Electronic-grade epitaxial (111) KTaO3 heterostructures.

KTaO3 heterostructures have recently attracted attention as model systems 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 heterostructure interfaces clean enough to reveal the intrinsic quantum properties. Here, we report superconducting heterostructures based on high-quality epitaxial (111) KTaO3 thin films using an adsorption-controlled hybrid PLD to overcome the vapor pressure mismatch. Electrical and structural characterizations reveal that the higher-quality heterostructure interface between amorphous LaAlO3 and KTaO3 thin films supports a two-dimensional electron gas with substantially higher electron mobility, superconducting transition temperature, and critical current density than that in bulk single-crystal KTaO3-based heterostructures. Our hybrid approach may enable epitaxial growth of other alkali metal-based oxides that lie beyond the capabilities of conventional methods.

Salt-Assisted Selective Growth of H-phase Monolayer VSe2 with Apparent Hole Transport Behavior.

Vanadium diselenide (VSe2) exhibits versatile electronic and magnetic properties in the trigonal prismatic (H-) and octahedral (T-) phases. Compared to the metallic T-phase, the H-phase with a tunable semiconductor property is predicted to be a ferrovalley material with spontaneous valley polarization. Herein we report an epitaxial growth of the monolayer 2D VSe2 on a mica substrate via the chemical vapor deposition (CVD) method by introducing salt in the precursor. Our first-principles calculations suggest that the monolayer H-phase VSe2 with a large lateral size is thermodynamically favorable. The honeycomb-like structure and the broken symmetry are directly observed by spherical aberration-corrected scanning transmission electron microscopy (STEM) and confirmed by giant second harmonic generation (SHG) intensity. The p-type transport behavior is further evidenced by the temperature-dependent resistance and field-effect device study. The present work introduces a new phase-stable 2D transition metal dichalcogenide, opening the prospect of novel electronic and spintronics device design.

Enhancing Moisture Stability of Sulfide Solid-State Electrolytes by Reversible Amphipathic Molecular Coating.

The all-solid-state battery (ASSB) is a promising next-generation energy storage technology for both consumer electronics and electric vehicles because of its high energy density and improved safety. Sulfide solid-state electrolytes (SSEs) have merits of low density, high ionic conductivity, and favorable mechanical properties compared to oxide ceramic and polymer materials. However, mass production and processing of sulfide SSEs remain a grand challenge because of their poor moisture stability. Here, we report a reversible surface coating strategy for enhancing the moisture stability of sulfide SSEs using amphipathic organic molecules. An ultrathin layer of 1-bromopentane is coated on the sulfide SSE surface (e.g., Li7P2S8Br0.5I0.5) via Van der Waals force. 1-Bromopentane has more negative adsorption energy with SSEs than H2O based on first-principles calculations, thereby enhancing the moisture stability of SSEs because the hydrophobic long-chain alkyl tail of 1-bromopentane repels water molecules. Moreover, this amphipathic molecular layer has a negligible effect on ionic conductivity and can be removed reversibly by heating at low temperatures (e.g., 160 °C). This finding opens a new pathway for the surface engineering of moisture-sensitive SSEs and other energy materials, thereby speeding up their deployment in ASSBs.

Atomic control of active-site ensembles in ordered alloys to enhance hydrogenation selectivity.

Intermetallic compounds offer unique opportunities for atom-by-atom manipulation of catalytic ensembles through precise stoichiometric control. The (Pd, M, Zn) γ-brass phase enables the controlled synthesis of Pd-M-Pd catalytic sites (M = Zn, Pd, Cu, Ag and Au) isolated in an inert Zn matrix. These multi-atom heteronuclear active sites are catalytically distinct from Pd single atoms and fully coordinated Pd. Here we quantify the unexpectedly large effect that active-site composition (that is, identity of the M atom in Pd-M-Pd sites) has on ethylene selectivity during acetylene semihydrogenation. Subtle stoichiometric control demonstrates that Pd-Pd-Pd sites are active for ethylene hydrogenation, whereas Pd-Zn-Pd sites show no measurable ethylene-to-ethane conversion. Agreement between experimental and density-functional-theory-predicted activities and selectivities demonstrates precise control of Pd-M-Pd active-site composition. This work demonstrates that the diversity and well-defined structure of intermetallics can be used to design active sites assembled with atomic-level precision.

Forming mechanism of equilibrium and non-equilibrium metallurgical phases in dissimilar aluminum/steel (Al-Fe) joints.

Forming metallurgical phases has a critical impact on the performance of dissimilar materials joints. Here, we shed light on the forming mechanism of equilibrium and non-equilibrium intermetallic compounds (IMCs) in dissimilar aluminum/steel joints with respect to processing history (e.g., the pressure and temperature profiles) and chemical composition, where the knowledge of free energy and atomic diffusion in the Al-Fe system was taken from first-principles phonon calculations and data available in the literature. We found that the metastable and ductile (judged by the presently predicted elastic constants) Al6Fe is a pressure (P) favored IMC observed in processes involving high pressures. The MoSi2-type Al2Fe is brittle and a strong P-favored IMC observed at high pressures. The stable, brittle η-Al5Fe2 is the most observed IMC (followed by θ-Al13Fe4) in almost all processes, such as fusion/solid-state welding and additive manufacturing (AM), since η-Al5Fe2 is temperature-favored, possessing high thermodynamic driving force of formation and the fastest atomic diffusivity among all Al-Fe IMCs. Notably, the ductile AlFe3, the less ductile AlFe, and most of the other IMCs can be formed during AM, making AM a superior process to achieve desired IMCs in dissimilar materials. In addition, the unknown configurations of Al2Fe and Al5Fe2 were also examined by machine learning based datamining together with first-principles verifications and structure predictions. All the IMCs that are not P-favored can be identified using the conventional equilibrium phase diagram and the Scheil-Gulliver non-equilibrium simulations.

Correlation analysis of materials properties by machine learning: illustrated with stacking fault energy from first-principles calculations in dilute fcc-based alloys.

Advances in machine learning (ML), especially in the cooperation between ML predictions, density functional theory (DFT) based first-principles calculations, and experimental verification are emerging as a key part of a new paradigm to understand fundamentals, verify, analyze, and predict data, and design and discover materials. Taking stacking fault energy (γSFE) as an example, we perform a correlation analysis ofγSFEin dilute Al-, Ni-, and Pt-based alloys by descriptors and ML algorithms. TheseγSFEvalues were predicted by DFT-based alias shear deformation approach, and up to 49 elemental descriptors and 21 regression algorithms were examined. The present work indicates that (i) the variation ofγSFEaffected by alloying elements can be quantified through 14 elemental attributes based on their statistical significances to decrease the mean absolute error (MAE) in ML predictions, and in particular, the number of p valence electrons, a descriptor second only to the covalent radius in importance to model performance, is unexpected; (ii) the alloys with elements close to Ni and Co in the periodic table possess higherγSFEvalues; (iii) the top four outliers of DFT predictions ofγSFEare for the alloys of Al23La, Pt23Au, Ni23Co, and Al23Be based on the analyses of statistical differences between DFT and ML predictions; and (iv) the best ML model to predictγSFEis produced by Gaussian process regression with an average MAE < 8 mJ m-2. Beyond detailed analysis of the Al-, Ni-, and Pt-based alloys, we also predict theγSFEvalues using the present ML models in other fcc-based dilute alloys (i.e., Cu, Ag, Au, Rh, Pd, and Ir) with the expected MAE < 17 mJ m-2and observe similar effects of alloying elements onγSFEas those in Pt23X or Ni23X.

Realization of Epitaxial Thin Films of the Topological Crystalline Insulator Sr3 SnO.

Topological materials are derived from the interplay between symmetry and topology. Advances in topological band theories have led to the prediction that the antiperovskite oxide Sr3 SnO is a topological crystalline insulator, a new electronic phase of matter where the conductivity in its (001) crystallographic planes is protected by crystallographic point group symmetries. Realization of this material, however, is challenging. Guided by thermodynamic calculations, a deposition approach is designed and implemented to achieve the adsorption-controlled growth of epitaxial Sr3 SnO single-crystal films by molecular-beam epitaxy (MBE). In situ transport and angle-resolved photoemission spectroscopy measurements reveal the metallic and electronic structure of the as-grown samples. Compared with conventional MBE, the used synthesis route results in superior sample quality and is readily adapted to other topological systems with antiperovskite structures. The successful realization of thin films of Sr3 SnO opens opportunities to manipulate topological states by tuning symmetries via strain engineering and heterostructuring.

Data set for diffusion coefficients and relative creep rate ratios of 26 dilute Ni-X alloy systems from first-principles calculations.

The development of future generations of Ni-base superalloys will depend on a systematic understanding of how each alloying element affects the fundamental properties of Ni-base superalloys, particularly with respect to their creep behavior. First, this article presents the temperature-dependent data of all factors entering into dilute impurity diffusion for 26 Ni-X alloy systems, including atomic jump frequencies, thermodynamic parameters, and diffusivity plots. Second, this article presents the data used to calculate the relative creep rate ratios showing the effect of each of the 26 alloying elements, X, on the dilute Ni-X alloy. The dataset refers to "A comprehensive first-principles study of solute elements in dilute Ni alloys: Diffusion coefficients and their implications to tailor creep rate" by Hargather et al. [1].

Fundamentals of Thermal Expansion and Thermal Contraction.

Thermal expansion is an important property of substances. Its theoretical prediction has been challenging, particularly in cases the volume decreases with temperature, i.e., thermal contraction or negative thermal expansion at high temperatures. In this paper, a new theory recently developed by the authors has been reviewed and further examined in the framework of fundamental thermodynamics and statistical mechanics. Its applications to cerium with colossal thermal expansion and Fe3Pt with thermal contraction in certain temperature ranges are discussed. It is anticipated that this theory is not limited to volume only and can be used to predict a wide range of properties at finite temperatures.

Origin of Outstanding Phase and Moisture Stability in a Na3P1-xAsxS4 Superionic Conductor.

Sodium ion (Na) solid-state electrolytes (SSEs) are critical to address notorious safety issues associated with liquid electrolytes used in the current Na ion batteries. Fulfilling multiple innovations is a grand challenge but is imperative for advanced Na ion SSEs, such as a combination of high ionic conductivity and excellent chemical stability. Here, our first-principles and phonon calculations reveal that Na3P1-xAsxS4 (0 ≤ x ≤ 1) is a solid-state superionic conductor stabilized at 0 K by zero-point vibrational energy and at finite temperatures by vibrational and configurational entropies. Especially, our integrated first-principles and experimental approach indicates that Na3P1-xAsxS4 is dry-air stable. Additionally, the alloying element arsenic greatly enhances the moisture (i.e., H2O) stability of Na3P1-xAsxS4 by shifting the reaction products from the easy-forming oxysulfides (such as Na3POS3 and Na3PO2S2 with H2S release) to the difficult-forming hydrates (such as Na3P1-xAsxS4·nH2O with n = 8 and/or 9) due mainly to a weaker As-O affinity compared to that of P-O. The present work demonstrates that alloying is able to achieve multiple innovations for solid-state electrolytes, such as a desirable superionic conductor with not only a high ionic conductivity (for example, 1.46 mS/cm at room temperature achieved in Na3P0.62As0.38S4) but also an excellent chemical stability with respect to temperature, composition, and moisture.

Exceptionally High Ionic Conductivity in Na3 P0.62 As0.38 S4 with Improved Moisture Stability for Solid-State Sodium-Ion Batteries.

A Na-ion solid-state electrolyte, Na3 P0.62 As0.38 S4 , is developed with an exceptionally high conductivity of 1.46 mS cm-1 at 25 °C and enhanced moisture stability. Dual effects of alloying element As (lattice expansion and a weaker AsS bond strength) are responsible for the superior conductivity. Improved moisture stability is regulated by shifting low-energy moisture reactions to high-energy ones due to As.

Lateral Versus Vertical Growth of Two-Dimensional Layered Transition-Metal Dichalcogenides: Thermodynamic Insight into MoS2.

Unprecedented interest has been spurred recently in two-dimensional (2D) layered transition metal dichalcogenides (TMDs) that possess tunable electronic and optical properties. However, synthesis of a wafer-scale TMD thin film with controlled layers and homogeneity remains highly challenging due mainly to the lack of thermodynamic and diffusion knowledge, which can be used to understand and design process conditions, but falls far behind the rapidly growing TMD field. Here, an integrated density functional theory (DFT) and calculation of phase diagram (CALPHAD) modeling approach is employed to provide thermodynamic insight into lateral versus vertical growth of the prototypical 2D material MoS2. Various DFT energies are predicted from the layer-dependent MoS2, 2D flake-size related mono- and bilayer MoS2, to Mo and S migrations with and without graphene and sapphire substrates, thus shedding light on the factors that control lateral versus vertical growth of 2D islands. For example, the monolayer MoS2 flake in a small 2D lateral size is thermodynamically favorable with respect to the bilayer counterpart, indicating the monolayer preference during the initial stage of nucleation; while the bilayer MoS2 flake becomes stable with increasing 2D lateral size. The critical 2D flake-size of phase stability between mono- and bilayer MoS2 is adjustable via the choice of substrate. In terms of DFT energies and CALPHAD modeling, the size dependent pressure-temperature-composition (P-T-x) growth windows are predicted for MoS2, indicating that the formation of MoS2 flake with reduced size appears in the middle but close to the lower T and higher P "Gas + MoS2" phase region. It further suggests that Mo diffusion is a controlling factor for MoS2 growth owing to its extremely low diffusivity compared to that of sulfur. Calculated MoS2 energies, Mo and S diffusivities, and size-dependent P-T-x growth windows are in good accord with available experiments, and the present data provide quantitative insight into the controlled growth of 2D layered MoS2.

Data set for diffusion coefficients of alloying elements in dilute Mg alloys from first-principles.

Diffusion coefficients of alloying elements in Mg are critical for the development of new Mg alloys for lightweight applications. Here we present the data set of the temperature-dependent dilute tracer diffusion coefficients for 47 substitutional alloying elements in hexagonal closed packed (hcp) Mg calculated from first-principles calculations based on density functional theory (DFT) by combining transition state theory and an 8-frequency model. Benchmark for the DFT calculations and systematic comparison with experimental diffusion data are also presented. The data set refers to "Diffusion coefficients of alloying elements in dilute Mg alloys: A comprehensive first-principles study" by Zhou et al. [1].

First-principles study of lattice dynamics and thermodynamics of TiO2 polymorphs.

The structural, phonon, and thermodynamic properties of six TiO(2) polymorphs, i.e., rutile, anatase, columbite, baddeleyite, orthorhombic I, and cotunnite, have been systematically investigated by density functional theory. The predicted volumes, bulk modulus, and Debye temperature are in good agreement with experiments. The phonon dispersions of the TiO(2) polymorphs were studied by the supercell approach, whereas the long-range dipole-dipole interactions were calculated by linear response theory to reproduce the LO-TO splitting, making accurate prediction of phonon frequencies for the polar material TiO(2). The calculated phonon dispersions show that all TiO(2) polymorphs are dynamically stable at ambient pressure, indicating the high-pressure phases might be quenched to ambient conditions as ultrahard materials. Furthermore, the finite temperature thermodynamic properties of TiO(2) polymorphs were predicted accurately from the obtained phonon density of states, which is critical in the future study of the pressure-temperature phase diagram of TiO(2). The calculated Gibbs energies reveal that rutile is more stable than anatase at ambient pressure. We derived the Gibbs energy and heat capacity functions for all TiO(2) polymorphs for use in thermodynamic modeling of phase equilibria.

Temperature-dependent elastic stiffness constants of α- and θ-Al2O3 from first-principles calculations.

Temperature-dependent elastic stiffness constants (c(ij)s), including both the isothermal and isoentropic ones, have been predicted for rhombohedral α-Al(2)O(3) and monoclinic θ-Al(2)O(3) in terms of a quasistatic approach, i.e., a combination of volume-dependent c(ij)s determined by a first-principles strain versus stress method and direction-dependent thermal expansions obtained by first-principles phonon calculations. A good agreement is observed between the predictions and the available experiments for α-Al(2)O(3), especially for the off-diagonal elastic constants. In addition, the temperature-dependent c(ij)s predicted herein, in particular the ones for metastable θ-Al(2)O(3), enable the stress analysis at elevated temperatures in thermally grown oxides containing α- and θ-Al(2)O(3), which are crucial to understand the failure of thermal barrier coatings in gas-turbine engines.

First-principles study of structural and elastic properties of monoclinic and orthorhombic BiMnO3.

The structural and elastic properties of BiMnO(3) with monoclinic (C 2/c) and orthorhombic (Pnma) ferromagnetic (FM) structures have been studied by first-principles calculations within LDA + U and GGA + U approaches. The equilibrium volumes and bulk moduli of BiMnO(3) phases are evaluated by equation of state (EOS) fittings, and the bulk properties predicted by LDA + U calculations are in better agreement with experiment. The orthorhombic phase is found to be more stable than the monoclinic phase at ambient pressure. A monoclinic to monoclinic phase transition is predicted to occur at a pressure of about 10 GPa, which is ascribed to magnetism versus volume instability of monoclinic BiMnO(3). The single-crystal elastic stiffness constants c(ij)s of the monoclinic and orthorhombic phases are investigated using the stress-strain method. The c(46) of the monoclinic phase is predicted to be negative. In addition, the polycrystalline elastic properties including bulk modulus, shear modulus, Young's modulus, bulk modulus-shear modulus ratio, Poisson's ratio, and elastic anisotropy ratio are determined based on the calculated elastic constants. The presently predicted phase transition and elastic properties open new directions for investigation of the phase transitions in BiMnO(3), and provide helpful guidance for the future elastic constant measurements.