First-principles Calculations Research Articles

Complex charge density waves in simple electronic systems of two-dimensional III2–VI3 materials

AbstractCharge density wave (CDW) is the phenomenon of a material that undergoes a spontaneous lattice distortion and modulation of the electron density. Typically, the formation of CDW is attributed to Fermi surface nesting or electron-phonon coupling, where the CDW vector (QCDW) corresponds to localized extreme points of electronic susceptibility or imaginary phonon frequencies. Here, we propose a new family of multiple CDW orders, including chiral Star-of-David configuration in nine 2D III2–VI3 van der Waals materials, backed by first-principles calculations. The distinct feature of this system is the presence of large and flat imaginary frequencies in the optical phonon branch across the Brillouin zone, which facilitates the formation of the diverse CDW phases. The electronic structures of 2D III2–VI3 materials are relatively simple, with only III-s,p and VI-p orbitals contributing to the formation of the CDW order. Despite that, the CDW transitions involve both metal-to-insulator and insulator-to-insulator transitions, accompanied by a significant increase in the bandgap caused by an enhanced electronic localization. Our study not only reveals a new dimension in the family of 2D CDWs, but is also expected to offer deeper insights into the origins of the CDWs.

First-principles study and mesoscopic modeling of two-dimensional spin and orbital fluctuations in FeSe

We calculated the structural, electronic, and magnetic properties of FeSe within density-functional theory at the generalized gradient approximation level. First, we studied how the bandwidth of the d-bands at the Fermi energy is renormalized by adding simple corrections: Hubbard U, Hund's J, and by introducing long-range magnetic orders. We found that introducing either a striped or a staggered dimer antiferromagnetic order brings the bandwidths—which are starkly overestimated at the generalized gradient approximation level—closer to those experimentally observed. Second, for the ferromagnetic, the striped, checkerboard, and staggered dimer antiferromagnetic order, we investigate the change in magnetic formation energy with local magnetic moment of Fe at a pressure up to 6 GPa. The bilinear and biquadratic exchange energies are derived from the Heisenberg model and noncollinear first-principles calculations, respectively. We found a nontrivial behavior of the spin-exchange parameters on the magnetization, and we put forward a field-theory model that rationalizes these results in terms of two-dimensional spin and orbital fluctuations. The character of these fluctuations can be either that of a standard density wave or a topological vortex. Topological vortices can result in mesoscopic magnetization structures. Published by the American Physical Society 2024

Strongly enhanced shift current at exciton resonances in a noncentrosymmetric wide-gap semiconductor.

Excitons are fundamental quasiparticles that are ubiquitous in photoexcited semiconductors and insulators. Despite causing a sharp and strong photoabsorption near the interband absorption edge, charge-neutral excitons do not yield photocurrent in conventional photovoltaic processes unless dissociated into free charge carriers. Here, we experimentally demonstrate that excitons can directly contribute to photocurrent generation through a nonlinear light-matter interaction in a noncentrosymmetric semiconductor CuI. Epitaxial thin films of CuI exhibit a substantial enhancement of photocurrent at exciton resonance energies even below the bandgap. From the light polarization dependence, this photocurrent is identified to be shift current, a nonlinear photocurrent driven by the change in the geometric Berry phase of electron wave functions upon the optical transition. The shift current at the exciton resonance is much larger than that induced above the band gap by free electron-hole excitation, and their signs are opposite. First-principles calculations elucidate that the sign and magnitude of the exciton shift current are strongly dependent on the strain in the thin film. The present study reveals the crucial role of excitons in enhancing the shift current magnitude and its strain sensitivity, and will open an unprecedented route for efficient manipulation of nonlinear optical effects.

First-principles calculations to investigate structural, electronic, elastic, and optical properties of orthorhombic LiBH2 for hydrogen storage and optoelectronic devices

First-principles calculations to investigate structural, electronic, elastic, and optical properties of orthorhombic LiBH2 for hydrogen storage and optoelectronic devices

Effect of Ta content on elastic properties and magnetic properties of Zr-Ta binary alloys via first-principles calculation

Abstract β-type Zirconium alloys are promising biomedical implant materials, the elastic and magnetic properties of which are of great importance to be studied. In this work, β-type Zr1-xTax binary alloys (x=0.0625, 0.125, 0.1875, 0.25, 0.3125, 0.375, 0.4375, 0.50, 0.5625, 0.625, 0.6875, 0.75, 0.8125, 0.875, 0.9375) were established. The effects of Ta content on lattice constant, elastic properties and magnetic properties of β-type Zr-Ta alloys were investigated via first-principles calculations, the calculated results were also verified through experiments. The results shown that with the increase of Ta content, the lattice constant and total energy of β-type Zr-Ta alloys gradually decreased, the elastic moduli of E, K and G increased on the whole, and the magnetic moment generally increased first and then decreased. The changing trend of elastic and magnetic properties were consistent between experimental and calculated results. Notably, Zr0.875Ta0.125 exhibited the lowest Young’s modulus and magnetic susceptibility among the β-type Zr-Ta alloys, which was one-third that of Ti-6Al-4V, meeting the requirements for low Young’s modulus and low magnetism, and can be anticipated to be promising biomedical implant materials.

Complex field-, temperature-, and angle-dependent Hall effects from intrinsic Fermi surface revealed by first-principles calculations

Complex field-, temperature-, and angle-dependent Hall effects from intrinsic Fermi surface revealed by first-principles calculations

First-principles calculations of the effect of vacancy defects on the optoelectronic and mechanical properties of the double perovskite Cs2NaInCl6

Abstract Cs2NaInCl6 have become a hot research topic in perovskite optoelectronic materials. However, there is no research on the vacancy properties of Cs2NaInCl6 at present. Herein，using density functional theory-based first-principles calculations, the impact of Cs, Na, In, and Cl single vacancies on the microstructure, electronic, optical, and mechanical properties of the double perovskite Cs2NaInCl6 were investigated. The research shows that the presence of vacancy defects leads to distortion of the Cs2NaInCl6 double perovskite structure and an increase in the unit cell volume. Cs vacancy (VCs) and Na vacancy (VNa) cause an increased band gap for Cs2NaInCl6, by 2.92eV and 3.1eV respectively, without changing the characteristics of the initial direct band gap; VIn and VCl cause the intrinsic semiconductor Cs2NaInCl6 to transform into p-type and n-type semiconductors, respectively, altering the conductivity of Cs2NaInCl6. In terms of optical properties, different vacancy defect systems exhibit different absorption abilities in the visible and ultraviolet light ranges. The defect system overall improves light absorption in the low energy region, and as the incident photon energy increases, the material exhibits the best optical performance at around 15eV. In addition, it is found that VCs, VNa, and VIn caused blue shift in the absorption edge of Cs2NaInCl6, while VCl caused red shift in the absorption edge. In terms of mechanical properties, defects cause varying degrees of reduction in Young's modulus (E), shear modulus (G), and bulk modulus (B) of Cs2NaInCl6, which to some extent alters the mechanical properties of Cs2NaInCl6. These research results provide theoretical guidance for understanding the influence of vacancies on the properties of Cs2NaInCl6 double perovskite and optimizing the performance of perovskite optoelectronic devices, and they also enhance its applications in photovoltaic cells, optoelectronic sensors, and other optoelectronic coupling devices.

First-principles study on thermal and electrical transport properties of NbGe2 and NbSi2: the role of electron-phonon coupling

Abstract We study coupled electron and phonon transport in NbX2 with X=Ge, Si, in which experimental evidence of strong electron-phonon coupling and hydrodynamic transport has been reported. Based on first-principles calculations at the density functional theory level, we report their thermal and electrical transport properties. We find that phonon-electron scattering strongly affects their phonon thermal conductivity (κ ph) and leads to weak temperature dependence of κ ph, instead of normal inverse temperature dependence when anharmonic three phonon scattering dominates. Moreover, κ ph contributes to quarter of the total thermal conductivity, which differs from typical metals where total thermal conductivity is predominantly from electron part. Different from previous numerical study, our results of electrical resistivity agree well with experimental measurement. The anisotropic property of the transport coeffcients is attributed to the electron and phonon dispersion relation. Moreover, we find negligible effect of electron-phonon drag on the transport property, contrary to expectation from a strongly coupled electron-phonon fluid.

Critical factors influencing electron and phonon thermal conductivity in metallic materials using first-principles calculations

Understanding the thermal transport of various metals is crucial for many energy-transfer applications. However, due to the complex transport mechanisms varying among different metals, current research on metallic thermal transport has been focusing on case studies of specific types of metallic materials. A general understanding of the transport mechanisms across a broad spectrum of metallic materials is still lacking. In this work, we perform first-principles calculations to determine the thermal conductivity of 40 representative metallic materials, within a range of 8-456 W mK-1. Our predicted values of electrical and thermal conductivity are in good agreement with available experimental results. Based on the data of separated electron and phonon thermal conductivity, we employ a statistical approach to examine nine factors derived from previous understandings and identify the critical factors determining these properties. For electrons, although a high electron density of states around the Fermi level implies more conductive electrons, we find it counterintuitively correlates with low electron thermal conductivity. This is attributed to the enlarged electron-phonon scattering channels induced by substantial electrons around the Fermi level. Regarding phonons, we demonstrate that among all the studied factors, Debye temperature plays the most significant role in determining the phonon thermal conductivity, despite the phonon-electron scattering being non-negligible in some transition metals. Correlation analysis suggests that Debye temperature has the highest positive correlation coefficient with phonon thermal conductivity, as it corresponds to a large phonon group velocity. Additionally, Young's modulus is found to be closely correlated with high phonon thermal conductivity and contribution. Our findings of simple factors that closely correlate with the electron and phonon thermal conductivity provide a general understanding of various metallic materials. They may facilitate the discovery of novel materials with extremely high or low thermal conductivity, or be used as descriptors in machine learning to accurately predict the thermal conductivity of metals in the future.

Active learning-based automated construction of Hamiltonian for structural phase transitions: a case study on BaTiO3

The effective Hamiltonians have been widely applied to simulate the phase transitions in polarizable materials, with coefficients obtained by fitting to accurate first-principles calculations. However, it is tedious to generate distorted structures with symmetry constraints, in particular when high-ordered terms are considered. In this work, we implement and apply a Bayesian optimization-based approach to sample potential energy surfaces, automating the effective Hamiltonian construction by selecting distorted structures via active learning. Taking BaTiO3(BTO) as an example, we demonstrate that the effective Hamiltonian can be obtained using fewer than 30 distorted structures. Follow-up Monte Carlo simulations can reproduce the structural phase transition temperatures of BTO, comparable to experimental values with an error<10%. Our approach can be straightforwardly applied on other polarizable materials and paves the way for quantitative atomistic modelling of diffusionless phase transitions.

H$_{3}$Se in the $Im\overline{3}m$ Phase: A High-Pressure Superconductor with $T_{\text{c}}$ Reaching 200 K at 64 GPa Mediated by Anharmonic Phonons

Abstract Hydrogen-based compounds have attracted significant attention in recent years due to the discovery of conventional superconductivity with high critical temperature under high pressure, rekindling hopes for searching room temperature superconductor. In this work, we investigated systematically the vibrational and superconducting properties of H$_{3}$Se in $Im\overline{3}m$ phase under pressures ranging from 50 to 200 GPa. Our approach combines the stochastic self-consistent harmonic approximation with first-principles calculations to address effects from the quantum and anharmonic vibrations of ions. It turns out that these effects significantly modify the crystal structure, increasing the inner pressure by about 8 GPa compared to situations where they are ignored. The phonon spectra suggest that with these effects included, the crystal can be stabilized at pressures as low as about 61 GPa, much lower than the previously predicted value of over 100 GPa. Our calculations also highlight the critical role of quantum and anharmonic effects on the electron-phonon coupling properties. Neglecting these factors could result in a substantial overestimation of the superconducting critical temperature $T_{\text{c}}$, by approximately 25 K at 125 GPa, for example. With anharmonic phonons, the $T_{\text{c}}$ derived from the Migdal-Eliashberg equations, reaches 200 K ($\mu^\star=0.1, \lambda$=4.1) as the pressure decreases to 64 GPa, making the crystal a rare high-$T_{\text{c}}$ superconductor at moderate pressures.

Tunable electronic and optoelectronic characteristics of two-dimensional β-AsP monolayer: a first-principles study.

Two-dimensional (2D) semiconductors have attracted a great deal of interest from the electrical engineering community due to their intriguing electronic properties. In this study, we have systematically investigated the electronic and optoelectronic properties of β-AsP monolayers by first-principles calculations combined with strain engineering. The results show that the β-AsP monolayer has a suitable indirect bandgap and a strain-tunable electronic structure. On this basis, the designed two-electrode photodetector based on β-AsP monolayer exhibits a strong photoelectric response in the near-ultraviolet region, and the maximum photocurrent can reach 74a02 per phonon under the applied bias voltage of 1 V. In particular, the strain engineering not only improves the photoelectric performance of the β-AsP-based photodetector, but also adjusts its photodetection range. These findings suggest that β-AsP monolayers are ideal candidates for the development of near-ultraviolet photodetectors and optoelectronic devices.

The Study of the Etching Resistance of YOF Coating Deposited by Atmospheric Plasma Spraying in HBr/O2 Plasma

Yttrium oxyfluoride (YOF) coatings with different oxygen content were prepared using atmospheric plasma spraying (APS) technology. The etching resistance of the coatings in HBr/O2 plasma was investigated. Shifts in diffraction peaks of the X-ray diffraction, along with XPS analysis conducted before and after etching, demonstrated that Br ions could replace O and F ions and fill the oxygen vacancies after exposure to HBr/O2 plasma, which is supported by the first-principles calculations. Br ions formed a protective layer on the surface of the YOF coating, slowing down further etching by Br ions. By adjusting the oxygen mass fraction in YOF powder, the oxygen vacancy concentration and Br ion filling were regulated to enhance etching resistance. YOF coatings with 6% oxygen content exhibited improved etching resistance compared to YOF coatings with 3% and 9% oxygen content. This improvement was primarily due to the increased Br ion concentration. These findings provide a new approach for developing coatings with enhanced etching resistance.

Magnetothermal effect and first-principles calculations of Zn-doped Mn5Ge3-based alloys

This study investigates the compound system Mn5−xZnxGe3 (x = 0.1, 0.2, and 0.3) through experimental investigations and theoretical calculations. Zn doping lowers the Curie temperature and magnetic entropy change of Mn5−xZnxGe3 alloys. Analysis of phenomenological curves, including Landau theories, normalized curves, and Arrott curves during the study of isothermal magnetization curves, reveals a second-order phase transition in this system. Through an extensive investigation of critical behavior using critical isotherm curves and the Kouvel–Fisher (KF) method, the consistency and reliability of these critical indices are validated by the prediction of the scaling theory in the critical region. By scaling the dependence of |ΔSM| on M and applying crucial exponen21t values, an efficient new approach is utilized to calculate the spontaneous magnetization that agrees well with the values deduced from the KF method. Additionally, first-principles calculations reveal that the Mn atoms' 3d orbitals are more significantly close to the Fermi energy level, with Zn doping generally reducing both the electronic density of states and the total magnetic moment of the Mn 3d orbitals. Consequently, the introduction of Zn leads to a decrease in the Mn–Mn atom exchange coupling, resulting in a deterioration of the total exchange interaction. This phenomenon also explains the decrease in the Curie temperature TC due to Zn doping, aligning with experimental observations.

NEXAFS spectroscopy of alkylated benzothienobenzothiophene thin films at the carbon and sulfur K-edges.

Alkylated benzothienobenzothiophenes are an important class of organic semiconductors that exhibit high performance in solution-processed organic field-effect transistors. In this work, we study the near-edge x-ray absorption fine-structure (NEXAFS) spectra of 2,7-didecyl[1]benzothieno[3,2-b][1]benzothiophene (C10-BTBT) at both the carbon and sulfur K-edges. Angle-resolved experiments of thin films are performed to characterize the dichroism associated with molecular orientation. First-principles calculations using the density functional theory-based many-body x-ray absorption spectroscopy (MBXAS) method are also performed to correlate the peaks observed and their dichroism with transitions to specific antibonding molecular orbitals. Interestingly, the dichroism of the dominant, lowest energy peak is opposite at the carbon and sulfur K-edges. While the low-energy peak at the carbon K-edge is assigned to carbon 1s → π* transitions with transition dipole moment (TDM) perpendicular to the planar BTBT core, the dominant low energy peak at the sulfur K-edge is assigned to sulfur 1s → σ* transitions with TDM oriented along the long axis of the BTBT core. These differences at the sulfur and carbon K-edges are understood through the MBAXS simulations that find a reordering of the energy of the lowest energy π* and σ* transitions at the sulfur K-edge due to the strong localization of the σ* orbital over the sulfur atom. This work highlights differences in the NEXAFS spectra of organic semiconductors at carbon and sulfur K-edges and provides new insights into peak assignment and x-ray dichroism relevant for studying the molecular orientation of organic semiconductor films.

Transverse Thermoelectric Conversion in the Mixed-Dimensional Semimetal WSi 2

Materials with axis-dependent conduction polarity are known as p×n-type or goniopolar conductors that can be used for transverse thermoelectric devices, allowing the longitudinal thermal current to be converted into the transverse electrical current. Here, we have performed experimental and computational studies on the transport properties of WSi2 single crystals, in which such axis-dependent conduction polarity of the thermopower and the Hall coefficient have recently been reported, and demonstrated the transverse thermoelectric effect by applying the temperature gradient in a direction rotated 45∘ from the crystallographic axis. We have observed strongly sample-dependent transport properties, which have also been observed in previous studies, and together with first-principles calculations we show that such sample-dependent transport properties originate from the band-dependent scattering rates of carriers. The calculated band-resolved Peltier conductivity shows that the mixed-dimensional electronic structure consisting of a quasi-one-dimensional electron Fermi surface and a quasi-two-dimensional hole surface is a key property for the axis-dependent conduction polarity. The directly obtained transverse thermoelectric figure of merit is comparable to that of the anomalous Nernst materials, implying that the present material is a potential candidate for transverse thermoelectric conversion. Published by the American Physical Society 2024

Two-Dimensional Pentagonal Materials with Parabolic Dispersion and High Carrier Mobility

Materials with high carrier mobility, represented by graphene, have garnered significant interest. However, the zero band gap arising from linear dispersion cannot achieve an ideal on–off ratio in field-effect transistors (FETs), limiting practical applications in certain fields. In contrast, parabolic dispersion usually exhibits extremely high carrier mobility and an appropriate band gap. In this work, we predicted a planar pentagonal lattice composed entirely of pentagons (namely penta-MX2 monolayer), where M = Ni, Pd and Pt, X = group V elements. Using first-principles calculations, we demonstrated a parabolic dispersion within this framework, which results in intriguing phenomena, such as a direct band gap (0.551–1.105 eV) and extraordinary high carrier mobility. For penta-MX2 monolayer, the carrier mobility can attain ~1 × 108 cm2 V−1 s−1 (PBE), surpassing those of black phosphorene, graphene and 2D hexagonal materials. This monolayer also displays anisotropic mechanical properties and significant absorption peaks in the ultraviolet spectrum. Remarkably, 2D penta-MX2 monolayers are promising for successful experimental exfoliation, particularly when X is a nitrogen element, opening up new possibilities for designing two-dimensional semiconductor materials characterized by high carrier mobility.

Synergistic effect of molybdenum dioxide wrapped nitrogen doped carbon nanotubes in binder-free anodes for enhanced lithium storage properties

Molybdenum dioxide (MoO2) is regarded as a potential anode for lithium-ion batteries due to its highly theoretical specific capacity. However, its further application in lithium-ion battery is largely limited by insufficient practical discharge capacity and cyclic performance. Here, MoO2nanoparticles are in-situ grown on three-dimensional nitrogen doped carbon nanotubes (NCNTs) on nickel foam substrate homogeneously using a simple electro-deposition method. The unique structural features are favorable for lithium ions insertion and extraction and charge transfer dynamics at electrode/electrolyte interface. As a proof of concept, the as-synthesized nanocomposites have been employed as anode for lithium-ion battery, exhibiting a reversible and significantly improved discharge capacity of ∼517 mA h g-1at the current density of 150 mA g-1as well as superior cycle and rate performance. The first-principle calculations based on density functional theory and electrochemical impedance spectroscopy results demonstrate a reduced energy barrier of lithium ions diffusion, improved lithium storage behavior, reduced structure collapse, and significantly enhanced charge transfer kinetics in MoO2/NCNTs nanocomposites with respect to MoO2powder. The excellent performance makes as-prepared MoO2/NCNTs nanocomposites promising binder-free anode for high performance lithium-ion batteries. This work also provides important theoretical insights for other state-of-the-art batteries design.

First-Principles Investigation of Structural, Electronic, Optical, Elastic, and Thermoelectric Properties of Cubic Francifluorite Perovskites FrXF3 (X = Si, Ge, and Sn) for Optoelectronic and Thermoelectric Device Applications

Abstract This study presents the results of first-principles calculations based on Density Functional Theory (DFT) implemented in the Wien2k code, investigating the properties of FrXF3 compounds where B represents Si, Ge, and Sn. Various exchange-correlation functionals, including Generalized Gradient Approximation (GGA) with Perdew-Burke-Ernzerhof (GGA-PBE), Perdew-Burke-Ernzerhof revised for Solids (GGA-PBEsol), Wu-Cohen exchange (GGA-WC), and Modified Becke-Johnson potential (TB-mBJ), were employed to comprehensively analyze the structural, electronic, optical, elastic, and thermoelectric characteristics of these compounds. The analysis of band structures and density of states revealed that all three compounds exhibit semiconducting behavior with direct band gaps, and the band gaps decrease as we move from Si to Sn. The calculated optical properties indicate strong optical responses in the visible to ultraviolet energy range, suggesting potential applications in optoelectronics. Furthermore, the study evaluated the thermoelectric parameters, including thermal and electrical conductivity, power factor, Seebeck coefficient, and figure of merit. The results demonstrate that the FrXF3 compounds possess remarkable thermoelectric potential, indicating their suitability for thermoelectric applications. Overall, this comprehensive investigation provides valuable insights into the structural, electronic, optical, elastic, and thermoelectric properties of FrXF3 compounds, highlighting their potential for various technological applications, particularly in the field of optoelectronics and thermoelectric devices.&amp;#xD;

Advances in machine learning methods in copper alloys: a review.

Advanced copper and copper alloys, as significant engineering structural materials, have recently been extensively used in energy, electron, transportation, and aviation domains. Higher requirements urge the emergence of high-performance copper alloys. However, the traditional trial-and-error experimental observations and computational simulation research used to design and develop novel materials are time-consuming and costly. With the accumulation of material research and rapid development of computational ability, the thorough application of material genome engineering has sped up the development of novel materials and facilitates the process of systematic engineering application. This review summarizes the benefits of data-driven machine learning techniques and the state of the art of machine learning research in the area of copper alloys. It also displays the widely used computational simulation approaches (e.g., the first-principles calculation, molecular dynamics simulation, phase-field simulations, and finite element analysis) and their combined applications in material design and property prediction. Finally, the limitations of machine learning research methods are outlined, and future development directions are proposed.