First-principles Calculations Research Articles

Visualization of spin-polarized surface resonances in Pb-based ternary topological insulators

The formation of the topological surface state originates from bulk band inversion at the top of the valence band and the bottom of the conduction band. The transition between normal and topological insulators is known as a topological phase transition. Here we show spin-polarized electronic states of Pb-based ternary topological insulators Pb(Bi1-xSbx)2Te4 (x = 0.55, 0.70, 0.79) investigated by spin- and angle-resolved photoemission spectroscopy and first-principles calculations. We visualize a pair of spin-polarized surface resonances dispersing along the upper edge of projected bulk bands in occupied states. Interestingly, a branch of the spin-polarized surface resonances continuously connects to the topological surface state. The coexistence of the topological surface state and the spin-polarized surface resonances can be explained by considering the topological phase transition.

Mechanical properties of TPDH-graphene: atomistic aspect

Abstract TPDH-graphene is a new type of two-dimensional carbon material predicted by first-principles calculations to have tetragonal (T), pentagonal (P), decagonal (D) and hexagonal (H) carbon ring structures. First-principles calculations show that this special structure gives it excellent mechanical properties and promising applications in nanoelectronics. In this paper, a comprehensive test of its mechanical properties was carried out using the classical molecular dynamics (MD), mainly exploring the effects of factors such as tensile direction and temperature on its mechanical properties, and exploring the effects of introducing rectangular and circular defects on its mechanical properties. The results show that: TPDH-graphene exhibits significant anisotropy in zigzag and armchair directions, and the material exhibits some tensile toughness in armchair direction; the mechanical properties of the material are weakened at higher temperatures; the adding of defects leads to the reduction of the mechanical properties of the material in different directions to different degrees, and the The tensile toughness in the armchair direction is weakened by the addition of defects.

Proximity-Induced Exchange Interaction and Prolonged Valley Lifetime in MoSe2/CrSBr Van-Der-Waals Heterostructure with Orthogonal Spin Textures.

Heterostructures, composed of semiconducting transition-metal dichalcogenides (TMDC) and magnetic van-der-Waals materials, offer exciting prospects for the manipulation of the TMDC valley properties via proximity interaction with the magnetic material. We show that the atomic proximity of monolayer MoSe2 and the antiferromagnetic van-der-Waals crystal CrSBr leads to an unexpected breaking of time-reversal symmetry, with originally perpendicular spin directions in both materials. The observed effect can be traced back to a proximity-induced exchange interaction via first-principles calculations. The resulting spin splitting in MoSe2 is determined experimentally and theoretically to be on the order of a few meV. Moreover, we find a more than 2 orders of magnitude longer valley lifetime of spin-polarized charge carriers in the heterostructure, as compared to monolayer MoSe2/SiO2, driven by a Mott transition in the type-III band-aligned heterostructure.

Control of coherent phonon dynamics in CoFeB/heavy metal heterojunction structures for future hybrid phononic and spintronic devices

Abstract The heterojunction structure of CoFeB/heavy metal has shown significant potential for spintronics, where both electrons and magnons potentially can serve as information carriers. However, another promising information carrier, coherent phonons, has not been fully explored for hybrid phononic and spintronic devices. In this study, we used time-resolved pump-probe spectroscopy to investigate the dynamic behavior of coherent phonons. We observed variations in reflectivity spectra, corresponding to changes in phonon frequency and relaxation times, with different thicknesses of the heavy metal and CoFeB layers. The experimental results demonstrated a decrease in coherent phonon oscillation frequency as the thickness of the CoFeB and heavy metal layers increased. These findings were further supported by first-principles calculations, which showed that the frequency of the optical modes is suppressed due to interface relaxation between the magnetic and heavy metal layers.

Proton transfer driven by the fluctuation of water molecules in chitin film.

Proton-transfer mechanisms and hydration states were investigated in chitin films possessing the functionality of fuel-cell electrolytes. The absolute hydration number per chitin molecule (N) as a function of relative humidity (RH) was determined from the OH stretching bands of H2O molecules, and the proton conductivity was found to enhance above N = 2 (80%RH). The FIR spectrum at 500-900cm-1 for 20%RH (N < 1) together with first-principles calculations clearly shows that the w1 site has the same hydration strength as the w2 site. The molecular dynamics simulations for N = 2 demonstrate that H2O molecules with tiny fluctuations are localized on w1 and w2, and the hydrogen-bond (HB) network is formed via the CH2OH group of chitin molecules. Shrinkage of the O-O distance (dOO), which synchronizes with the barrier height, is required for proton transfer from H3O+ to adjacent CH2OH groups or H2O molecules. Nevertheless, dOO is hardly modulated for N = 2 because H2O molecules are strongly constrained on w1 and w2, and therefore, the transfer probability becomes small. For N = 3, novel HBs emerged between the additional H2O molecules broadly distributed on the w3 site and H2O molecules on w1 and w2. The transfer probability is enhanced because large fluctuations and diffusions in the whole H2O molecule yield large modulations of dOO. Consequently, long-range proton hopping is driven by the Zundel-type protonated hydrates in the water network.

Enhancing Thermoelectric Performance of Mg3Sb2 Through Substitutional Doping: Sustainable Energy Solutions via First-Principles Calculations

Mg3Sb2-based materials, part of the Zintl compound family, are known for their low thermal conductivity but face challenges in thermoelectric applications due to their low energy conversion efficiency. This study addressed these limitations through first-principles calculations using the CASTEP module in Materials Studio 8.0, aiming to enhance the thermoelectric performance of Mg3Sb2 via strategic doping. Density functional theory (DFT) calculations were performed to analyze electronic properties, including band structure and density of states (D.O.S.), providing insights into the influence of various dopants. The semiclassical Boltzmann transport theory, implemented in BoltzTrap (version 1.2.5), was used to evaluate key thermoelectric properties such as the Seebeck coefficient, electrical conductivity, electronic thermal conductivity, and electronic figure of merit (eZT). The results indicate that doping significantly improved the thermoelectric properties of Mg3Sb2, facilitating a transition from p-type to n-type behavior. Bi doping reduced the band gap from 0.401 eV to 0.144 eV, increasing carrier concentration and mobility, resulting in an electrical conductivity of 1.66 × 106 S/m and an eZT of 0.757. Ge doping increased the Seebeck coefficient to −392.1 μV/K at 300 K and reduced the band gap to 0.09 eV, achieving an electronic ZT of 0.859 with low thermal conductivity (11 W/mK). Si doping enhanced stability and achieved an electrical conductivity of 1.627 × 106 S/m with an electronic thermal conductivity of 11.3 W/mK, improving thermoelectric performance. These findings established the potential of doped Mg3Sb2 as a highly efficient thermoelectric material, paving the way for future research and applications in sustainable energy solutions.

Emergence of superconductivity and superionicity in the electride [formula omitted]La under extreme conditions

Superconducting electrides, a unique type of conventional superconductors, have recently attracted considerable attention. Inspired by the discovery of high critical temperature (Tc) in lanthanum hydrides and the feasibility of forming electrides in lithium-based compounds, we have conducted a systematic investigation the phase diagram and superconductivity of Li-La alloys under high pressure. Using the crystal structure prediction method and first-principles calculations, we uncovered three pressure-stabilized compounds with stoichiometries LiLa3, LiLa2 and Li6La. All three compounds exhibit metallic behavior with electrons transferred from Li to La atoms. Notably, Li6La emerges as a prototypical superconducting electride with Tc of 11.6 K at 350 GPa, which increases to 16.3 K as pressure decreases to 200 GPa. Electron–phonon analysis reveal that the enhancement of superconductivity mainly originates from the coupling between the increased interstitial quasiatoms (ISQs) and low-frequencies phonons. Additionally, akin to lanthanum hydrides, Li6La is predicted to enter a superionic phase characterized by high lithium diffusion coefficients under high pressure and temperature. Our findings indicate the coexistence of superconductivity and superionicity in the electride Li6La, which may prompt further experimental investigations.

AlN Nanotube Decorated with Small Tin Oxide Clusters as a Novel CH4 Sensing Material.

The success of carbon nanotubes has triggered a great deal of research interest in other one-dimensional nanomaterials with the aim of designing innovative nanostructures with attractive and distinctive attributes for applications in sensing gas molecules and toxic substances. In the present study, first-principles density functional theory calculations were exploited to assess the capability of the small tin oxide cluster (SnxOy)-decorated (6,0)aluminum nitride (AlN) nanotube for detecting methane(CH4) in terms of energetic, structural, and electronic properties. We found that SnxOy clusters were chemisorbed on the surface of the AlN nanotube due to the considerable adsorption energy and the notable charge transfer from the former to the latter. Further calculations demonstrate that the energy band gap and work function of the AlN nanotube were reduced in the presence of additives. Benefiting from the higher affinity of SnxOy toward the CH4 molecule, the Sn3O3-decorated AlN nanotube exhibited the greatest CH4 adsorption energy. The electrical conductivity increased as the energy band gap and effective mass decreased dramatically. Additionally, the type of Sn3O3-decorated AlN nanotube changed from a p-type semiconductor to an n-type one after adsorbing the CH4 molecule. Therefore, the Sn3O3-decorated AlN nanotube endows great promise as a thermopower-based, resistance-based, and Seebeck-effect-based CH4 sensing material.

Fe2O3 Nanoflakes - WS2 Nanosheets Heterojunctions for Multi-Fold Enhancement in Photoelectrochemical Solar Energy Conversion.

Fe2O3-based photoanodes show great potential in photoelectrochemical water splitting due to their excellent stability, moderate band gap, and abundance. However, a short hole diffusion length limits its photocurrent density. Here, a multi-fold enhancement in photocurrent density from Fe2O3 nanoflakes - WS2 nanosheets heterojunction is reported. The heterojunction exhibits a synergistic photocurrent density of 0.52mA cm-2 at 1.3V (versus RHE) under AM 1.5G simulated sunlight, which is 2.23 times higher than pristine Fe2O3 nanoflakes. The Mott-Schottky and Nyquist plots indicate a higher charge density with lower charge transfer resistance at the semiconductor-electrolyte junction. The density functional theory (DFT) -based first-principles calculations are performed by designing a heterostructure between Fe2O3(110) and WS2(001) similar to the experimentally found arrangement of crystal planes. Free energy analysis and relative band extrema positions, obtained from DFT calculations and valence band spectroscopy, indicate the formation of type II heterojunction with partial oxygen terminated surface of Fe2O3. The type-II band alignment with a charge transfer of 4.8 × 10-4 e per interfacial WS2 to Fe2O3, helps in easy separation of photogenerated charges. The work establishes both an experimental design and a theoretical framework of highly crystalline nanoflakes-nanosheet heterojunctions for efficient photoelectrochemical solar energy conversion.

Electron work function guided tailoring of (W4-x, Mx)C4 /doped Ni matrix interfacial bonding: Insights from first-principles calculations

Heavy tungsten carbide (WC) may cause inhomogeneous distributions in WC-metal matrix composite hardfacing overlays, thus negatively affecting its performance as reinforcement. WC can be lightened by partially substituting W with lighter metals, e.g., Mo and Cr, while maintaining its strength. However, the bonding between modified WC and matrix metals such as nickel (a typical metal-matrix for overlays) is uncertain. This article reports a study on the interfacial bonding between (W4-x, Mx)C4 (M=Mo or Cr) and Ni matrix via first-principle calculations. Different atomic interactions i.e., metal-metal and metal-carbon interactions, at the interface were studied to understand the interfacial bonding through analyses of electron work function (EWF), electron localization function, electronic density of states, bond order, and net charge. It was demonstrated that the lighter (W4-x, Mx)C4 carbides exhibit strong bonding with Ni, comparable to or even stronger than that of WC/Ni interface, and the interfacial bonding includes covalent, ionic and metallic bond components. It is demonstrated that the interfacial bonding can be tuned by doping elements in the Ni matrix with different EWFs, e.g., Mn, Cu, Au, Pt, and Se. Efforts have been made to verify a hypothesis that EWF is an indicator, which can be used to guide selecting effective dopants for tailoring the interfacial bond strength.

Mapping the energy-momentum dispersion of hBN excitons and hybrid plasmons in hBN-WSe2 heterostructures

Heterostructures obtained by combining two-dimensional (2D) sheets are widely investigated as a platform for designing new materials with customised characteristics. Transition metal dichalcogenides (TMDCs) are often combined with hexagonal boron nitride (hBN) to enhance their excitonic resonances. However, little is known about how stacking affects excitons and plasmons in TMDCs or their mutual interactions. Here, we combine momentum-resolved electron energy-loss spectroscopy with first-principles calculations to study the energy-momentum dispersion of plasmons in multi-layer WSe2-hBN heterostructures as well as in their isolated components. The dispersion of the high-momentum excitons of hBN, alone and in combination with WSe2, is mapped across the entire Brillouin zone. Signatures of hybridisation in the plasmon resonances and some of the excitons suggest that the contribution of hBN cannot be neglected when interpreting the response of such a heterostructure. The consequences of using hBN as an encapsulant for TMDCs are also discussed.

Growth of L-asparagine monohydrate organic single crystals: An experimental and DFT computational approach for nonlinear optical applications

Good optical quality of L-asparagine monohydrate (C4H8N2O3.H2O) organic single crystal has been grown by adopting natural slow evaporation process at room temperature from aqueous solutions. The lattice parameters obtained by powder X-ray diffraction data revealed orthorhombic crystal system of the harvested crystal. The morphology and planes of the crystal have been identified. The molecular vibrations and functional groups have been specified by Fourier transform infrared (FTIR) spectroscopy studies. Energy dispersive X-ray (EDX) study has been availed to find out the elements constituting the crystal. Scanning electron microscopy, (SEM), provided the surface morphology of the crystal. The dependence of dielectric properties on frequency and temperature have been investigated and the electronic polarizability (α) has been determined. UV–vis spectral analysis shows that the crystal possesses good optical transmittance in the visible part of the energy spectrum. The optical band gap and the Urbach energy have been determined from lower absorption edge. Third order nonlinear susceptibility χ(3), nonlinear refractive index (n2), and linear susceptibility χ(1) have been calculated by Miller's generalized rule. The first-principle computation of band structure of electrons and the electron density of states have been discussed, which suggest that the crystals possess direct band gap. Density Functional Theory (DFT) with B3LYP function by Gaussian09W software was utilized to calculate HOMO-LUMO energy gap as well as non-linear optical parameters namely, linear polarizability (α), hyperpolarizability (β and γ) and dipole moment (μ) of L-asparagine monohydrate crystal. All the findings prove that L-asparagine monohydrate is a promising NLO crystal.

Topological Band Engineering of One-Dimensional π-d Conjugated Metal-Organic Frameworks.

One-dimensional (1D) π-d conjugated metal-organic frameworks (c-MOFs) have garnered widespread research interest in chemical energy storage and conversion. In this work, we introduce a universal principle to engineer the topological bands of 1D c-MOFs. Connected by d orbitals of transition metals, two equivalent hidden molecular π orbitals in 1D c-MOFs can generate a staggered hopping within and between the organic ligands, forming Su-Schrieffer-Heeger-shaped 1D topological bands. Guided by this discovery, we investigate the electronic structures of the typical 1D c-MOF assembled from Ni atoms and 2HQDI (QDI = 2,5-diamino-1,4-benzoquinonediimine) precursors (NiQDI) by first-principles calculations, revealing 1D topological bands around the Fermi level. Due to local bonding variations at the QDI terminations, these two hidden molecular π orbitals become atomically bonded but electronically separated at the edge QDI, creating spatially localized in-gap topological edge states at the end of the NiQDI chain. This definitive signature for 1D topological bands is identified through differential conductance spectra in scanning tunneling microscopy measurements. Our results provide conclusive experimental evidence for topological bands in 1D c-MOFs, paving the way for exploring the topological physics in organic materials through frontier molecular orbitals.

LaAgSiS4: Increasing Optical Birefringence in Rare Earth Chalcogenide by Addition of Planar [AgS3] Groups.

Optoelectronic materials with excellent birefringent properties are of significant importance in the fields of optical communications and laser technology. Recently, rare earth (RE) chalcogenides with anisotropic [RESn] groups have been proven to be high-performance infrared birefringent materials. Herein, we demonstrate that the addition of planar groups can further increase the birefringence in RE chalcogenides, as realized by incorporating planar [AgS3] groups into the RE-I-IV-S4 family for the first time. The newly obtained LaAgSiS4 compound shows higher polarity anisotropy than its homologue LaLiSiS4 and LaKSiS4, which resulted in a larger birefringence (0.12@600 nm) at least twice as large as that of the latter two compounds (0.05/0.06@600 nm). The structure-property relationship of LaAgSiS4 was investigated through structural analysis and first-principles calculations. The results indicate that the increased optical birefringence in LaAgSiS4 originates from the synergic effects of the distorted [LaSn] polyhedra and planar [AgS3] triangles. This work provides an effective strategy for enhancing optical birefringence in IR chalcogenides.

Ultralow thermal conductivity in Si–Ge nanograin mixtures: A cost-effective granular material for thermoelectric applications

This paper presents a theoretical study of the thermal conductivity of Si–Ge nanograin mixtures using a multiscale computational methodology based on solving the Boltzmann transport equation for phonons with first-principles techniques. A size-dependent correction factor is developed to account for the spatial dependence of the phonon distribution function on nanograin size, with parameters derived from the phonon properties of infinite Si and Ge crystals. This approach makes it possible to accurately calculate the thermal conductivity within a single nanograin, using force constants obtained from first-principles calculations. Thermal energy transport by phonons across grain boundaries is modeled by accounting for phonon transmission by two-phonon processes, weighting specular, and diffuse transmission for each phonon mode as a function of the root-mean-square roughness of the boundary relative to the phonon wavelength. The boundary thermal conductance model, previously validated against experimental data, is implemented using first-principles techniques. This approach excludes specular transmission for phonon modes with specific symmetries while ensuring conservation of the total number of modes in each symmetry class. The study examines the influence of grain size, nanograin mixture composition, temperature, and boundary asperities on the thermal conductivity of nanograin mixtures.

Effect of Vacancy Defects on the Electronic Structure and Optical Properties of Bi4O5Br2: First-Principles Calculations

First-principles calculations based on density functional theory are employed to investigate the impact of vacancy defects on the optoelectronic properties of Bi4O5Br2. The results indicate that vacancy defects induce minimal lattice distortion in Bi4O5Br2 without compromising its structural stability. Oxygen or bromine vacancies are more likely to occur than bismuth vacancies. The introduction of a bismuth vacancy leads to n-type semiconductor behavior in the Bi4O5Br2 system, while the creation of an oxygen vacancy reduces the bandgap and enhances the light absorption capacity. Bi4O5Br2 with three coordinated oxygen vacancies exhibits a higher effective electron–hole pair mass ratio, which is advantageous for the efficient separation of electron–hole pairs. Bi4O5Br2 with three coordinated oxygen vacancies exhibits enhanced absorption and reflection coefficients in the visible-light region compared to other systems, indicating that oxygen vacancy defects significantly promote visible-light absorption and electron–hole separation. This research provides new theoretical insights for understanding and optimizing the performance of photocatalysts based on Bi4O5Br2.

Tailoring the Electronic Structure and Properties of Graphdiyne by Cyano Groups.

Two-dimensional (2D) materials, such as 2D carbon-based systems, have been recently the subject of intense studies, thanks to their optoelectronic properties and promising electronic performances. 2D carbon-based materials such as graphdiyne (GDY) represent an optimal platform for tuning the optoelectronic properties via precise chemical functionalization. Here, we report a synthetic strategy to precisely introduce cyano groups into the 2D GDY backbone in order to tune the electronic properties of GDY. Three kinds of cyano-modified GDY have been synthesized, namely, bearing one cyano group (CNGDY), two CN in meta (m-CNGDY), and two in para (p-CNGDY) positions. A variety of experimental data as well as first-principles calculations allowed us to elucidate the role of the cyano groups in tuning the structural and functional properties of GDYs. We found that an increase in the number of cyano groups reduces the interlayer spacing between GDY layers, increases the lithium adsorption amount, as well as impacts the lithium diffusion rate, while changes in meta- or para-position impact the energy band gap.

Strain-Engineered Ferroelectricity in 2H Bilayer MoS2.

The exploration of two-dimensional (2D) materials exhibiting out-of-plane ferroelectric and piezoelectric properties through interlayer twist/translation or strain, known as sliding ferroelectricity, has become a focal point in the quest for low-power electronic devices, capitalizing on weak van der Waals interactions. Herein, we delve into the behavior of strained bilayer molybdenum disulfide (2L-MoS2) transferred onto a nanocone-patterned substrate. An intriguing observation is the emergence of unexpected vertical ferroelectricity in MoS2, irrespective of whether it was prepared using chemical vapor deposition or mechanical exfoliation from the bulk crystal. Such an observation underscores the versatility and reproducibility of the emerging ferroelectricity across different preparation methods. Furthermore, the piezoelectric coefficients recorded are exceptionally high, with the values of 37.54 and 24.80 pm V-1 for monolayer and bilayer MoS2, respectively, outperforming most currently discovered 2D piezoelectrics. The presence of room-temperature out-of-plane ferroelectricity in strained 2L-MoS2 is confirmed through first-principles calculations and piezoresponse force microscopy. This ferroelectric behavior can be attributed to the symmetry breaking and interlayer sliding within the strained 2L-MoS2 structure. Our findings not only deepen the understanding of ferroelectricity in 2D materials but also offer insights for the design of 2D ferroelectrics, thereby enabling diverse functionalities and applications in ferroelectricity.

Multiscale modeling of metal-hydride interphases—quantification of decoupled chemo-mechanical energies

The quantification of interphase properties between metals and their corresponding hydrides is crucial for modeling the thermodynamics and kinetics of the hydrogenation processes in solid-state hydrogen storage materials. In particular, interphase boundary energies assume a pivotal role in determining the kinetics of nucleation, growth, and coarsening of hydrides, alongside accompanying morphological evolution during hydrogenation. The total interphase energy arises from both chemical bonding and mechanical strains in these solid-state systems. Since these contributions are usually coupled, it is challenging to distinguish via conventional computational approaches. Here, a comprehensive atomistic modeling methodology is developed to decouple chemical and mechanical energy contributions using first-principles calculations, of which feasibility is demonstrated by quantifying chemical and elastic strain energies of key interfaces within the FeTi metal-hydride system. Derived materials parameters are then employed for mesoscopic micromechanical analysis, predicting crystallographic orientations in line with experimental observations. The multiscale approach outlined verifies the importance of the chemo-mechanical interplay in the morphological evolution of growing hydride phases, and can be generalized to investigate other systems. In addition, it can streamline the design of atomistic models for the quantitative evaluation of interphase properties between dissimilar phases and allow for efficient predictions of their preferred phase boundary orientations.

Convolutional network learning of self-consistent electron density via grid-projected atomic fingerprints

The self-consistent field (SCF) generation of the three-dimensional (3D) electron density distribution (ρ) represents a fundamental aspect of density functional theory (DFT) and related first-principles calculations, and how one can shorten or bypass the SCF loop represents a critical question in electronic structure theory from both practical and fundamental standpoints. Herein, a machine learning strategy, DeepSCF, is presented in which the map between the SCF ρ and the initial guess density (ρ0) constructed by the summation of neutral atomic densities is learned using 3D convolutional neural networks (CNNs). High accuracy and transferability of DeepSCF are achieved by first encoding ρ0 on a 3D grid and then expanding the input features to include atomic fingerprints beyond ρ0. The prediction of the residual density (δρ) rather than ρ itself is targeted, and given that δρ is indicative of chemical bonding information, a dataset of small-sized organic molecules featuring diverse bonding characters is adopted. The fidelity of DeepSCF is finally enhanced by subjecting the atomic geometries of the dataset to random rotations and strains. The effectiveness of DeepSCF is demonstrated using a complex carbon nanotube-based DNA sequencer model. This work evidences that the nearsightedness in electronic structure can be optimally represented via the spatial locality in CNNs, offering insight into the success of various machine learning-based atomistic materials simulations.