [001] to [110] and enhancement of the on-site magnetic moment by one order of magnitude while maintaining a metallic state with the collinear antiferromagnetism. The AHE with vanishing net moment in the Ru$_{0.8}$Cr$_{0.2}$O$_2$ exhibits an orientation dependence consistent with the [110]-oriented N\'eel vector. These results open a new avenue to manipulate AHE in antiferromagnetic metals.

3.Monolithic Selenium/Silicon Tandem Solar Cells

Authors:Rasmus Nielsen, Andrea Crovetto, Alireza Assar, Ole Hansen, Ib Chorkendorff, Peter C. K. Vesborg

Abstract: Selenium is experiencing renewed interest as a promising candidate for the wide bandgap photoabsorber in tandem solar cells. However, despite the potential of selenium-based tandems to surpass the theoretical efficiency limit of single junction devices, such a device has never been demonstrated. In this study, we present the first monolithically integrated selenium/silicon tandem solar cell. Guided by device simulations, we investigate various carrier-selective contact materials and achieve encouraging results, including an open-circuit voltage of V$_\text{oc}$=1.68 V from suns-V$_\text{oc}$ measurements. The high open-circuit voltage positions selenium/silicon tandem solar cells as serious contenders to the industrially dominant single junction technologies. Furthermore, we quantify a pseudo fill factor of more than 80% using injection-level-dependent open-circuit voltage measurements, indicating that a significant fraction of the photovoltaic losses can be attributed to parasitic series resistance. This work provides valuable insights into the key challenges that need to be addressed for realizing higher efficiency selenium/silicon tandem solar cells.

4.Spin-polarized correlated insulator in monolayer MoTe2-x

Authors:Zemin Pan, Wenqi Xiong, Jiaqi Dai, Yunhua Wang, Tao Jian, Xingxia Cui, Jinghao Deng, Xiaoyu Lin, Zhengbo Cheng, Yusong Bai, Chao Zhu, Da Huo, Geng Li, Min Feng, Jun He, Wei Ji, Shengjun Yuan, Fengcheng Wu, Chendong Zhang, Hong-Jun Gao

Abstract: Flat electronic bands near the Fermi level provide a fertile playground for realizing interaction-driven correlated physics. To date, related experiments have mostly been limited to engineered multilayer systems (e.g., moir\'e systems). Herein, we report an experimental realization of nearly flat bands across the Fermi level in monolayer MoTe2-x by fabricating a uniformly ordered mirror-twin boundary superlattice (corresponding to a stoichiometry of MoTe56/33). The kagome flat bands are discovered by combining scanning tunnelling microscopy and theoretical calculations. The partial filling nature of flat bands yields a correlated insulating state exhibiting a hard gap as large as 15 meV. Moreover, we observe pronounced responses of the correlated states to magnetic fields, providing evidence for a spin-polarized ground state. Our work introduces a monolayer platform that manifests strong correlation effects arising from flattened electronic bands.

5.Temperature dependent magnetoelectric response of lead-free Na$_{0.4}$K$_{0.1}$Bi$_{0.5}$TiO$_3$-NiFe$_2$O$_4$ laminated composites

Authors:Adityanarayan Pandey, Amritesh Kumar, Pravin Varade, K. Miriyala, A. Arockiarajan, Ajit. R. Kulkarni, N. Venkataramani

Abstract: This study investigates the temperature-dependent quasi-static magnetoelectric (ME) response of electrically poled lead-free Na$_{0.4}$K$_{0.1}$Bi$_{0.5}$TiO$_3$-NiFe$_2$O$_4$ (NKBT-NFO) laminated composites. The aim is to understand the temperature stability of ME-based sensors and devices. The relaxor ferroelectric nature of NKBT is confirmed through impedance and polarization-electric (PE) hysteresis loop studies, with a depolarization temperature (Td) of approximately 110$^\circ$C. Heating causes a decrease and disappearance of planar electromechanical coupling, charge coefficient, and remnant polarization above Td. The temperature rise also leads to a reduction in magnetostriction and magnetostriction coefficient of NFO by approximately 33% and 25%, respectively, up to approximately 125$^\circ$C. At room temperature, the bilayer and trilayer configurations exhibit maximum ME responses of approximately 33 mV/cm.Oe and 80 mV/cm.Oe, respectively, under low magnetic field conditions (300-450 Oe). The ME response of NKBT/NFO is highly sensitive to temperature, decreasing with heating in accordance with the individual temperature-dependent properties of NKBT and NFO. This study demonstrates a temperature window for the effective utilization of NKBT-NFO-based laminated composite ME devices.

6.Giant non-volatile electric field control of proximity induced magnetism in the spin-orbit semimetal SrIrO3

Authors:Arun Kumar Jaiswal, Robert Eder, Di Wang, Vanessa Wollersen, Matthieu Le Tacon, Dirk Fuchs

Abstract: With its potential for drastically reduced operation power of information processing devices, electric field control of magnetism has generated huge research interest. Recently, novel perspectives offered by the inherently large spin-orbit coupling of 5d transition metals have emerged. Here, we demonstrate non-volatile electrical control of the proximity induced magnetism in SrIrO3 based back-gated heterostructures. We report up to a 700 % variation of the anomalous Hall conductivity {\sigma}_AHE and Hall angle {\theta}_AHE as function of the applied gate voltage Vg. In contrast, the Curie temperature TC = 100K and magnetic anisotropy of the system remain essentially unaffected by Vg indicating a robust ferromagnetic state in SrIrO3 which strongly hints to gating-induced changes of the anomalous Berry curvature. The electric-field induced ferroelectric-like state of SrTiO3 enables non-volatile switching behavior of {\sigma}_AHE and {\theta}_AHE below 60 K. The large tunability of this system, opens new avenues towards efficient electric-field manipulation of magnetism.

7.In silico Ptychography of Lithium-ion Cathode Materials from Subsampled 4-D STEM Data

Authors:Alex W. Robinson, Amirafshar Moshtaghpour, Jack Wells, Daniel Nicholls, Zoe Broad, Angus I. Kirkland, Beata L. Mehdi, Nigel D. Browning

Abstract: High quality scanning transmission electron microscopy (STEM) data acquisition and analysis has become increasingly important due to the commercial demand for investigating the properties of complex materials such as battery cathodes; however, multidimensional techniques (such as 4-D STEM) which can improve resolution and sample information are ultimately limited by the beam-damage properties of the materials or the signal-to-noise ratio of the result. subsampling offers a solution to this problem by retaining high signal, but distributing the dose across the sample such that the damage can be reduced. It is for these reasons that we propose a method of subsampling for 4-D STEM, which can take advantage of the redundancy within said data to recover functionally identical results to the ground truth. We apply these ideas to a simulated 4-D STEM data set of a LiMnO2 sample and we obtained high quality reconstruction of phase images using 12.5% subsampling.

8.Structural, electronic, thermal and mechanical properties of C60-based fullerene two-dimensional networks explored by first-principles and machine learning

Authors:Bohayra Mortazavi

Abstract: Recent experimental reports on the realizations of two-dimensional (2D) networks of the C60-based fullerenes with anisotropic and nanoporous lattices represent a significant advance, and create exciting prospects for the development of a new class of nanomaterials. In this work, we employed theoretical calculations to explore novel C60-based fullerene lattices and subsequently evaluate their stability and key physical properties. After the energy minimization of extensive structures, we could detect novel 2D, 1D and porous carbon C60-based networks, with close energies to that of the isolated C60 cage. Density functional theory results confirm that the C60-based networks can exhibit remarkable thermal stability, and depending on their atomic structure show metallic, semimetallic or semiconducting electronic nature. Using the machine learning interatomic potentials, thermal and mechanical responses of the predicted nanoporous 2D lattices were investigated. The estimated thermal conductivity of the quasi-hexagonal-phase of C60 fullerene is shown to be in an excellent agreement with the experimental measurements. Despite of different atomic structures, the anisotropic room temperature lattice thermal conductivity of the fullerene nanosheets are estimated to be in the order of 10 W/mK. Unlike the majority of carbon-based 2D materials, C60-based counterparts noticeably are predicted to show positive thermal expansion coefficients. Porous carbon C60-based networks are found to exhibit superior mechanical properties, with tensile strengths and elastic modulus reaching extraordinary values of 50 and 300 GPa, respectively. The theoretical results presented in this work provide a comprehensive vision on the structural, energetic, electronic, thermal and mechanical properties of the C60-based fullerene networks.

9.Tuning the Intrinsic Spin Hall Effect by Charge Density Wave Order in Topological Kagome Metals

Authors:Diana Golovanova, Hengxin Tan, Tobias Holder, Binghai Yan

Abstract: Kagome metals are topological materials with a rich phase diagram featuring various charge density wave orders and even unconventional superconductivity. However, little is still known about possible spin-polarized responses in these non-magnetic compounds. Here, we perform ab-initio calculations of the intrinsic spin Hall effect (SHE) in the kagome metals AV$_3$Sb$_5$ (A=Cs, Rb, K), CsTi$_3$Bi$_5$ and ScV$_6$Sn$_6$. We report large spin Hall conductivities, comparable with the Weyl semimetal TaAs. Additionally, in CsV$_3$Sb$_5$ the SHE is strongly renormalized by the CDW order. We can understand these results based on the topological properties of band structures, demonstrating that the SHE is dominated by the position and shape of the Dirac nodal lines in the kagome sublattice. Our results suggest kagome materials as a promising, tunable platform for future spintronics applications.

10.A thermodynamic band gap model for photoinduced phase segregation in mixed-halide perovskites

Authors:Anthony Ruth, Halyna Okrepka, Prashant Kamat, Masaru Kuno

Abstract: Provided is a comprehensive description of a band gap thermodynamic model, which predicts and explains key features of photosegregation in lead-based, mixed-halide perovskites. The model provides a prescription for illustrating halide migration driven by photocarrier energies. Where possible, model predictions are compared to experimental results. Free energy derivations are provided for three assumptions: (1) halide mixing in the dark, (2) a fixed number of photogenerated carriers funneling to and localizing in low band gap inclusions of the alloy, and (3) the statistical occupancy of said inclusions from a bath of thermalized photocarriers in the parent material. Model predictions include: excitation intensity ($I_{\textrm{exc}}$)-dependent terminal halide stoichiometries ($x_{\textrm{terminal}}$), excitation intensity thresholds ($I_{\textrm{exc,threshold}}$) below which photosegregation is suppressed, reduced segregation in nanocrystals as compared to thin films, the possibility to kinetically manipulate photosegregation rates via control of underlying mediators, asymmetries in forward and reverse photosegregation rate constants/activation energies, and a preference for high band gap products to recombine with the parent phase. What emerges is a cohesive framework for understanding ubiquitous photosegregation in mixed-halide perovskites and a rational basis by which to manage the phenomenon.

11.Extrinsic Anomalous Hall effect in Mn Doped GeSnTe Semiconductors in the Bad Metal Hopping Regime

Authors:A. Khaliq, R. Minikaev, S. Zakar, M. Arciszewska, A. Avdonin, V. E. Slynko, L. Kilanski

Abstract: We present high field magnetotransport studies of Ge1-x-y(SnxMny)Te bulk multiferroics with diamagnetic Sn and paramagnetic Mn concentration x = 0.38 to 0.79 and y = 0.02 to 0.086, respectively. The zero field resistivity, {\rho}(T) takes significant contribution from defects below T = 20 K however, a mixed scattering contribution from dynamic disorder and unusual sources is estimated from T = 20 K to 300 K. The carrier mobility shows anomalous temperature dependence from T0.2 to T0.5 which hints towards possible presence of polaronic effects resulting from coupling of holes with phonons. This anomalous behavior cannot be understood in terms of pure phononic scattering mechanism at high temperature. From point of view of high field results, the transverse component of magnetoresistivity manifests anomalous Hall effect originating from extrinsic scattering sources, particularly the side jump mechanism reveals a larger contribution. We also find that the correlation between the transverse and longitudinal conductivities follow the universal scaling law {\sigma}xy ~ {\sigma}xxn where n = 1.6 in the low conductivity limit. The values n = 1.5 to 1.8 obtained for the present GSMT alloys justify the bad metal hopping regime since the results fall in the low conductivity ferromagnetic family with {\sigma}xx ~ 104 ohmcm-1. The interpretation of the n = 1.6 scaling in the low conductivity regime is thus far not fully understood. However, the anomalous Hall resistivity scaling with modified relation by Tian et al is indicative of the dominant side jump scattering along with noticeable role of skew scattering.

1.Microstructure of a spark-plasma-sintered Fe2VAl-type Heusler alloy for thermoelectric application

Authors:Leonie Gomell, Imants Dirba, Hanna Bishara, Zhongji Sun, Łukasz. Żrodowski, Tomasz Choma, Bartosz Morończyk, Gerhard Dehm, Konstantin P. Skokov, Oliver Gutfleisch, B. Gault

Abstract: The influence of microstructure on thermoelectricity is increasingly recognized. Approaches for microstructural engineering can hence be exploited to enhance thermoelectric performance, particularly through manipulating crystalline defects, their structure, and composition. Here, we focus on a full-Heusler Fe2VAl-based compound that is one of the most promising thermoelectric materials containing only Earth-abundant, non-toxic elements. A Fe2VTa0.05Al0.95 cast alloy was atomized under a nitrogen-rich atmosphere to induce nitride precipitation. Nanometer- to micrometer-scale microstructural investigations by advanced scanning electron microscopy and atom probe tomography (APT) are performed on the powder first and then on the material consolidated by spark-plasma sintering for an increasing time. APT reveals an unexpected pick-up of additional impurities from atomization, namely W and Mo. The microstructure is then correlated with local and global measurements of the thermoelectric properties. At grain boundaries, segregation and precipitation locally reduce the electrical resistivity, as evidenced by in-situ four-point probe measurements. The final microstructure contains a hierarchy of structural defects, including individual point defects, dislocations, grain boundaries, and precipitates, that allow for a strong decrease in thermal conductivity. In combination, these effects provide an appreciable increase in thermoelectric performance.

2.The curvature-induced magnetization in CrI3 bilayer: flexomagnetic effect enhancement in van der Waals antiferromagnets

Authors:Lei Qiao, Jan Sladek, Vladimir Sladek, Alexey S. Kaminskiy, Alexander P. Pyatakov, Wei Ren

Abstract: The bilayer of CrI3 is a prototypical van der Waals 2D antiferromagnetic material with magnetoelectric effect. It is not generally known, however, that for symmetry reasons the flexomagnetic effect, i.e., the strain gradient-induced magnetization, is also possible in this material. In the present paper, based on the first principle calculations, we estimate the flexomagnetic effect to be 200 {\mu}B{\AA} that is two orders of magnitude higher than it was predicted for the referent antiperovskite flexomagnetic material Mn3GaN. The two major factors of flexomagnetic effect enhancement related to the peculiarities of antiferromagnetic structure of van der Waals magnets is revealed: the strain-dependent ferromagnetic coupling in each layer and large interlayer distance separating antiferromagnetically coupled ions. Since 2D systems are naturally prone to mechanical deformation, the emerging field of flexomagnetism is of special interest for application in spintronics of van der Waals materials and straintronics in particular.

3.Group theoretical and ab-initio description of color center candidates in fluorographene

Authors:M. S. Tacca, M. B. Plenio

Abstract: We present a group theoretical and ab-initio analysis of lattice point defects in fluorographene, with a focus on neutral and negative $\text{V}_{\text{CF}}$ vacancies. By using a combination of density functional theory calculations and group theory analysis, we investigate the many-body configurations of the defects and calculate the vertical absorption and zero-phonon line energies of the excited states and their dependence with strain. The description of the defects is extended by computing their formation energy, as well as further relevant parameters as the Jahn-Teller energy for neutral $\text{V}_{\text{CF}}$ and the zero field splitting for negative $\text{V}_{\text{CF}}$ vacancies. Based on our results, we discuss possible quantum applications of these color centers when coupled to mechanical oscillation modes of the hosting two-dimensional material. The symmetry and active orbitals of the defects exhibit a parallelism with those of the extensively studied NV centers in diamond. In this context, the studied defects emerge as interesting candidates for the development of two-dimensional quantum devices based on fluorographene.

4.Data-driven machine learning approach for predicting yield strength of additively manufactured multi-principal element alloys

Authors:Abhinav Chandraker, Nichenametla Jai Sai, Ankur Chauhan

Abstract: Additive manufacturing (AM) of multi-principal element alloys (MPEAs) has gained significant attention in recent years. However, the intricate nature of phenomena such as rapid solidification, heat gradients, and residual stresses presents challenges in controlling the properties of printed components. To overcome these challenges, this study utilized machine learning (ML) approach to investigate the correlations between composition, processing parameters, testing conditions, and yield strength of single-phase MPEAs within the CoCrFeMnNi system, produced via laser-melt deposition and laser powder-bed fusion. Multiple algorithms, including Random Forest, Gradient Boosting, and Extreme Gradient Boosting, were trained, and tested. SHapley Additive exPlanations algorithm was employed to analyze the contributions of input features. All models exhibited reasonable accuracy, with Random Forest performing the best. The impact of data sparsity was examined, and minimal sensitivity to data splitting was observed. Notably, the research yielded valuable insights into the key features influencing the yield strength of MPEAs, showcasing the potential of ML in accurately modeling the material properties of additively manufactured components.

5.Comprehensive first-principles insights into the physical properties of intermetallic Zr$_3$Ir: a noncentrosymmetric superconductor

Authors:Razu Ahmed, Md. Sajidul Islam, M. M. Hossain, M. A. Ali, M. M. Uddin, S. H. Naqib

Abstract: We have looked into the structural, mechanical, optoelectronic, superconducting state and thermophysical aspects of intermetallic compound Zr$_3$Ir using the density functional theory (DFT). Many of the physical properties, including direction dependent mechanical properties, Vickers hardness, optical properties, chemical bonding nature, and charge density distributions, are being investigated for the first time. According to this study, Zr$_3$Ir exhibits ductile features, high machinability, significant metallic bonding, a low Vickers hardness with low Debye temperature, and a modest level of elastic anisotropy. The mechanical and dynamical stabilities of Zr$_3$Ir have been confirmed. The metallic nature of Zr$_3$Ir is seen in the electronic band structures with a high electronic energy density of states at the Fermi level. The bonding nature has been explored by the charge density mapping and bond population analysis. The tetragonal Zr$_3$Ir shows a remarkable electronic stability, as confirmed by the presence of a pseudogap in the electronic energy density of states at the Fermi level between the bonding and antibonding states. Optical parameters show very good agreement with the electronic properties. The reflectivity spectra reveal that Zr$_3$Ir is a good reflector in the infrared and near-visible regions. Zr$_3$Ir is an excellent ultra-violet (UV) radiation absorber. High refractive index at visible photon energies indicates that Zr$_3$Ir could be used to improve the visual aspects of electronic displays. All the optical constants exhibit a moderate degree of anisotropy. Zr$_3$Ir has a moderate melting point, high damage tolerance, and very low minimum thermal conductivity. The thermomechanical characteristics of Zr$_3$Ir reveal that it is a potential thermal barrier coating material. The superconducting state parameters of Zr$_3$Ir are also explored.

6.Two-dimensional bimetal-embedded expanded phthalocyanine monolayers: a class of multifunctional materials with fascinating properties

Authors:De-Bing Long, Nikolay V. Tkachenko, Qingqing Feng, Xingxing Li, Alexander I. Boldyrev, Jinlong Yang, Li-Ming Yang

Abstract: The expanded phthalocyanine (EPc) single-layer sheets with double transition metals (labeled as TM2EPc, TM = Sc-Zn) are predicted to be a new class of two-dimensional (2D) metal-organic materials with a series of favorable functional properties by means of systematic first-principle calculations and molecular dynamics simulations. The strong coordination between metal and EPc substrate accounts for the excellent structural stability. Chemical bonding analysis has demonstrated the absence of TM-TM bonding. Each metal center is isolated, but connected to the organic framework by four 2c-2e TM-N {\sigma}-bonds to form an extended 2D network. Unexpectedly, it is found that the V2EPc is an antiferromagnetic metal with Dirac cone, while Cr2EPc exhibits ferromagnetic Dirac half-metallicity, which is not common in 2D materials. Excitingly, the ferromagnetic Cr2EPc and antiferromagnetic Mn2- and Fe2-EPc have high magnetic transition temperatures of 223, 217, and 325 K, respectively, which are crucial for the practical applications of spintronics. Cr2EPc can maintain the Dirac half-metallicity under -6 % ~ 2 % biaxial strains, and Fe2EPc can transform from semiconductor to half-metal by applying -6 % ~ -10 % compressive strains. Additionally, the TM2EPc monolayers exhibit a full response to visible light and some materials have strong absorption in the ultraviolet and infrared regions in addition to visible light, showing extraordinary solar light-harvesting ability. Notably, the designed type-II heterojunctions Fe2EPc/SnC, Co2EPc/GeS, and Ni2EPc/2H-WSe2 have high power conversion efficiency (PCE > 15%), especially the PCE of Ni2EPc/2H-WSe2 reaches 25.19%, which has great potential in solar cell applications. All these desired properties render 2D TM2EPc monolayers promising candidates for future applications in nanoelectronics, spintronics,optoelectronics, and photovoltaic devices.

7.Atomic-Scale Insights into Damage Produced by Swift Heavy Ions in Polyethylene

Authors:P. Babaev, F. Akhmetov, S. Gorbunov, N. Medvedev, R. Rymzhanov, R. Voronkov, A. E. Volkov

Abstract: We describe the formation of swift heavy ion tracks in polyethylene (PE) by combining the Monte Carlo code TREKIS, which models electronic excitation in nanometric proximity of the ion trajectory, with the molecular dynamics simulating a response of the atomic system to the perturbation. The model predicts circular tracks in amorphous PE but elliptical ones in crystalline PE caused by preferential propagation of excitation along polymer chains during the cooling stage. The obtained track sizes and shapes agree well with the high-resolution microscopy of tracks in PE. The velocity effect in PE is shown: the track parameters differ for ions with the same energy losses but different velocities.

8.Slip intermittency and dwell fatigue in titanium alloys: a discrete dislocation plasticity analysis

Authors:Yilun Xu, Felicity Worsnop, David Dye, Fionn P. E. Dunne

Abstract: Slip intermittency and stress oscillations in titanium alloy Ti-7Al-O that were observed using in-situ far-field high energy X-ray diffraction microscopy (ff-HEDM) are investigated using a discrete dislocation plasticity (DDP) model. The mechanistic foundation of slip intermittency and stress oscillations are shown to be dislocation escape from obstacles during stress holds, governed by a thermal activation constitutive law. The stress drop events due to <a>-basal slip are larger in magnitude than those along <a>-prism, which is a consequence of their differing rate sensitivities, previously found from micropillar testing. It is suggested that interstitial oxygen suppresses stress oscillations by inhibiting the thermal activation process. Understanding of these mechanisms is of benefit to the design and safety assessment of jet engine titanium alloys subjected to dwell fatigue.

9.Stabilization of Ferroelectric Hf0.5Zr0.5O2 Epitaxial Films via Monolayer Reconstruction Driven by Interfacial Redox Reaction

Authors:Yufan Shen, Mitsutaka Haruta, I-Ching Lin, Lingling Xie, Daisuke Kan, Yuichi Shimakawa

Abstract: The binary fluorite oxide Hf0.5Zr0.5O2 tends to grab a significant amount of notice due to the distinct and superior ferroelectricity found in its metastable phase. Stabilizing the metastable ferroelectric phase and delineating the underlying growth mechanism, however, are still challenging. Recent discoveries of metastable ferroelectric Hf0.5Zr0.5O2 epitaxially grown on structurally dissimilar perovskite oxides have triggered intensive investigations on the ferroelectricity in materials that are nonpolar in bulk form. Nonetheless, the growth mechanism for the unique fluorite/perovskite heterostructures has yet to be fully explored. Here we show that the metastable ferroelectric Hf0.5Zr0.5O2 films can be stabilized even on a one-unit-cell-thick perovskite La0.67Sr0.33MnO3 buffer layer. In collaboration with scanning transmittance electron microscopy (STEM) based characterizations, we show that monolayer reconstruction driven by interfacial redox reactions plays a vital role in the formation of a unique heterointerface between the two structurally dissimilar oxides, providing the template monolayer that facilitates the epitaxial growth of the metastable HZO films. Our findings offer significant insights into the stabilization mechanism of the ferroelectric Hf0.5Zr0.5O2, and this mechanism could be extended for exploring functional metastable phases of various metal oxides.

10.Tensor gradiometry with a diamond magnetometer

Authors:A. J. Newman, S. M. Graham, A. M. Edmonds, D. J. Twitchen, M. L. Markham, G. W. Morley

Abstract: Vector magnetometry provides more information than scalar measurements for magnetic surveys utilized in space, defense, medical, geological and industrial applications. These areas would benefit from a mobile vector magnetometer that can operate in extreme conditions. Here we present a scanning fiber-coupled nitrogen vacancy (NV) center vector magnetometer. Feedback control of the microwave excitation frequency is employed to improve dynamic range and maintain sensitivity during movement of the sensor head. Tracking of the excitation frequency shifts for all four orientations of the NV center allow us to image the vector magnetic field of a damaged steel plate. We calculate the magnetic tensor gradiometry images in real time, and they allow us to detect smaller damage than is possible with vector or scalar imaging.

1.MD-HIT: Machine learning for materials property prediction with dataset redundancy control

Authors:Qin Li, Nihang Fu, Sadman Sadeed Omee, Jianjun Hu

Abstract: Materials datasets are usually featured by the existence of many redundant (highly similar) materials due to the tinkering material design practice over the history of materials research. For example, the materials project database has many perovskite cubic structure materials similar to SrTiO$_3$. This sample redundancy within the dataset makes the random splitting of machine learning model evaluation to fail so that the ML models tend to achieve over-estimated predictive performance which is misleading for the materials science community. This issue is well known in the field of bioinformatics for protein function prediction, in which a redundancy reduction procedure (CD-Hit) is always applied to reduce the sample redundancy by ensuring no pair of samples has a sequence similarity greater than a given threshold. This paper surveys the overestimated ML performance in the literature for both composition based and structure based material property prediction. We then propose a material dataset redundancy reduction algorithm called MD-HIT and evaluate it with several composition and structure based distance threshold sfor reducing data set sample redundancy. We show that with this control, the predicted performance tends to better reflect their true prediction capability. Our MD-hit code can be freely accessed at

2.Novel Carbon allotropes with mixed hybridizations: ene-C10, and ene-yne-C14. Crystal chemistry and first principles investigations

Authors:Samir F. Matar

Abstract: Based on C8, carbon 4C, with cfc topology, two hybrid carbon allotropes generated by inserting C(sp2) and C(sp1) carbon atoms into C8 diamond-like lattice were identified and labeled ene-C10 containing C(sp2) and ene-yne-C14 containing C(sp2 and sp1). The introduced double and triple chemical descriptions were illustrated from the projected charge densities. The crystal density and the cohesive energy were found to decrease due to the enhanced openness of the structures from inserted sp2/sp1 carbons, with a resulting decrease of the hardness along the series C8, C10, C12, and C14. The novel hybrid allotropes were found stable mechanically (elastic constants and their combinations) and dynamically (phonons band structures). The thermal properties from the temperature dependence of the heat capacity CV were found to increasingly depart from diamond-like C8 to higher values. From the electronic band structures, the inserted carbons were found to add up bands rigidly to diamond-like C8 while being characterized by metallic-like behavior for ene-C10 and ene-yne-C14.

3.ADAQ-SYM: Automated Symmetry Analysis of Defect Orbitals

Authors:William Stenlund, Joel Davidsson, Viktor Ivády, Rickard Armiento, Igor A. Abrikosov

Abstract: Quantum technologies like single photon emitters and qubits can be enabled by point defects in semiconductors, with the NV-center in diamond being the most prominent example. There are many different semiconductors, each potentially hosting interesting defects. High-throughput methods and automated workflows become necessary when searching for novel point defects in a large chemical space. The symmetry properties of the point defect orbitals can yield useful information about the behavior of the system, such as the interaction with polarized light. We have developed an automated code to perform symmetry analysis of point defect orbitals obtained by plane-wave density functional theory simulations. The code, named ADAQ-SYM, calculates the characters for each orbital, finds the irreducible representations, and uses selection rules to find which optical transitions are allowed. The capabilities of ADAQ-SYM are demonstrated on several defects in diamond and 4H-SiC. The symmetry analysis explains the different zero phonon line (ZPL) polarization of the hk and kh divacancies in 4H-SiC. ADAQ-SYM is automated, making it suitable for high-throughput screening of point defects.

4.Spin transport properties of spinel vanadate-based heterostructures

Authors:Antonio Peña Corredor, Alberto Anadón, Laurent Schlur, Jérôme Robert, Héloïse Damas, Juan-Carlos Rojas-Sánchez, Sébastien Petit-Watelot, Nathalie Viart, Daniele Preziosi, Christophe Lefevre

Abstract: Spin-orbit coupling and breaking of inversion symmetry are necessary ingredients to enable a pure spin current-based manipulation of the magnetization via the spin-orbit torque effect. Currently, magnetic insulator oxides with non-dissipative characteristics are being explored. When combined with non-magnetic heavy metals, known for their large spin-orbit coupling, they offer promising potential for energy-efficient spin-orbitronics applications. The intrinsic electronic correlations characterizing those strongly correlated oxides hold the promises to add extra control-knobs to the desired efficient spin-wave propagation and abrupt magnetization switching phenomena. Spinel vanadate FeV2O4 (FVO) exhibits several structural phase transitions which are accompanied by an intricate interplay of magnetic, charge and orbital orderings. When grown as a thin film onto SrTiO3, the compressive strain state induces a perpendicular magnetic anisotropy, making FVO-based heterostructures desirable for spin-orbitronics applications. In this study, we have optimised the deposition of stoichiometric and epitaxial Pt/FVO heterostructures by Pulsed Laser Deposition and examined their spin-related phenomena. From angle-dependent magnetotransport measurements, we observed both Anisotropic Magnetoresistance (AMR) and Spin Hall Magnetoresistance (SMR) effects. Our findings show the SMR component as the primary contributor to the overall magnetoresistance, whose high value of 0.12% is only comparable to properly optimized oxide-based systems.

5.Physical Insights of Low Thermal Expansion Coefficient Electrode Stress Effect on Hafnia-Based Switching Speed

Authors:Y. -T. Tsai, C. -R. Liu, Y. -T. Chen, S. -M. Wang, Z. -K. Chen, C. -S. Pai, Z. -R. Haung, F. -S. Chang, Z. -X. Li, K. -Y. Hsiang, M. -H. Lee, Y. -T. Tang

Abstract: In this report, we investigate the effect of low coefficient of thermal expansion (CTE) metals on the operating speed of hafnium-based oxide capacitance. We found that the cooling process of low CTE metals during rapid thermal annealing (RTA) generates in-plane tensile stresses in the film, This facilitates an increase in the volume fraction of the o-phase and significantly improves the domain switching speed. However, no significant benefit was observed at electric fields less than 1 MV/cm. This is because at low voltage operation, the defective resistance (dead layer) within the interface prevents electron migration and the increased RC delay. Minimizing interface defects will be an important key to extending endurance and retention.

6.Transformative Effect of Oxygen Plasma to Upshot the Structural and Electrical Properties of Pr0.5Sr0.5MnO3 Manganites

Authors:Pronita Chettri, Bhakta Kunwar, Gurukrishna, Suraj Mangavati, Arun Sarma, Ashok Rao, C. Devaraja, Utpal Deka

Abstract: A methodical inquiry of the outcome of oxygen plasma exposure in low bandwidth compounds belonging to the perovskite family Pr1-xSrxMnO3 manganites where x = 0.5, has been presented in this communication by comparing the structural and transport properties of the untreated and plasma treated samples. It is witnessed that the high-temperature transmission is carried out by small polarons while the low-temperature transmission is attributed to variable range polarons. The changes in the transport properties may be attributed to the structural modification due to plasma exposure as revealed by the Rietveld analysis of the X-ray diffraction pattern. Further, oxygen plasma exposure boosts the conductivity due to the integration of oxygen ions in the plasma-exposed samples, thereby rendering them oxygen-rich.

7.Silver-Platinum nanoparticles and nanodroplets supported on silica surfaces: structure and chemical ordering

Authors:F. Ait Hellal, J. Puibasset, C. Andreazza-Vignolle, P. Andreazza

Abstract: Stable and metastable metallic nanoparticles exhibit unique properties compared to the bulk, with potentially important applications for catalysis. This is in particular the case for the AgPt alloy that can exhibit the ordered L1$_1$ structure (alternation of pure Ag and Pt (111) planes) in nanometer size particles. However, for such small systems, the interfaces play an important role. Therefore, the support used to elaborate the nanoparticles in ultrahigh vacuum experiments may influence their properties, even in the case of weakly interacting substrates like amorphous carbon or silica. This work focuses on the AgPt nanoparticles deposited on silica, and investigates the effect of the support disorder and roughness on the structure and chemical ordering, in particular at the interface with the substrate, by Monte Carlo calculations of the atomic density profiles with semi-empiric potentials.

8.Designing of Organic Bridging Linkers of Metal-Organic Frameworks for Enhanced Carbon Dioxide Adsorption

Authors:Kahkasha Parveen, Srimanta Pakhira

Abstract: The global rate of anthropogenic CO2 emission is rising, which urges the development of efficient carbon capture and storage (CCS) technologies. Among the various CO2 capture methods, adsorption by the linkers of the Metal-Organic Frameworks (MOFs) materials has received more interest as excellent CO2 adsorbents because of their important role in understanding the interaction mechanism for CO2 adsorption. Here, we investigate the adsorption of CO2 molecules at the center and side positions of several MOF-linkers using molecular cluster models. The interaction between CO2 and the linkers is approximated by computing the binding enthalpy ({\Delta}H) through the first principles-based Density Functional Theory with Grimmes dispersion correction (i.e., B3LYP-D3) and second-order Moller Plesset Theory (MP2). The computed values of {\Delta}H indicate the weak nature of CO2 adsorption on the pristine linkers, hence the strategy of lithium decoration is used to see its impact on the binding strength. Among the various linkers tested, CO2 adsorbing at the side position of the DFBDC-2 linker has strong adsorption with {\Delta}H value of about -35.32 kJ/mol computed by the B3LYP-D3 method. The Energy Decomposition Analysis (EDA) study reveals that among all the energy terms, the contribution of electrostatic and polarization energy terms to the {\Delta}H value are the most dominant one. Furthermore, the results of Frontier Molecular Orbital Analysis (FMO) revealed that all the linkers remained stable even after Li-decoration. The results of our investigations will direct towards the development and synthesis of novel adsorbents with enhanced CO2 adsorption.

9.Topological engineered 3D printing of Architecturally Interlocked Petal-Schwarzites

Authors:Rushikesh S. Ambekar, Leonardo V. Bastos, Douglas S. Galvao, Chandra S. Tiwary, Cristiano F. Woellner

Abstract: The topologically engineered complex Schwarzites architecture has been used to build novel and unique structural components with a high specific strength. The mechanical properties of these building blocks can be further tuned, reinforcing with stronger and high surface area architecture. In the current work, we have built six different Schwarzites structures with multiple interlocked layers, which we named architecturally interlocked petal-schwarzites (AIPS). These complex structures are 3D printed into macroscopic dimensions and compressed using uniaxial compression. The experimental results show a strong dependency of mechanical response on the number of layers and topology of the layers. Fully atomistic molecular dynamics compressive simulations were also carried out, and the results are in good agreement with experimental observations. They can explain the underlying AIPS mechanism of high specific strength and energy absorption. The proposed approach opens a new perspective on developing new 3D-printed materials with tunable and enhanced mechanical properties.

10.Porous CrO$_2$: a ferromagnetic half-metallic member in sparse hollandite oxide family

Authors:Sujoy Datta

Abstract: A stable polymorph of CrO$_2$ is predicted using PBE+U method. The porous material is isostructural with $\alpha$-MnO$_2$ making it the second transition metal oxide in sparse hollandite group of materials. However, unlike the anti-ferromagnetic semiconducting character of the $\alpha$-MnO$_2$, it is found to be a ferromagnetic half-metal. At Fermi level, the hole pocket has ample contribution from O-2$p$ orbital, though, the electron pocket is mostly contributed by Cr-3$d_{xy}$ and Cr-3d$_{x^2-y^2}$. A combination of negative charge transfer through orbital mixing and extended anti-bonding state near Fermi level is responsible for the half-metallic ferromagnetic character of the structure. A comparative study of rutile and hollandite CrO$_2$ and hollandite MnO$_2$ structures delineate the interplay between structural, electronic and magnetic properties. The material shows a robust magnetic character under hydrothermal pressure, as well as, the band topology is conserved under uniaxial strain. Moderate magneto-crystalline anisotropy is observed and it shows a correspondence with the anisotropy of elastic constants.

11.Endotaxial Stabilization of 2D Charge Density Waves with Long-range Order

Authors:Suk Hyun Sung, Nishkarsh Agarwal, Ismail El Baggari, Yin Min Goh, Patrick Kezer, Noah Schnitzer, Yu Liu, Wenjian Lu, Yuping Sun, Lena F. Kourkoutis, John T. Heron, Kai Sun, Robert Hovden

Abstract: Charge density waves are emergent quantum states that spontaneously reduce crystal symmetry, drive metal-insulator transitions, and precede superconductivity. In low-dimensions, distinct quantum states arise, however, thermal fluctuations and external disorder destroy long-range order. Here we stabilize ordered two-dimensional (2D) charge density waves through endotaxial synthesis of confined monolayers of 1T-TaS$_2$. Specifically, an ordered incommensurate charge density wave (oIC-CDW) is realized in 2D with dramatically enhanced amplitude and resistivity. By enhancing CDW order, the hexatic nature of charge density waves becomes observable. Upon heating via in-situ TEM, the CDW continuously melts in a reversible hexatic process wherein topological defects form in the charge density wave. From these results, new regimes of the CDW phase diagram for 1T-TaS$_2$ are derived and consistent with the predicted emergence of vestigial quantum order.

12.Design and processing as ultrathin films of a sublimable Iron(II) spin crossover material exhibiting efficient and fast light-induced spin transition

Authors:Miguel Gavara-Edo, Francisco Javier Valverde-Muñoz, M. Carmen Muñoz, Safaa Elidrissi Moubtassim, Francisco Marques-Moros, Javier Herrero-Martín, Kateryna Znovjyak, Maksym Seredyuk, José Antonio Real, Eugenio Coronado

Abstract: Materials based on spin crossover (SCO) molecules have centred the attention in Molecular Magnetism for more than forty years as they provide unique examples of multifunctional and stimuli-responsive materials, which can be then integrated into electronic devices to exploit their molecular bistability. This process often requires the preparation of thermally stable SCO molecules that can sublime and remain intact in contact with surfaces. However, the number of robust sublimable SCO molecules is still very scarce. Here we report a novel example of this kind. It is based on a neutral iron (II) coordination complex formulated as [FeII(neoim)2], where neoimH is the ionogenic ligand 2-(1H-imidazol-2-yl)-9-methyl-1,10-phenanthroline. In the first part a comprehensive study, which covers the synthesis and magneto-structural characterization of the [FeII(neoim)2] complex as a bulk microcrystalline material, is reported. Then, in the second part we investigate the suitability of this material to form thin films through high vacuum (HV) sublimation. Finally, the retainment of all present SCO capabilities in the bulk when the material is processed is thoroughly studied by means of X-ray absorption spectroscopy. In particular, a very efficient and fast light-induced spin transition (LIESST effect) has been observed, even for ultrathin films of 15 nm.

13.DeePTB: A deep learning-based tight-binding approach with $ab$ $initio$ accuracy

Authors:Qiangqiang Gu, Zhanghao Zhouyin, Shishir Kumar Pandey, Peng Zhang, Linfeng Zhang, Weinan E

Abstract: Simulating electronic behavior in materials and devices with realistic large system sizes remains a formidable task within the $ab$ $initio$ framework. We propose DeePTB, an efficient deep learning-based tight-binding (TB) approach with $ab$ $initio$ accuracy to address this issue. By training with $ab$ $initio$ eigenvalues, our method can efficiently predict TB Hamiltonians for unseen structures. This capability facilitates efficient simulation of large-size systems under external perturbations like strain, which are vital for semiconductor band gap engineering. Moreover, DeePTB, combined with molecular dynamics, can be used to perform efficient and accurate finite temperature simulations of both atomic and electronic behavior simultaneously. This is demonstrated by computing the temperature-dependent properties of a GaP system with $10^6$ atoms.

14.Reversal of the skyrmion topological deflection across ferrimagnetic angular momentum compensation

Authors:L. Berges, R. Weil, A. Mougin, J. Sampaio

Abstract: Due to their non-trivial topology, skyrmions describe deflected trajectories, which hinders their straight propagation in nanotracks and can lead to their annihilation at the track edges. This deflection is caused by a gyrotropic force proportional to the topological charge and the angular momentum density of the host film. In this article we present clear evidence of the reversal of the topological deflection angle of skyrmions with the sign of angular momentum density. We measured the skyrmion trajectories across the angular momentum compensation temperature (TAC) in GdCo thin films, a rare earth/transition metal ferrimagnetic alloy. The sample composition was used to engineer the skyrmion stability below and above the TAC. A refined comparison of their dynamical properties evidenced a reversal of the skyrmions deflection angle with the total angular momentum density. This reversal is a clear demonstration of the possibility of tuning the skyrmion deflection angle in ferrimagnetic materials and paves the way for deflection-free skyrmion devices.

15.Ultrafast demagnetization in bulk nickel induced by X-ray photons tuned to Ni $M_{3}$ and $L_3$ absorption edges

Authors:Konrad J. Kapcia, Victor Tkachenko, Flavio Capotondi, Alexander Lichtenstein, Serguei Molodtsov, Przemysław Piekarz, Beata Ziaja

Abstract: Studies of light-induced demagnetization started with the experiment performed by Beaupaire et al. on nickel. Here, we present theoretical predictions for X-ray induced demagnetization of nickel, with X-ray photon energies tuned to its $M_3$ and $L_3$ absorption edges. We show that the specific feature in the density of states of the d-band of Ni, a sharp peak located just above the Fermi level, strongly influences the change of the predicted magnetic signal, making it stronger than in the previously studied case of cobalt. We believe that this finding will inspire future experiments on magnetic processes in X-ray irradiated nickel.

1.Robust atmospherically stable hybrid SrVO3/Graphene//SrTiO3 template for fast and facile large-area transfer of complex oxides onto Si

Authors:Asraful Haque, Suman Kumar Mandal, Antony Jeyaseelan, Sandeep Vura, Pavan Nukala, Srinivasan Raghavan

Abstract: Heterogenous integration of complex epitaxial oxides onto Si and other target substrates is recently gaining traction. One of the popular methods involves growing a water-soluble and highly reactive sacrificial buffer layer, such as Sr3Al2O6 (SAO) at the interface, and a functional oxide on top of this. To improve the versatility of layer transfer techniques, it is desired to utilize stable (less reactive) sacrificial layers, without compromising on the transfer rates. In this study, we utilized a combination of chemical vapor deposited (CVD) graphene as a 2D material at the interface and pulsed laser deposited (PLD) water-soluble SrVO3 (SVO) as a sacrificial buffer layer. We show that the graphene layer enhances the dissolution rate of SVO over ten times without compromising its atmospheric stability. We demonstrate the versatility of our hybrid template by growing ferroelectric BaTiO3 (BTO) via PLD and Pb(Zr, Ti)O3 (PZT) via Chemical Solution Deposition (CSD) technique and transferring them onto the target substrates and establishing their ferroelectric properties. Our hybrid templates allow for the realization of the potential of complex oxides in a plethora of device applications for MEMS, electro-optics, and flexible electronics.

2.Magnetically and electrically controllable valley splittings in MXene monolayers

Authors:Huiqian Wang, Li Liang, Xiaohui Wang, Xiaoyu Wang, Xiao Li

Abstract: The modulation of the valley structure in two-dimensional valley materials is vital in the field of valleytronics. The multiferroicity provides possibility for multiple modulations of the valley, including the magnetic and electric means. Based on the first-principle calculations, we study the valley properties and associated manipulations of multiferroic Co$_2$CF$_2$ monolayers with different stacking patterns. Our calculations show that the Co$_2$CF$_2$ monolayer in the H$^{\prime}$ phase is a ferrovalley material, with sizable valley splittings. By rotating the magnetization direction, the valley splittings can be tuned for both the magnitude and sign. The electric field, driving the reversal of the electric polarization, can also change the magnitude of the valley splittings. Besides, a metastable T$^{\prime}$ phase exhibits valley splittings as well, of which the magnitude and sign can be simultaneously controlled by applied magnetic and electric fields. These findings offer a practical way for realizing highly tunable valleys by multiferroic couplings.

3.Synthesis of a mesoscale ordered 2D-conjugated polymer with semiconducting properties

Authors:Gianluca Galeotti, Fabrizio De Marchi, Ehsan Hamzehpoor, Oliver MacLean, Malakalapalli Rajeswara Rao, Yulan Chen, Lucas Vazquez Besteiro, Dominik Dettmann, Luisa Ferrari, Federico Frezza, Polina M. Sheverdyaeva, R. Liu, Asish K. Kundu, Paolo Moras, Maryam Ebrahimi, Mark C. Gallagher, Federico Rosei, Dmytro F. Perepichka, Giorgio Contini

Abstract: 2D materials with high charge carrier mobility and tunable electronic band gaps have attracted intense research effort for their potential use as active components in nanoelectronics. 2D-conjugated polymers (2DCP) constitute a promising sub-class due to the fact that the electronic band structure can be manipulated by varying the molecular building blocks, while at the same time preserving the key features of 2D materials such as Dirac cones and high charge mobility. The major challenge for their use in technological applications is to fabricate mesoscale ordered 2DCP networks since current synthetic routes yield only small domains with a high density of defects. Here we demonstrate the synthesis of a mesoscale ordered 2DCP with semiconducting properties and Dirac cone structures via Ullmann coupling on Au(111). This material has been obtained by combining rigid azatriangulene precursors and a hot dosing approach which favours molecular diffusion and reduces the formation of voids in the network. These results open opportunities for the synthesis of 2DCP Dirac cone materials and their integration into devices.

4.Anomalous Nernst effect in perpendicularly magnetised τ-MnAl thin films

Authors:Daniel Scheffler, Sebastian Beckert, Helena Reichlova, Thomas G. Woodcock, Sebastian T. B. Goennenwein, Andy Thomas

Abstract: $\tau$-MnAl is interesting for spintronic applications as a ferromagnet with perpendicular magnetic anisotropy due to its high uniaxial magnetocrystalline anisotropy. Here we report on the anomalous Nernst effect of sputter deposited $\tau$-MnAl thin films. We demonstrate a robust anomalous Nernst effect at temperatures of 200 K and 300 K with a hysteresis similar to the anomalous Hall effect and the magnetisation of the material. The anomalous Nernst coefficient of (0.6$\pm$0.24) $\mu$V/K at 300 K is comparable to other perpendicular magnetic anisotropy thin films. Therefore $\tau$-MnAl is a promising candidate for spin-caloritronic research.

5.Observation of the anomalous Hall effect in a layered polar semiconductor

Authors:Seo-Jin Kim, Jihang Zhu, Mario M. Piva, Marcus Schmidt, Dorsa Fartab, Andrew P. Mackenzie, Michael Baenitz, Michael Nicklas, Helge Rosner, Ashley M. Cook, Rafael González-Hernández, Libor Šmejkal, Haijing Zhang

Abstract: Progress in magnetoelectric materials is hindered by apparently contradictory requirements for time-reversal symmetry broken and polar ferroelectric electronic structure in common ferromagnets and antiferromagnets. Alternative routes could be provided by recent discoveries of a time-reversal symmetry breaking anomalous Hall effect in noncollinear magnets and altermagnets, but hitherto reported bulk materials are not polar. Here, we report the observation of a spontaneous anomalous Hall effect in doped AgCrSe$_2$, a layered polar semiconductor with an antiferromagnetic coupling between Cr spins in adjacent layers. The anomalous Hall resistivity 3 $\mu\Omega$ cm is comparable to the largest observed in compensated magnetic systems to date, and is rapidly switched off when the angle of an applied magnetic field is rotated to $\sim 80^{\circ}$ from the crystalline $c$-axis. Our ionic gating experiments show that the anomalous Hall conductivity magnitude can be enhanced by modulating the $p$-type carrier density. We also present theoretical results that suggest the anomalous Hall effect is driven by Berry curvature due to noncollinear antiferromagnetic correlations among Cr spins, which are consistent with the previously suggested magnetic ordering in AgCrSe$_2$. Our results open the possibility to study the interplay of magnetic and ferroelectric-like responses in this fascinating class of materials.

6.Investigation about the electrochemical reduction in 3YSZ, related phase transition and consequences

Authors:C. Bechteler, R. I. Todd

Abstract: In this research the electrochemical reduction of 3YSZ was investigated in various atmospheres with different oxygen partial pressures under an electric field of 25 V/cm at an environmental temperature of 800 {\deg}C. At a certain oxygen partial pressure insufficient incorporation of oxygen in the sample led to electrochemical reduction of YSZ which shows two clearly distinguishable states. First, greying of the material without a significant change in properties was detected which then transitioned into a second stage where a fundamental phase transition in the material happened within seconds from tetragonal 3YSZ towards FCC rocksalt ZrO or ZrON, dependent on the atmosphere. This phase transition is accompanied by blackening of the material, sudden increase in electrical conductivity, current concentration, and an obvious change in Raman spectrum.

7.The interplay between ferroelectricity and electrochemical reactivity on the surface of binary ferroelectric Al$_x$B$_{1-x}$N

Authors:Yongtao Liu, Anton Ievlev, Joseph Casamento, John Hayden, Susan Trolier-McKinstry, Jon-Paul Maria, Sergei V. Kalinin, Kyle P. Kelley

Abstract: Polarization dynamics and domain structure evolution in ferroelectric Al$_{0.93}$B$_{0.07}$N are studied using piezoresponse force microscopy and spectroscopies in ambient and controlled atmosphere environments. The application of negative unipolar, and bipolar first-order reverse curve (FORC) waveforms leads to a protrusion-like feature on the Al$_{0.93}$B$_{0.07}$N surface and reduction of electromechanical response due to electrochemical reactivity. A surface change is also observed on the application of fast alternating current bias. At the same time, the application of positive biases does not lead to surface changes. Comparatively in a controlled glove box atmosphere, stable polarization patterns can be observed, with minuscule changes in surface morphology. This surface morphology change is not isolated to applying biases to free surface, a similar topographical change is also observed at the electrode edges when cycling a capacitor in ambient environment. The study suggests that surface electrochemical reactivity may have a significant impact on the functionality of this material in the ambient environment. However, even in the controlled atmosphere, the participation of the surface ions in polarization switching phenomena and ionic compensation is possible.

8.State of the Art Development on Solid-State Lithium Batteries

Authors:L. J. Zhang

Abstract: Solid-state lithium batteries (SLBs) offers a promising avenue for the development of next-generation lithium-ion batteries with ultrahigh energy density and safety performance. This review provides a quick overview of the state-of-the-art development of anode, cathode, solid electrolyte of SLBs and the observation of ion transport in the cell during the past half year in 2023. Other important developments for SLIBs such as high safety and performance strategies have also been provided.

9.Mechanical Properties of Silicon Nanowires with Native Oxide Surface State

Authors:Sina Zare Pakzad, Mohammad Nasr Esfahani, B. Erdem Alaca

Abstract: Silicon nanowires have attracted considerable interest due to their wide-ranging applications in nanoelectromechanical systems and nanoelectronics. Molecular dynamics simulations are powerful tools for studying the mechanical properties of nanowires. However, these simulations encounter challenges in interpreting the mechanical behavior and brittle to ductile transition of silicon nanowires, primarily due to surface effects such as the assumption of an unreconstructed surface state. This study specifically focuses on the tensile deformation of silicon nanowires with a native oxide layer, considering critical parameters such as cross-sectional shape, length-to-critical dimension ratio, temperature, the presence of nano-voids, and strain rate. By incorporating the native oxide layer, the article aims to provide a more realistic representation of the mechanical behavior for different critical dimensions and crystallographic orientations of silicon nanowires. The findings contribute to the advancement of knowledge regarding size-dependent elastic properties and strength of silicon nanowires.

10.Modeling intercalation chemistry with multi-redox reactions by sparse lattice models in disordered rocksalt cathodes

Authors:Peichen Zhong, Fengyu Xie, Luis Barroso-Luque, Liliang Huang, Gerbrand Ceder

Abstract: Modern battery materials can contain many elements with substantial site disorder, and their configurational state has been shown to be critical for their performance. The intercalation voltage profile is a critical parameter to evaluate the performance of energy storage. The application of commonly used cluster expansion techniques to model the intercalation thermodynamics of such systems from \textit{ab-initio} is challenged by the combinatorial increase in configurational degrees of freedom as the number of species grows. Such challenges necessitate efficient generation of lattice models without over-fitting and proper sampling of the configurational space under charge balance in ionic systems. In this work, we introduce a combined approach that addresses these challenges by (1) constructing a robust cluster-expansion Hamiltonian using the sparse regression technique, including $\ell_0\ell_2$-norm regularization and structural hierarchy; and (2) implementing semigrand-canonical Monte Carlo to sample charge-balanced ionic configurations using the table-exchange method and an ensemble-average approach. These techniques are applied to a disordered rocksalt oxyfluoride Li$_{1.3-x}$Mn$_{0.4}$Nb$_{0.3}$O$_{1.6}$F$_{0.4}$ (LMNOF) which is part of a family of promising earth-abundant cathode materials. The simulated voltage profile is found to be in good agreement with experimental data and particularly provides a clear demonstration of the Mn and oxygen contribution to the redox potential as a function of Li content.

11.Formulation Graphs for Mapping Structure-Composition of Battery Electrolytes to Device Performance

Authors:Vidushi Sharma, Maxwell Giammona, Dmitry Zubarev, Andy Tek, Khanh Nugyuen, Linda Sundberg, Daniele Congiu, Young-Hye La

Abstract: Advanced computational methods are being actively sought for addressing the challenges associated with discovery and development of new combinatorial material such as formulations. A widely adopted approach involves domain informed high-throughput screening of individual components that can be combined into a formulation. This manages to accelerate the discovery of new compounds for a target application but still leave the process of identifying the right 'formulation' from the shortlisted chemical space largely a laboratory experiment-driven process. We report a deep learning model, Formulation Graph Convolution Network (F-GCN), that can map structure-composition relationship of the individual components to the property of liquid formulation as whole. Multiple GCNs are assembled in parallel that featurize formulation constituents domain-intuitively on the fly. The resulting molecular descriptors are scaled based on respective constituent's molar percentage in the formulation, followed by formalizing into a combined descriptor that represents a complete formulation to an external learning architecture. The use case of proposed formulation learning model is demonstrated for battery electrolytes by training and testing it on two exemplary datasets representing electrolyte formulations vs battery performance -- one dataset is sourced from literature about Li/Cu half-cells, while the other is obtained by lab-experiments related to lithium-iodide full-cell chemistry. The model is shown to predict the performance metrics like Coulombic Efficiency (CE) and specific capacity of new electrolyte formulations with lowest reported errors. The best performing F-GCN model uses molecular descriptors derived from molecular graphs that are informed with HOMO-LUMO and electric moment properties of the molecules using a knowledge transfer technique.

12.Photodegradation and Thermal Effects in Violet Phosphorus

Authors:Mahdi Ghafariasl, Sarabpreet Singh, Sampath Gamage, Timothy Prusnick, Michael Snure, Yohannes Abate

Abstract: Violet phosphorus (VP) has garnered attention for its appealing physical properties and potential applications in optoelectronics. We present a comprehensive investigation of the photo degradation and thermal effects of exfoliated VP on SiO2 substrate. The degradation rate of VP was found to be strongly influenced by the excitation wavelength and light exposure duration. Light exposure to above bandgap light (> 532 nm) leads to significantly faster degradation, attributed to interactions with reactive oxygen species (ROS) generated by the laser. In contrast, lower energy excitation resulted in slower degradation due to reduced ROS generation. Analysis of photoluminescence (PL) spectra showed a gradual decline in the exciton population, signifying reduced lifetime and alterations in formation and stability, ultimately affecting VP's quantum efficiency. Power-dependent PL measurements at low temperature (4 K) showed that the intensities of neutral excitons and trions linearly increased with excitation power, while the energy difference between their peak energies decreased, indicating changes in the exciton energy gap due to degradation at higher laser power. At ambient temperature VP exhibited visible neutral exciton (X0) and trion (T) peaks with higher X0 spectral weight, indicating reduced thermal stability of T in VP crystals. Temperature dependent Raman showed the presence of VP up to 673K and back down to room temperature; however, peak intensities decreased and two new unknown peaks were observed indicating some level of thermal degradation. Our results provide deeper understanding of VP's degradation behavior and implications for optoelectronic applications.

13.DFT Based LDA Study on Tailoring the Optical and Electrical Properties of SnO and In-Doped SnO

Authors:Mohammad Mahafuzur Rahamana, Md. Abdul Momin, Abhijit Majumdar, Mohammad Jellur Rahman

Abstract: In this paper, the structural, electronic and optical properties of tin-monoxide and the impact of Indium (In) doping into tin-monoxide are computed by Local Density Approximation (LDA) under density function theory (DFT) framework. The calculated bond length of Sn-O in tin-monoxide is 2.285 angstrom and that deviates greater than 3 percent from the experimental value. The Sn-O and In-O bond lengths in In-doped tin-monoxide are calculated to be 2.3094 and 2.266 angstrom, respectively. Interestingly, the band gap of pure tin-monoxide is calculated to be 2.61 eV whereas it is significantly dropped down to 2.00 eV in the case of In doped tin-monoxide. The Total Density of State (DOS), Partial DOS and electron density are depicted for tin-monoxide and In-doped tin-monoxide films. As a consequence of In-doping static value of the refractive index and real part of the dielectric function for tin-monoxide decrease from 1.9 to 1.4 and 3.6 to 1.97, respectively. Therefore, In-doping enhances the properties of the tin-monoxide film, which may lead the material to be applied in future to develop electronic and opto-electronic devices.

14.Physics of band-filling correction in defect calculations of solid-state materials

Authors:Harshan Reddy Gopidi, Lovelesh Vashist, Oleksandr I. Malyi

Abstract: In solid-state physics/chemistry, a precise understanding of defect formation and its impact on the electronic properties of wide-bandgap insulators is a cornerstone of modern semiconductor technology. However, complexities arise in the electronic structure theory of defect formation when the latter triggers partial occupation of the conduction/valence band, necessitating accurate post-process correction to the energy calculations. Herein, we dissect these complexities, focusing specifically on the post-process band-filling corrections, a crucial element that often demands thorough treatment in defect formation studies. We recognize the importance of these corrections in maintaining the accuracy of electronic properties predictions in wide-bandgap insulators and their role in reinforcing the importance of a reliable common reference state for defect formation energy calculations. We explored solutions such as aligning deep states and electrostatic potentials, both of which have been used in previous works, showing the effect of band alignment on defect formation energy. Our findings demonstrate that the impact of defect formation on electronic structure (even deep states) can be significantly dependent on the supercell size. We also show that within band-filling calculations, one needs to account for the possible change of electronic structure induced by defect formation, which requires sufficient convergence of electronic structure with supercell size. Thus, this work emphasizes the critical steps to predict defect formation energy better and paves the way for future research to overcome these challenges and advance the field with more efficient and reliable predictive models.

1.Selenium / Tellurium Two-Dimensional Structures: from Isovalent Se Dopants in Te to Atomically Thin Se Films

Authors:Guangyao Miao, Nuoyu Su, Ze Yu, Bo Li, Xiaochun Huang, Weiliang Zhong, Qinlin Guo, Miao Liu, Weihua Wang, Jiandong Guo

Abstract: Two-dimensional (2D) elemental semiconductors have great potential for device applications, but their performance is limited by the lack of efficient doping methods. Here, combining molecular beam epitaxy, scanning tunneling microscopy/spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations, we investigate the evolution of the structural and electronic properties of 2D selenium/tellurium films with increased Se dosages on graphene/6H-SiC(0001) substrates. We found that Se atoms form isovalent dopants by replacing surface Te atoms, which introduces efficient electron doping and lowers the work function of Te films. With the Se dosage increasing, two types of elemental 2D crystalline Se structures, trigonal Se and Se8 molecular assembly films, are obtained on ultrathin Te films, which are distinct from the amorphous Se acquired by depositing Se directly on graphene/6H-SiC(0001). Our results shed light on tuning the electronic properties of 2D elemental semiconductors by isovalent doping and constructing heterostructures of isovalent 2D elemental materials.

2.NiCrAl piston-cylinder cell for magnetic susceptibility measurements under high pressures in pulsed high magnetic fields

Authors:Katsuki Nihongi, Takanori Kida, Yasuo Narumi, Nobuyuki Kurita, Hidekazu Tanaka, Yoshiya Uwatoko, Koichi Kindo, Masayuki Hagiwara

Abstract: We developed a metallic pressure cell made of nickel-chromium-aluminum (NiCrAl) for use with a non-destructive pulse magnet and a magnetic susceptibility measurement apparatus with a proximity detector oscillator (PDO) in pulsed magnetic fields of up to 51 T under pressures of up to 2.1 GPa. Both the sample and sensor coil of the PDO were placed in the cell so that the magnetic signal from NiCrAl would not overlay the intrinsic magnetic susceptibility of the sample. A systematic investigation of the Joule heating originating from metallic parts of the pressure cell revealed that the temperature at the sample position remains at almost 1.4 K until approximately 80 $\%$ of the maximum applied magnetic field ($H_{\rm max}$) in the field-ascending process (e.g., 40 T for $H_{\rm max}$ of 51 T). The effectiveness of our apparatus was demonstrated, by investigating the pressure dependence of the magnetization process of the triangular-lattice antiferromagnet Ba$_3$CoSb$_2$O$_9$.

3.Ultrafast Third-Order Nonlinear Optical Response of Charge Coupled Gold Nanoparticle-Ge24Se76 Heterostructure

Authors:Vinod Kumar, Rituraj Sharma, Abhishek Bhatt, I. Csarnovics, Petr Nemec, H. Jain, K. V. Adarsh

Abstract: The donor-acceptor interaction of a charge-coupled heterostructure encompassing a metal and an amorphous semiconductor subjected to a laser field has many potential applications in the realm of nonlinear optics. In this work, we fabricate an electron donor gold nanoparticle (AuNP) and acceptor amorphous Ge24Se76 heterostructure on a quartz substrate using a sequential thermal evaporation technique. In this charge-coupled heterostructure, we demonstrate the ultrafast third-order nonlinear absorptive and refractive response and their sign reversal compared to pristine Ge24Se76. Enhanced optical nonlinearity in these heterostructures of varying plasmonic wavelengths is due to charge transfer, verified by the Raman spectroscopy. Further, the ultrafast transient absorption measurements support the thesis of charge transfer in the AuNP/Ge24Se76 heterostructure. These findings open up exciting opportunities for developing novel device technologies with far-reaching applications in nonlinear optics.

4.Tuning the Magnetism in Ultrathin CrxTey Films by Lattice Dimensionality

Authors:Guangyao Miao, Minghui Gu, Nuoyu Su, Weiliang Zhong, Zhihan Zhang, Yugui Yao, Wei Jiang, Meng Meng, Weihua Wang, Jiandong Guo

Abstract: Two-dimensional (2D) magnetic transition metal compounds with atomic thickness exhibit intriguing physics in fundamental research and great potential for device applications. Understanding the correlations between their macrosopic magnetic properties and the dimensionality of microscopic magnetic exchange interactions are valuable for the designing and applications of 2D magnetic crystals. Here, using spin-polarized scanning tunneling microscopy, magnetization and magneto-transport measurements, we identify the zigzag-antiferromagnetism in monolayer CrTe2, incipient ferromagnetism in bilayer CrTe2, and robust ferromagnetism in bilayer Cr3Te4 films. Our density functional theory calculations unravel that the magnetic ordering in ultrathin CrTe2 is sensitive to the lattice parameters, while robust ferromagnetism with large perpendicular magnetic anisotropy in Cr3Te4 is stabilized through its anisotropic 3D magnetic exchange interactions.

5.Emergence of half-metallic ferromagnetism in transition metal substituted Na$_{0.5}$Bi$_{0.5}$TiO$_3$

Authors:Chandan Kumar Vishwakarma, B. K. Mani

Abstract: The multifunctional materials with prominent properties such as electrical, ferroelectric, magnetic, optical and magneto-optical are of keen interest to several practical implications. In the roadmap of designing such materials, in the present work, using density functional theory based first-principles calculations, we have investigated the functional properties of transition metal substituted-NBT. Our calculations predict the emergence of half-metallic ferromagnetism in the system. A nonzero magnetic moment of 1.49 $\mu_{\rm B}/{\rm f.u.}$ is obtained for 25\% concentration of Ni. Our data on optical properties for pure NBT is in excellent agreement with available theory and experiments. For Ni-NBT, we observed a diverging nature of static dielectric constant, which could be attributed to the induced metallic character in the material. Our simulations on MOKE predict a significant Kerr signal of 0.7$^\circ$ for 6.25\% Ni-concentration.

6.Morphology-Dependent Influences on the Performance of Battery Cells with a Hierarchically Structured Positive Electrode

Authors:Johanna Naumann, Nicole Bohn, Oleg Birkholz, Matthias Neumann, Marcus Müller, Joachim R. Binder, Marc Kamlah

Abstract: The rising demand for high-performing batteries requires new technological concepts. To facilitate fast charge and discharge, hierarchically structured electrodes offer short diffusion paths in the active material. However, there are still gaps in understanding the influences on the cell performance of such electrodes. Here, we employed a cell model to demonstrate that the morphology of the hierarchically structured electrode determines which electrochemical processes dictate the cell performance. The potentially limiting processes include electronic conductivity within the porous secondary particles, solid diffusion within the primary particles, and ionic transport in the electrolyte surrounding the secondary particles. Our insights enable a goal-oriented tailoring of hierarchically structured electrodes for high-power applications.

7.Boron-doped graphene -- DFT study of the role of dopant concentration and oxidation on sodium and aluminium storage applications

Authors:Milica S. Ritopečki, Natalia V. Skorodumova, Ana S. Dobrota, Igor A. Pašti

Abstract: Graphene is thought to be a promising materials for many applications. However, pristine graphene is not suitable for most electrochemical devices, where defect engineering is crucial for its performance. We demonstrate how boron doping of graphene can alter its reactivity, electrical conductivity and potential application for sodium and aluminium storage, with the emphasis on novel metal-ion batteries. Using DFT calculations, we investigate both the influence of boron concentration and the oxidation of the material, on the mentioned properties. It is demonstrated that the presence of boron in graphene increases its reactivity towards atomic hydrogen and oxygen-containing species, in other words, it makes B-doped graphene more prone to oxidation. Additionally, the presence of these surface functional groups significantly alters the type and strength of the interaction of Na and Al with the given materials. Boron-doping and oxidation of graphene is found to increase Na storage capacity of graphene by the factor of up to 4.

8.Misfit layer compounds as ultra-tunable field effect transistors: from charge transfer control to emergent superconductivity

Authors:Ludovica Zullo, Giovanni Marini, Tristan Cren, Matteo Calandra

Abstract: Misfit layer compounds are heterostructures composed of rocksalt units stacked with few layers transition metal dichalcogenides. They host Ising superconductivity, charge density waves and good thermoelectricity. The design of misfits emergent properties is, however, hindered by the lack of a global understanding of the electronic transfer among the constituents. Here, by performing first principles calculations, we unveil the mechanism controlling the charge transfer and demonstrate that rocksalt units are always donor and dichalcogenides acceptors. We show that misfits behave as a periodic arrangement of ultra-tunable field effect transistors where a charging as large as 6\times10^{14} e^-cm^{-2} can be reached and controlled efficiently by the La-Pb alloying in the rocksalt. Finally, we identify a strategy to design emergent superconductivity and demonstrate its applicability in (LaSe)_{1.27}(SnSe_2)_2. Our work paves the way to the design synthesis of misfit compounds with tailored physical properties.

9.Amplitude phase-field crystal model for the hexagonal close-packed lattice

Authors:Marcello De Donno, Marco Salvalaglio

Abstract: The phase field crystal model allows the study of materials on atomic length and diffusive time scales. It accounts for elastic and plastic deformation in crystal lattices, including several processes such as growth, dislocation dynamics, and microstructure evolution. The amplitude expansion of the phase field crystal model (APFC) describes the atomic density by a small set of Fourier modes with slowly-varying amplitudes characterizing lattice deformations. This approach allows for tackling large, three-dimensional systems. However, it has been used mostly for modeling basic lattice symmetries. In this work, we present a coarse-grained description of the hexagonal closed-packed (HCP) lattice that supports lattice deformation and defects. It builds on recent developments of the APFC model and introduces specific modeling aspects for this crystal structure. After illustrating the general modeling framework, we show that the proposed approach allows for simulating relatively large three-dimensional HCP systems hosting complex defect networks.

10.Trajectory sampling and finite-size effects in first-principles stopping power calculations

Authors:Alina Kononov, Thomas Hentschel, Stephanie B. Hansen, Andrew D. Baczewski

Abstract: Real-time time-dependent density functional theory (TDDFT) is presently the most accurate available method for computing electronic stopping powers from first principles. However, obtaining application-relevant results often involves either costly averages over multiple calculations or ad hoc selection of a representative ion trajectory. We consider a broadly applicable, quantitative metric for evaluating and optimizing trajectories in this context. This methodology enables rigorous analysis of the failure modes of various common trajectory choices in crystalline materials. Although randomly selecting trajectories is common practice in stopping power calculations in solids, we show that nearly 30% of random trajectories in an FCC aluminium crystal will not representatively sample the material over the time and length scales feasibly simulated with TDDFT, and unrepresentative choices incur errors of up to 60%. We also show that finite-size effects depend on ion trajectory via "ouroboros" effects beyond the prevailing plasmon-based interpretation, and we propose a cost-reducing scheme to obtain converged results even when expensive core-electron contributions preclude large supercells. This work helps to mitigate poorly controlled approximations in first-principles stopping power calculations, allowing 1-2 order of magnitude cost reductions for obtaining representatively averaged and converged results.

11.Transformation of 2-line ferrihydrite to goethite at alkaline pH

Authors:Fabio E. Furcas, Barbara Lothenbach, Shishir Mundra, Camelia Borca, Cristhiana C. Albert, O. Burkan Isgor, Thomas Huthwelker, Ueli M. Angst

Abstract: The transformation of 2-line ferrihydrite to goethite from supersaturated solutions at alkaline pH >= 13.0 was studied using a combination of benchtop and advanced synchrotron techniques such as X-ray diffraction, thermogravimetric analysis and X-ray absorption spectroscopy. In comparison to the transformation rates at acidic to mildly alkaline environments, the half-life,t_1/2, of 2-line ferrihydrite reduces from several months at pH = 2.0, and approximately 15 days at pH = 10.0, to just under 5 hours at pH = 14.0. Calculated first order rate constants of transformation, k, increase exponentially with respect to the pH and follow the progression log_10 k = log_10 k_0 + a*pH^E3. Simultaneous monitoring of the aqueous Fe(III) concentration via inductively coupled plasma optical emission spectroscopy demonstrates that (i) goethite likely precipitates from solution and (ii) its formation is rate-limited by the comparatively slow re-dissolution of 2-line ferrihydrite. The analysis presented can be used to estimate the transformation rate of naturally occurring 2-line ferrihydrite in aqueous electrolytes characteristic to mine and radioactive waste tailings as well as the formation of corrosion products in cementitious pore solutions.

1.What dictates soft clay-like Lithium superionic conductor formation from rigid-salts mixture

Authors:Sunny Gupta, Xiaochen Yang, Gerbrand Ceder

Abstract: Soft clay-like Li-superionic conductors have been recently synthesized by mixing rigid-salts. Through computational and experimental analysis, we clarify how a soft clay-like material can be created from a mixture of rigid-salts. Using molecular dynamics simulations with a deep learning-based interatomic potential energy model, we uncover the microscopic features responsible for soft clay-formation from ionic solid mixtures. We find that salt mixtures capable of forming molecular solid units on anion exchange, along with the slow kinetics of such reactions, are key to soft-clay formation. Molecular solid units serve as sites for shear transformation zones, and their inherent softness enables plasticity at low stress. Extended X-ray absorption fine structure spectroscopy confirms the formation of molecular solid units. A general strategy for creating soft clay-like materials from ionic solid mixtures is formulated.

2.Glass-like thermal conductivity and narrow insulating gap of EuTiO$_3$

Authors:Alexandre Jaoui, Shan Jiang, Xiaokang Li, Yasuhide Tomioka, Isao H. Inoue, Johannes Engelmayer, Rohit Sharma, Lara Pätzold, Thomas Lorenz, Benoît Fauqué, Kamran Behnia

Abstract: Crystals and glasses differ by the amplitude and the temperature dependence of their thermal conductivity. However, there are crystals known to display glass-like thermal conductivity. Here, we show that EuTiO$_3$, a quantum paraelectric known to order antiferromagnetically at 5.5 K, is one such system. The temperature dependence of resistivity and Seebeck coefficient yield an insulating band gap of $\sim 0.22$ eV. Thermal conductivity is drastically reduced. Its amplitude and temperature dependence are akin to what is seen in amorphous silica. Comparison with non-magnetic perovskite solids, SrTiO$_3$, KTaO$_3$, and EuCoO$_3$, shows that what impedes heat transport are $4f$ spins at Eu$^{2+}$ sites, which couple to phonons well above the ordering temperature. Thus, in this case, superexchange and valence fluctuations, not magnetic frustration, are the drivers of the glass-like thermal conductivity.

3.Multi-level recording in dual-layer FePt-C granular film for heat-assisted magnetic recording

Authors:P. Tozman, S. Isogami, I. Suzuki, A. Bolyachkin, H. Sepehri-Amin, S. J. Greaves, H. Suto, Y. Sasaki, H. T. Y. Chang, Y Kubota, P. Steiner, P. -W. Huang, K. Hono, Y. K. Takahashi

Abstract: Multi-level magnetic recording is a new concept for increasing the data storage capacity of hard disk drives. However, its implementation has been limited by a lack of suitable media capable of storing information at multiple levels. Herein, we overcome this problem by developing dual FePt-C nanogranular films separated by a Ru-C breaking layer with a cubic crystal structure. The FePt grains in the bottom and top layers of the developed media exhibited different effective magnetocrystalline anisotropies and Curie temperatures. The former is realized by different degrees of ordering in the L10-FePt grains, whereas the latter was attributed to the diffusion of Ru, thereby enabling separate magnetic recordings at each layer under different magnetic fields and temperatures. Furthermore, the magnetic measurements and heat-assisted magnetic recording simulations showed that these media enabled 3-level recording and could potentially be extended to 4-level recording, as the up-down and down-up states exhibited non-zero magnetization.

4.Room-Temperature Ferromagnetism in Fe-doped SnSe Bulk Single Crystalline Semiconductor

Authors:Guangqiang Mei, Wei Tan, Xingxia Cui, Cong Wang, Qing Yuan, Yafei Li, Cancan Lou, Xuefeng Hou, Mengmeng Zhao, Yong Liu, Wei Ji, Xiaona Zhang, Min Feng, Limin Cao

Abstract: The quest for pragmatic room-temperature (RT) magnetic semiconductors (MSs) with a suitable bandgap constitutes one of the contemporary opportunities to be exploited. This may provide a materials platform for to bring new-generation ideal information device technologies into real-world applications where the otherwise conventionally separately utilized charge and spin are simultaneously exploited. Here we present RT ferromagnetism in an Fe-doped SnSe (Fe:SnSe) van der Waals (vdW) single crystalline ferromagnetic semiconductor (FMS) with a semiconducting bandgap of ~1.19 eV (comparable to those of Si and GaAs). The synthesized Fe:SnSe single crystals feature a dilute Fe content of less than 1.0 at%, a Curie temperature of ~310 K, a layered vdW structure identical to that of pristine SnSe, and the absence of in-gap defect states. The Fe:SnSe vdW diluted magnetic semiconductor (DMS) single crystals are grown using a simple temperature-gradient melt-growth process, in which the magnetic Fe atom doping is realized uniquely using FeI2 as the dopant precursor whose melting point is low with respect to crystal growth, and which in principle possesses industrially unlimited scalability. Our work adds a new member in the family of long-searching RT magnetic semiconductors, and may establish a generalized strategy for large-volume production of related DMSs.

5.Cylindrical void growth vs. grain fragmentation in FCC single crystals: CPFEM study for two types of loading conditions

Authors:Saketh Virupakshi, Katarzyna Kowalczyk-Gajewska

Abstract: The crystal plasticity finite element method (CPFEM) is used to investigate the coupling between the cylindrical void growth or collapse and grain refinement in face-centered cubic (FCC) single crystals. A 2D plane strain model with one void is used. The effect of the initial lattice orientation, similarities, and differences between stress- and strain-driven loading scenarios are explored. To this end, boundary conditions are enforced in two different ways. The first one is based on maintaining constant in-plane stress biaxiality via a dedicated truss element, while the second one is imposing a constant displacement biaxiality factor. Uniaxial and biaxial loading cases are studied. For the uniaxial loading case a special configuration, which enforces an equivalent pattern of plastic deformation in the pristine crystal, is selected in order to investigate the mutual interactions between the evolving void and the developed lattice rotation heterogeneity. Next, biaxial loading cases are considered for three crystal orientations, one of which is not symmetric with respect to loading directions. It is analysed how stress or strain biaxility factors and initial lattice orientation influence the void evolution in terms of its size and shape. Moreover, the consequences of variations in the resulting heterogeneity of lattice rotation are studied in the context of the grain refinement phenomenon accompanying the void evolution. Scenarios that may lead to more advanced grain fragmentation are identified.

6.Equivariant graph neural network interatomic potential for Green-Kubo thermal conductivity in phase change materials

Authors:Sung-Ho Lee, Jing Li, Valerio Olevano, Benoit Sklénard

Abstract: Thermal conductivity is a fundamental material property that plays an essential role in technology, but its accurate evaluation presents a challenge for theory. In this letter, we demonstrate the application of E(3)-equivariant neutral network interatomic potentials within Green-Kubo formalism to determine the lattice thermal conductivity in amorphous and crystalline materials. We apply this method to study the thermal conductivity of germanium telluride (GeTe) as a prototypical phase change material. A single deep learning interatomic potential is able to describe the phase transitions between the amorphous, rhombohedral and cubic phases, with critical temperatures in good agreement with experiments. Furthermore, this approach accurately captures the pronounced anharmonicity present in GeTe, enabling precise calculations of thermal conductivity. In contrast, the Boltzmann transport equation tends to overestimate it by approximately a factor of two in the crystalline phases.

7.Composition variations in Cu(In,Ga)(S,Se)2 solar cells: not a gradient, but an interlaced network of two phases

Authors:Aubin JC. M. Prot, Michele Melchiorre, Felix Dingwell, Anastasia Zelenina, Hossam Elanzeery, Alberto Lomuscio, Thomas Dalibor, Maxim Guc, Robert Fonoll-Rubio, Victor Izquierdo-Roca, Gunnar Kusch, Rachel A. Oliver, Susanne Siebentritt

Abstract: Record efficiency in chalcopyrite-based solar cells Cu(In,Ga)(S,Se)2 is achieved using a gallium gradient to increase the band gap of the absorber towards the back side. Although this structure has successfully reduced recombination at the back contact, we demonstrate that in industrial absorbers grown in the pilot line of Avancis, the back part is a source of non-radiative recombination. Depth-resolved photoluminescence (PL) measurements reveal two main radiative recombination paths at 1.04 eV and 1.5-1.6 eV, attributed to two phases of low and high band gap material, respectively. Instead of a continuous change in the band gap throughout the thickness of the absorber, we propose a model where discrete band gap phases interlace, creating an apparent gradient. Cathodoluminescence and Raman scattering spectroscopy confirm this result. Additionally, deep defects associated to the high gap phase reduce the absorber performance. Etching away the back part of the absorber leads to an increase of one order of magnitude in the PL intensity, i.e., 60 meV in quasi Fermi level splitting. Non-radiative voltage losses correlate linearly with the relative contribution of the high energy PL peak, suggesting that reducing the high gap phase could increase the open circuit voltage by up to 180 mV.

8.Mechanical Energy Absorption of Architecturally Interlocked Petal-Schwarzites

Authors:Leonardo V. Bastos, Rushikesh S. Ambekar, Chandra S. Tiwary, Douglas S. Galvao, Cristiano F. Woellner

Abstract: We carried out fully atomistic reactive molecular dynamics simulations to study the mechanical behavior of six newly proposed hybrid schwarzite-based structures (interlocked petal-schwarzites). Schwarzites are carbon crystalline nanostructures with negative Gaussian curvature created by mapping a TPMS (Triply Periodic Minimal Surface) with carbon rings containing six to eight atoms. Our simulations have shown that petal-schwarzite structures can withstand uni-axial compressive stress up to the order of GPa and can be compressed past 50 percent strain without structural collapse. Our most resistant hierarchical structure has a calculated compressive strength of 260~GPa and specific energy absorption (SEA) of 45.95 MJ/kg, while possessing a mass density of only 685 kg/m$^3$. These results show that these structures could be excellent lightweight materials for applications that require mechanical energy absorption.

1.Two-Dimensional Band Dispersion of Ultra-Flat Hexagonal Bismuthene Grown on Ag(111) Bulk and Quantum-Well Films

Authors:Kazutoshi Takahashi, Masaki Imamura, Haruto Ikeda, Ryosuke Koyama, Isamu Yamamoto, Junpei Azuma

Abstract: Two-dimensional band dispersion of (2$\times$2) superstructure with Bi grown on Ag(111), which has been urged as an ultraflat hexagonal bismuthene, is investigated using angle-resolved photoemission spectroscopy (ARPES). The (2$\times$2)-Bi superstructure can be grown on the Ag(111) surface at low temperatures; it transforms into a surface alloy with a ($\sqrt{3}\times\sqrt{3}$) superstructure at 300 K. ARPES measurements reveal the consistency with the band structure of ultraflat bismuthene in previous reports. The band structure of (2$\times$2)-Bi surface remains unchanged with decreasing Ag layer thickness, indicating the limited penetration of Bi p-orbitals into the Ag layer.

2.Disentangling the Role of Electrons and Phonons in the Photoinduced CO Desorption and CO Oxidation on (O,CO)-Ru(0001)

Authors:Auguste Tetenoire, J. I. Juaristi, M. Alducin

Abstract: The role played by electronic and phononic excitations in the femtosecond laser induced desorption and oxidation of CO coadsorbed with O on Ru(0001) is investigated using ab initio molecular dynamics with electronic friction. To this aim, simulations that account for both kind of excitations and that only consider electronic excitations are performed. Results for three different surface coverages are obtained. We unequivocally demonstrate that CO desorption is governed by phononic excitations. In the case of oxidation the low statistics does not allow to give a categorical answer. However, the analysis of the adsorbates kinetic energy gain and displacements strongly suggest that phononic excitations and surface distortion also play an important role in the oxidation process.

3.Robust crystal structure identification at extreme conditions using a density-independent spectral descriptor and supervised learning

Authors:Paul Lafourcade, Jean-Bernard Maillet, Christophe Denoual, Eléonore Duval, Arnaud Allera, Alexandra M. Goryaeva, Mihai-Cosmin Marinica

Abstract: The increased time- and length-scale of classical molecular dynamics simulations have led to raw data flows surpassing storage capacities, necessitating on-the-fly integration of structural analysis algorithms. As a result, algorithms must be computationally efficient, accurate, and stable at finite temperature to reliably extract the relevant features of the data at simulation time. In this work, we leverage spectral descriptors to encode local atomic environments and build crystal structure classification models. In addition to the classical way spectral descriptors are computed, i.e. over a fixed radius neighborhood sphere around a central atom, we propose an extension to make them independent from the material's density. Models are trained on defect-free crystal structures with moderate thermal noise and elastic deformation, using the linear discriminant analysis (LDA) method for dimensionality reduction and logistic regression (LR) for subsequent classification. The proposed classification model is intentionally designed to be simple, incorporating only a limited number of parameters. This deliberate simplicity enables the model to be trained effectively even when working with small databases. Despite the limited training data, the model still demonstrates inherent transferability, making it applicable to a broader range of scenarios and datasets. The accuracy of our models in extreme conditions is compared to traditional algorithms from the literature, namely adaptive common neighbor analysis (a-CNA), polyhedral template matching (PTM) and diamond structure identification (IDS). Finally, we showcase two applications of our method: tracking a solid-solid BCC-to-HCP phase transformation in Zirconium at high pressure up to high temperature, and visualizing stress-induced dislocation loop expansion in single crystal FCC Aluminum containing a Frank-Read source, at high temperature.

4.Efficient computation of optical excitations in two-dimensional materials with the Xatu code

Authors:Alejandro José Uría-Álvarez, Juan José Esteve-Paredes, Manuel Antonio García-Blázquez, Juan José Palacios

Abstract: Here we describe an efficient numerical implementation of the Bethe-Salpeter equation to obtain the excitonic spectrum of semiconductors. This is done on the electronic structure calculated either at the simplest tight-binding level or through density funcional theory calculations based on local orbitals. We use a simplified model for the electron-electron interactions which considers atomic orbitals as point-like orbitals and a phenomenological screening. The optical conductivity can then be optionally computed within the Kubo formalism. Our results for paradigmatic two-dimensional materials such as hBN and MoS2, when compared with those of more sophisticated first-principles methods, are excellent and envision a practical use of our implementation beyond the computational limitations of such methods.

5.Electronic structure of the Ge/Si(105) hetero-interface

Authors:Polina M. Sheverdyaeva, Conor Hogan, Anna Sgarlata, Laura Fazi, Massimo Fanfoni, Luca Persichetti, Paolo Moras, Adalberto Balzarotti

Abstract: Thin Ge layers deposited on Si(105) form a stable single-domain film structure with large terraces and rebonded-step surface termination, thus realizing an extended and ordered Ge/Si planar hetero-junction. At the coverage of four Ge monolayers angle-resolved photoemission spectroscopy reveals the presence of two-dimensional surface and film bands displaying energy-momentum dispersion compatible with the 5x4 periodicity of the system. The good agreement between experiment and first-principles electronic structure calculations confirms the validity of the rebonded-step structural model. The direct observation of surface features within 1 eV below the valence band maximum corroborates previously reported analysis of the electronic and optical behavior of the Ge/Si hetero-interface.

6.Intermittent in-situ high-resolution X-ray microscopy of 400-nm porous glass under uniaxial compression: study of pore changes and crack formation

Authors:Sebastian Schäfer, François Willot, Mansoureh Norouzi Rad, Stephen T. Kelly, Dirk Enke, Juliana Martins de Souza e Silva

Abstract: The properties of porous glasses and their field of application strongly depend on the characteristics of the void space. Understanding the relationship between their porous structure and failure behaviour can contribute to the development of porous glasses with long-term reliability optimized for specific applications. In the present work, we used X-ray computed tomography with nanometric resolution (nano-CT) to image a controlled pore glass (CPG) with 400 nm-sized pores whilst undergoing uniaxial compression in-situ to emulate a stress process. Our results show that in-situ nano-CT provides an ideal platform for identifying the mechanisms of damage within glass with pores of 400 nm, as it allowed the tracking of the pores and struts change of shape during compression until specimen failure. We have also applied computational tools to quantify the microstructural changes within the CPG sample by mapping the displacements and strain fields, and to numerically simulate the behaviour of the CPG using a Fast Fourier Transform/phase-field method. Both experimental and numerical data show local shear deformation, organized along bands, consistent with the appearance and propagation of +/- 45 degrees cracks.

7.Discovery of the high thermoelectric performance in low-cost Cu8SiSxSe6-x argyrodites

Authors:Taras Parashchuk, Oleksandr Cherniushok, Raul Cardoso-Gil, Janusz Tobola, Yuri Grin, Krzysztof T. Wojciechowski

Abstract: Cu-based argyrodites have gained much attention as a new class of thermoelectric materials for energy harvesting. However, the phase transition occurring in these materials and low energy conversion performance limited their broad application in thermoelectric converters. In this work, we disclose a newly discovered highly efficient Cu8SiSxSe6-x argyrodite with stabilized high-symmetry cubic phase at above 282 K opening the practical potential of this material for the mid-temperature region applications. The temperature range broadening of the high-symmetry phase existence was possible due to the successful substitution of Se with S in Cu8SiSxSe6-x, which enhances the configurational entropy. The developed argyrodites show excellent thermoelectric performance thanks to the increased density of states effective mass and ultralow lattice thermal conductivity. Further tuning of the carrier concentration through the Cu-deviation improves the thermoelectric performance significantly. The dimensionless thermoelectric figure of merit ZT and estimated energy conversion efficiency {\eta} for Cu7.95SiS3Se3 achieve outstanding values of the 1.45 and 13 %, respectively, offering this argyrodite as a low-cost and Te-free alternative for the thermoelectric energy conversion applications.

8.Learning a reactive potential for silica-water through uncertainty attribution

Authors:Swagata Roy, Johannes P. Dürholt, Thomas S. Asche, Federico Zipoli, Rafael Gómez-Bombarelli

Abstract: The reactivity of silicates in an aqueous solution is relevant to various chemistries ranging from silicate minerals in geology, to the C-S-H phase in cement, nanoporous zeolite catalysts, or highly porous precipitated silica. While simulations of chemical reactions can provide insight at the molecular level, balancing accuracy and scale in reactive simulations in the condensed phase is a challenge. Here, we demonstrate how a machine-learning reactive interatomic potential can accurately capture silicate-water reactivity. The model was trained on a new dataset comprising 400,000 energies and forces of molecular clusters at the $\omega$-B97XD def2-TVZP level. To ensure the robustness of the model, we introduce a new and general active learning strategy based on the attribution of the model uncertainty, that automatically isolates uncertain regions of bulk simulations to be calculated as small-sized clusters. Our trained potential is found to reproduce static and dynamic properties of liquid water and solid crystalline silicates, despite having been trained exclusively on cluster data. Furthermore, we utilize enhanced sampling simulations to recover the self-ionization reactivity of water accurately, and the acidity of silicate oligomers, and lastly study the silicate dimerization reaction in a water solution at neutral conditions and find that the reaction occurs through a flanking mechanism.

9.Boundary Flat Bands with Topological Spin Textures Protected by Sub-chiral Symmetry

Authors:Yijie Mo, Xiao-Jiao Wang, Rui Yu, Zhongbo Yan

Abstract: Chiral symmetry plays an indispensable role in topological classifications as well as in the understanding of the origin of bulk or boundary flat bands. The conventional definition of chiral symmetry refers to the existence of a constant unitary matrix anticommuting with the Hamiltonian. As a constant unitary matrix has constant eigenvectors, boundary flat bands enforced by chiral symmetry, which share the same eigenvectors with the chiral symmetry operator, are known to carry fixed (pseudo)spin polarizations and be featureless in quantum geometry. In this work, we generalize the chiral symmetry and introduce a concept termed sub-chiral symmetry. Unlike the conventional chiral symmetry operator defined as constant, the sub-chiral symmetry operator depends on partial components of the momentum vector, so as its eigenvectors. We show that topological gapped or gapless systems without the chiral symmetry but with the sub-chiral symmetry can support boundary flat bands, which exhibit topological spin textures and quantized Berry phases. We expect that such intriguing boundary flat bands could give rise to a variety of exotic physics in the presence of interactions or disorders.

10.Phonon-induced magnetization dynamics in Co-doped iron garnets

Authors:A. Frej, C. S. Davies, A. Kirilyuk, A. Stupakiewicz

Abstract: The developing field of strain-induced magnetization dynamics offers a promising path toward efficiently controlling spins and phase transitions. Understanding the underlying mechanisms is crucial in finding the optimal parameters supporting the phononic switching of magnetization. Here, we present an experimental and numerical study of time-resolved magnetization dynamics driven by the resonant excitation of an optical phonon mode in iron