Atomic Occupancies Research Articles

Superior Piezo-/Ferro-Electricity in Antiferroelectric AgxNbO3-δ Thin Films by Nanopillar Local Structure Design.

Antiferroelectrics are fundamental mother compounds critical in developing innovative lead-free piezoelectrics and ferroelectrics and hold great promise for wide-ranging applications in energy conversion and electronic devices. However, harnessing their superior properties presents a significant challenge due to the delicate balance required between their various states. In this study, through the unique design of nanopillar structures to alleviate the local polar heterogeneity, we have achieved significantly improved piezo-/ferro-electricity in classic lead-free antiferroelectric AgxNbO3-δ (x = 1, 0.9, and 0.8) epitaxial thin films. The effective piezoelectric coefficient reaches 440 pm V-1, 1 order of magnitude larger than the stoichiometric AgNbO3, rivaling classic lead zirconate titanate piezoelectrics. Atomic-scale electron microscopy investigations unravel the underlying mechanisms. The nanopillars, characterized by antisite occupancy of both Ag and Nb atoms and forming out-of-phase boundaries with the matrix, reduce the local crystal symmetry via interphase strain. This leads to the creation of flexible multinanodomain structures that significantly facilitate polarization rotation, thus substantially enhancing the piezoelectric performance. This study demonstrates the feasibility of engineering local heterogeneity through nanopillar design, offering a generally applicable method for property improvement of a wide range of antiferroelectrics.

Effect of element doping on the structural stability, magnetic properties and electronic structure of SmCo5-based rare earth permanent magnets

Doping transition metals has been proven as an effective method to enhance the performance of Sm-Co based rare earth permanent magnets. However, due to the complex interactions involved, the specific effects on magnetic properties, atomic occupancy preferences and structural stability mechanisms are still to be further investigated. In this study, we systematically investigated the influence of various transition metal dopants on the structural stability, magnetic properties and electronic structure of SmCo5 rare earth permanent magnet using first-principles calculations. Our calculations show that Ti, V, Cr, Mn, Ni, Cu, Zn elements preferentially occupy the 3 g site, while Sc and Zr tend to occupy the 1a site, and Fe elements have a preference for the 2c site. Regarding structural stability, doping with Sc, Cr, Mn, Fe, Ni, Cu, Zn and Zr all contribute to enhancing structural stability, while Ti and V doping exhibit adverse effects. Magnetic calculations indicate that doping with Mn and Fe significantly increases the total magnetic moment of the SmCo5 system. Notably, at a high doping concentration of 60 at%, the Ni and Zn-doped systems exhibit an exceptionally large magnetocrystalline anisotropy energy Additionally, a change in the magnetic easy axis direction occurs when the doping concentrations of Cr, Fe, Cu and Zn reach 60 at%, 40 at%, 40 at% (and 60 at%), 40 at% (and 60 at%), respectively. Our work provides important theoretical guidance for further optimizing the performance of Sm-Co based rare earth permanent magnets.

Symbolic transform optimized convolutional neural network model for high-performance prediction and analysis of MXenes hydrogen evolution reaction catalysts

Two-dimensional MXenes materials are expected to be cost-effective and efficient catalysts for hydrogen evolution reaction (HER) due to their tunable surface electronic structure. To optimize its catalytic activity, this study proposes a data-driven framework (CROSST) to generate descriptors through feature engineering and integrate them into a convolutional neural network to predict the HER performance of transition-metal (TM) anchored bis-transition-metal carbon-nitride (TM-M′2M′′CNO2) catalysts. The STCNN model achieves a coefficient of determination of more than 0.93, showing the ability to predict the Gibbs free energy of hydrogen adsorption (ΔGH) with high accuracy. We explored the microscopic mechanisms of HER activity through density functional theory and machine learning analysis. It was found that TM anchoring altered the charge distribution of the MXenes material, elevated the atomic orbital occupancy of neighboring O sites, and weakened the O adsorption of H, thus affecting the HER activity. These results provide a theoretical basis for the design of high-performance MXenes HER catalysts and contribute new research perspectives.

Thermal stability and properties of silicon-germanium nanocrystals

Using first-principles calculations and ensemble theory, we have calculated the ground-state energy and electronic properties of SixGe10−xH16 nanocrystals, and analyzed their stability and properties at finite temperatures. We have determined the numerical correspondence between chemical potential and the proportion of element in SixGe10−xH16. The probability of various structures appearing within SixGe10−xH16 nanocrystals depends on temperature and chemical potential environment. The influence of vibrational free energy, as investigated by theoretical computations, is also summarized. The research results show that vibrational free energy enhances the structure stability by the occupation of Ge atoms and results in a more concentrated distribution of the gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital.

Controllable Regulation of MoS2 Surface Atomic Exposure for Boosting Interfacial Polarization and Microwave Absorption

AbstractAtomic‐level surface design of 2D materials, which benefits from their ultra‐high occupancy of surface atoms, has demonstrated significant potential for regulating electronic states. Despite efforts to explore heterojunctions on 2D surfaces, the stacking‐dominated surface electronic structures and their influences on dielectric polarization remain unclear. Herein, a confined growth strategy is proposed to accurately adjust the surface atom occupancy of MoS2 nanoflakes and thereby boost the polarization‐dominated microwave absorption (MA). By altering the stacking layer number from single layers to tens of layers of MoS2, the charge transfer from graphite substrate to MoS2 surface atoms, accompanied by the formation of local electric fields, reaches its highest intensity at two layers and then degrades dramatically with thicker MoS2 nanoflakes. The strengthened dielectric properties eventually enhance the MA performance, increasing the maximum absorption intensity (41.9 dB) by 346% and the effective absorption bandwidth (3 GHz) by 750%. These discoveries shed new light on the electronic modification of 2D materials and their electromagnetic functionalization.

A multi-orbital Hund´s rules-based Ionic Hamiltonian for transition metal atoms: High-order Equation of Motion Method approach and Kondo resonances.

A multi-orbital ionic Hamiltonian is presented to analyze the many-body properties of the d-transition metal atoms. This Hamiltonian considers all the atomic states obeying the first Hund´s rule and also includes all orbital degeneracy, as well as the interaction of the atom with a metal. We analyze the solution of this ionic Hamiltonian by means of the Equation of Motion (EOM) method up to the fourth order, V4, in the atom-metal interaction. Equations for the appropriate Green-functions for analyzing the chemical and transport properties of the system are given for different atom occupancies. In particular, we introduce a full analysis of the multi-orbital Hamiltonian including atomic configurations with N, N+1 and N-1 electrons, and discuss its Kondo properties. The shells d1, d2 and d3 are analyzed in detail and Kondo energies are deduced in all these cases showing good agreement with the conventional known results.&#xD.

VASE: A High-Entropy Alloy Short-Range Order Structural Descriptor for Machine Learning.

The short-range order (SRO) structure in high-entropy alloys (HEAs) is closely associated with many properties, which can be studied through density functional theory (DFT) calculations. Atomic-scale modeling and calculations require substantial computational resources, and machine learning can provide rapid estimations of DFT results. To describe SRO information in HEAs, a new descriptor based on Voronoi Analysis and Shannon Entropy (VASE) is proposed. Based on Voronoi analysis, the Shannon entropy is introduced to directly characterize atomic spatial arrangement information except for composition and atomic interactions, which is necessary for describing the disorder atomic occupancy in HEAs. The new descriptor is used for predicting the formation energy of FeCoNiAlTiCu system based on machine learning model, which is more accurate than other descriptors (Coulomb matrices, partial radial distribution functions, and Voronoi analysis). Moreover, the model trained based on VASE descriptors exhibits the best predictive performance for unrelaxed structures (24.06 meV/atom). The introduction of Shannon entropy provides an effective representation of atomic arrangement information in HEAs, which is a powerful tool for investigating the SRO phenomena.

Evolution of structure, magnetism, and electronic/thermal-transports of Ti(Cr)-substituted Fe2CrV all-d-metal Heusler ferromagnets

All-d-metal full-Heusler alloys possess superior mechanical properties and high spin polarization, which would play an important role in spintronic applications. Despite this, their electrical and thermal transport properties have not been comprehensively investigated till now. In this work, we present an analysis on the evolution of structural, magnetic and transport properties of Cr- and Ti-substituted Fe2CrV all-d-metal Heusler alloys by combining theoretical calculations and experiments. Both series of alloys crystallize in Hg2CuTi-type structure. With increasing Ti doping, the calculated total magnetic moments of Fe50Cr25V25-xTix decrease linearly. The experimental saturation magnetization is highly consistent with theoretical calculations and Slater-Pauling rule when x < 4, indicating the highly ordered atomic occupation. The magnetization and Curie temperature can be significantly tuned by altering spin polarizations and exchange interactions. The introduction of the foreign atom, Ti, results in a linear increase in residual resistivity, while electron-phonon scattering keeps relatively constant. The maximum values for electrical and thermal transport properties are observed in the stoichiometric Fe2CrV composition.

Atomic arrangement and mechanical properties of high-entropy nonoxide ceramics simulated via location preference-based disordered random structure

The cell structures and mechanical properties (i.e., hardness, Young's modulus, shear modulus, and Poisson's ratio) of (Hf0.2Zr0.2Ti0.2Nb0.2Ta0.2)C (HEC) and (Hf0.2Zr0.2Ti0.2Nb0.2Ta0.2)N (HEN) high-entropy ceramics were simulated by special quasi-random structure (SQS) and general random structure (GRS) with atomic occupation preference based on the first-principles density functional theory. The results show that compared to SQS, the cell structure constructed by GRS is more realistic, which is verified via scanning electron microscopy, high resolution transmission electron microscopy and energy dispersive spectroscopy. The mechanical properties simulated by GRS were also determined by microhardness and dynamic elastic modulus testers. The hardness, Young's modulus，shear modulus and Poisson's ratio predicted by GRS are 23.07 GPa, 449.71 GPa, 183.28 and 0.227 for HEC and 22.96 GPa, 413.71 GPa, 162.47 and 0.241 for HEN, which are in a reasonable agreement with the measured results (i.e., 22.05 ± 0.32 GPa, 433 ± 12 GPa, 172 ± 18 GPa, 0.21 for HEC and 22.12 ± 0.13 GPa, 372 ± 23 GPa, 158 ± 11 GPa, 0.23 for HEN). This work can provide a promising reference for preparing high-entropy non-oxide ceramics via the prediction.

Effect of elastic strain energy on precipitation process of Co81Al5V14 alloy based on microscopic phase field method

The L12 phase volume fraction, size, microstructure significantly influences alloy's important physical and mechanical properties in Co-Al-V superalloy. Based on microscopic phase field method and microelasticity theory, precipitation of ordered L12 phase in Co81Al5V14 alloy were studied. The results indicate that precipitation sequence of Co81Al5V14 alloy is minimally influenced by elastic strain energy and precipitation sequence can be divided into four stages. Elastic strain energy does not significantly affect incubation period of alloy, but it does promote the formation of transitional ordered phase L10 with a single orientation and facilitates precipitation of ordered phase L12. Elastic strain energy causes precipitates to grow and coarsen along specific elastic "soft" direction ([100] and [001]). Elastic strain energy promotes process of ordering and atomic occupancy of the alloy. The effects of elastic strain energy on precipitation mechanism, microstructure and atomic occupancy are discussed in this work, which provides theoretical guidance for the design of Co-Al-V alloys with better properties.

Synthesis and in-depth structure determination of a novel metastable high-pressure CrTe3 phase

This study reports the synthesis and crystal structure determination of a novel CrTe3 phase using various experimental and theoretical methods. The average stoichiometry and local phase separation of this quenched high-pressure phase were characterized by ex situ synchrotron powder X-ray diffraction and total scattering. Several structural models were obtained using simulated annealing, but all suffered from an imperfect Rietveld refinement, especially at higher diffraction angles. Finally, a novel stoichiometrically correct crystal structure model was proposed on the basis of electron diffraction data and refined against powder diffraction data using the Rietveld method. Scanning electron microscopy–energy-dispersive X-ray spectrometry (EDX) measurements verified the targeted 1:3 (Cr:Te) average stoichiometry for the starting compound and for the quenched high-pressure phase within experimental errors. Scanning transmission electron microscopy (STEM)–EDX was used to examine minute variations of the Cr-to-Te ratio at the nanoscale. Precession electron diffraction (PED) experiments were applied for the nanoscale structure analysis of the quenched high-pressure phase. The proposed monoclinic model from PED experiments provided an improved fit to the X-ray patterns, especially after introducing atomic anisotropic displacement parameters and partial occupancy of Cr atoms. Atomic resolution STEM and simulations were conducted to identify variations in the Cr-atom site-occupancy factor. No significant variations were observed experimentally for several zone axes. The magnetic properties of the novel CrTe3 phase were investigated through temperature- and field-dependent magnetization measurements. In order to understand these properties, auxiliary theoretical investigations have been performed by first-principles electronic structure calculations and Monte Carlo simulations. The obtained results allow the observed magnetization behavior to be interpreted as the consequence of competition between the applied magnetic field and the Cr–Cr exchange interactions, leading to a decrease of the magnetization towards T = 0 K typical for antiferromagnetic systems, as well as a field-induced enhanced magnetization around the critical temperature due to the high magnetic susceptibility in this region.

Atomic-scale investigation on the evolution of T1 precipitates in an aged Al-Cu-Li-Mg-Ag alloy

The T1 (Al2CuLi) phase is one of the most effective strengthening nanoscale-precipitate in Al-Cu alloys with Li. However, its formation and evolution still need to be further clarified during aging due to the complex precipitation sequences. Here, a detailed investigation has been carried out on the atomic structural evolution of T1 precipitate in an aged Al-Cu-Li-Mg-Ag alloy using state-of-the-art Cs-corrected high-angle annular dark field (HAADF)- coupled with integrated differential phase contrast (iDPC)-scanning transmission electron microscopy (STEM) and energy-dispersive X-ray spectroscopy (EDXS) techniques. An intermediate T1’ phase between T1p and T1 phase, with a crystal structure and orientation relationship consistent with T1, but exhibiting different atomic occupancy and chemical composition was found. We observed the atomic structural transformation from T1p to T1’ phase (fcc→hcp), involving only 1/12<112>Al shear component. DFT calculation results validated our proposed structural models and the precipitation sequence. Besides, the distributions of minor solute elements (Ag, Mg, and Zn) in the precipitates exhibited significant differences. These findings may contribute to a further understanding of the nucleation mechanism of T1 precipitate.

Unraveling the role of the BCC-B2 transition and V occupancies in the contradictory magnetism-ductility relationship of FeCoV alloys

The contradictory relationship between magnetism and ductility restricts further applications of FeCoV alloys in high-performance electrical machines. The role of the BCC-B2 transition, accompanied by vanadium (V) site occupancies, in magnetic moments and ductility has been explored using first-principles calculations. The variations in magnetism and ductility of FeCoV alloys are attributed to the coupling of the BCC-B2 transition and V occupancies. When V replaces Fe atoms in the equiatomic B2-FeCo alloy, the superior magnetism observed in B2-Fe50-cCo50Vc alloys is a consequence of the enhanced local magnetic moment of Fe and the ferrimagnetic-ferromagnetic transition in the magnetic state. Moreover, due to the preferential V occupancy in the B2 phase, the B2-Fe46Co50V4 alloy exhibits comparable ductility to the BCC-Fe50Co46V4 alloy. The results indicate that the increased brittleness in the B2 phase arises from the raised Peierls stress and the enhanced covalent component in interatomic bonding, which is caused by the strong hybridization between Fe and Co atoms. Pearson correlation analysis illustrates that valence electron concentration (VEC) and V content are significant factors in the contradictory relationship between magnetization and ductility. The theoretical results demonstrate that tuning the V content and atomic occupancies is helpful to achieve a trade-off between magnetization and ductility in B2-FeCoV alloys.

Atomic-Scale Interface for Pt Nanoparticles on SrTiO3 (001).

The interfacial structure formed by Pt nanoparticles grown epitaxially on a SrTiO3 (001) surface by pulsed laser deposition was studied by X-ray standing-wave (XSW) excited core-level photoelectron emission. The XSW-generated 3D atomic map of the Pt and interfacial oxygens for the oxidized Pt/SrTiO3 interface differs significantly from that of the as-deposited interface. After oxidation, the Pt atoms shifted upward and their atomic occupation at fcc-like sites evolved as the oxidation temperature increased. Interfacial oxygen atoms were differentiated from bulk O atoms by the chemical shift in the binding energy of their 1s electrons. After oxidation, the interfacial oxygen atoms rearranged to form a TiO2 bilayer at the interface. These results provide a more complete description of the strong metal-support interaction process at the interface.

Temperature dependence of phase stabilities of hexagonal hemicarbides from first principles

Transition metal hemicarbides, specifically M2C (where M = V, Nb, Ta, Mo and W), have received considerable attention in the fields of catalysis and metallurgy. However, the determination of the exact phase of each compound can still be challenging due to the close energetic proximity of its various polymorphs. This study uses first-principles calculations to carefully consider the subtle differences between different polymorphs, with temperature as a key factor. It is found that the energies of each polymorph of M2C are close, but can be distinguished when temperature effects are considered. This means that temperature plays an important role in the polymorph transformations. In addition, these phases exhibit dynamic stability at both zero and finite temperatures, in part due to the particular ordering of C atom occupancy in the metal lattice interstices. The study can provide calculations of a range of properties that help to identify stable structures and deepen the understanding of these materials in terms of chemical bonding, structural changes, lattice thermal vibrations and molecular dynamics.

Superstructure of Fe5-xGeTe2 Determined by Te K-Edge Extended X-ray Absorption Fine Structure and Te Kα X-ray Fluorescence Holography.

The local structure of the two-dimensional van der Waals material, Fe5-xGeTe2, which exhibits unique structural/magnetic phase transitions, was investigated by Te K-edge extended X-ray absorption fine structure (EXAFS) and Te Kα X-ray fluorescence holography (XFH) over a wide temperature range. The formation of a trimer of Te atoms at low temperatures has been fully explored using these methods. An increase in the Te-Fe distance at approximately 150 K was suggested by EXAFS and presumably indicates the formation of a Te trimer. Moreover, XFH displayed clear atomic images of Te atoms. Additionally, the distance between the Te atoms shortened, as confirmed from the atomic images reconstructed from XFH, indicating the formation of a trimer of Te atoms, i.e., a charge-ordered superstructure. Furthermore, Te Kα XFH provided unambiguous atomic images of Fe atoms occupying the Fe1 site; the images were not clearly observed in the Ge Kα XFH that was previously reported because of the low occupancy of Fe and Ge atoms. In this study, EXAFS and XFH clearly showed the local structure around the Te atom; in particular, the formation of Te trimers caused by charge-ordered phase transitions was clearly confirmed. The charge-ordered phase transition is fully discussed based on the structural variation at low temperatures, as established from EXAFS and XFH.

Interactions between irradiation-induced defects and dislocations in concentrated solid solution alloys

Dislocation is a common structural feature in metallic alloys. Under irradiation, interactions between dislocations and irradiation-induced defects play a crucial role in governing various microstructural changes and the irradiation response of materials. Though such interaction has been intensively studied in elemental metals, little is known about it in concentrated solid solution alloys (CSAs). In this work, we study defect-dislocation interactions in NiFe CSAs through both elastic theory and atomistic simulations. Unexpectedly, we find that dislocations interact more strongly with defects in CSAs than in pure metals due to their higher elastic moduli, which is adverse to their irradiation performance based on conventional understanding. By comparing random models (Rand) and average atom models (Ave) for NiFe, we show that the random occupancy of atoms in the Rand model compared to the Ave model can reduce the interaction between dislocations and defects, thereby diminishing the dislocation bias factor. We further perform defect kinetic simulations and find that the complex energy landscape for defect motion in NiFe tends to restrict the movement of defects and weaken the ability of dislocations to absorb interstitials. Therefore, the chemical disorder in CSAs can partly reduce the defect-dislocation interaction strength thermodynamically and, more importantly, limit the movement of defects kinetically, both of which suppress the absorption ability of dislocations toward defects. Our integrated efforts shed light on the mechanisms governing defect-dislocation interactions in CSAs, providing insight into the reasons for the superior irradiation resistance of CSAs and offering possible directions to tune their irradiation performance.

Synergistic manipulation of physical properties of Ni-Mn-In-B alloys by atomic occupancy and magnetic states

The physical properties of the Ni-Mn-In-B alloys synergistically modulated by atomic occupancy and magnetic states are systematically investigated. The results indicate that B atoms are indirectly substituted at the Mn2 position in the Ni2Mn1.5In0.5 alloy (i.e., B→In→Mn2). When B is doped in interstitial positions, the B atoms tend to be closer to Mn atoms rather than In atoms. Additionally, the higher the concentration of Mn around the B atom, the lower the formation energy of the austenite (A) phase. The lattice parameters of the A phase decreases with increasing x content, while c/a and phase stability gradually decrease for the 4 O, 6 M, and NM martensites in the ferrimagnetic (FIM) state. The magnetostrain of the alloy shows an increasing trend with increasing B content due to the decrease in c/a resulting in a decrease in the tangent variable S= |c/a-a/c|; however, the elastocaloric properties decrease due to the decrease in the volume change ΔV/VA after the transformation. The Ni2Mn1.5-xIn0.5Bx (0≤x≤0.042) alloys undergo an AFM→6 MFIM→NMFIM transformation. The total magnetic moment of the A phase decreases, whereas those of the 4O, 6M, and NM phases increase with increasing x content. The phase stability is explained by analyzing the total densities of states (TDOS) from an electronic structure perspective.

A Strontium Quantum-Gas Microscope

The development of quantum-gas microscopes has brought novel ways of probing quantum degenerate many-body systems at the single-atom level. Until now, most of these setups have focused on alkali atoms. Expanding quantum-gas microscopy to alkaline-earth elements will provide new tools, such as SU(N)-symmetric fermionic isotopes or ultranarrow optical transitions, to the field of quantum simulation. Here we demonstrate the site-resolved imaging of a 84Sr bosonic quantum gas in a Hubbard-regime optical lattice. The quantum gas is confined by a two-dimensional in-plane lattice and a light-sheet potential, which operate at the strontium clock-magic wavelength of 813.4 nm. We realize fluorescence imaging using the broad 461-nm transition, which provides high spatial resolution. Simultaneously, we perform attractive Sisyphus cooling with the narrow 689-nm intercombination line. We reconstruct the atomic occupation from the fluorescence images, obtaining imaging fidelities above 94%. Finally, we realize a 84Sr superfluid in the Bose-Hubbard regime. We observe its interference pattern upon expansion, a probe of phase coherence, with single-atom resolution. Our strontium quantum-gas microscope provides a new platform to study dissipative Hubbard models, quantum optics in atomic arrays, and SU(N) fermions at the microscopic level. Published by the American Physical Society 2024

First-principles study of electronic and magnetic properties in site dependent Fe-doped chalcopyrite ZnSnAs2semiconductors: Comparison with those of Mn- and Cr-doped ZnSnAs2

The electronic and magnetic properties of Fe-doped ZnSnAs2 within chalcopyrite structures have been studied by first-principles calculations using the density functional theory (DFT) full-potential linearized augmented-plane-wave method and the plane-wave pseudopotential methods. The band gap of ZnSnAs2 was determined to be 0.816 eV using the modified Beck-Jonson (mBJ) exchange potential. When Fe dopants substitutionally replace Sn atoms, half-metallic ferromagnetism is observed in ZnSnAs2 where in the spin-down band at the Fermi level is entirely unoccupied. The magnetic exchange interaction between two Fe atoms substituting Zn and Sn sites in the supercell with different geometries has been studied. The total energy difference (ΔE) between the antiferromagnetic (AFM) and ferromagnetic (FM) configurations suggests that Fe atom occupation of Zn sites in ZnSnAs2 leads to a predominantly AFM state, while the Fe atom occupation of Sn sites prefers the FM state.