Materials Science (cond-mat.mtrl-sci)

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

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.

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 $\tau_h=0.3443(1)$.

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.

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.

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.

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.

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.

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.

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.