Materials Science (cond-mat.mtrl-sci)

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.