Considerable efforts are being made to transition current lithium-ion and sodium-ion batteries towards the use of solid-state electrolytes.Computational methods,specifically nudged elastic band(NEB)and molecular dynam...Considerable efforts are being made to transition current lithium-ion and sodium-ion batteries towards the use of solid-state electrolytes.Computational methods,specifically nudged elastic band(NEB)and molecular dynamics(MD)methods,provide powerful tools for the design of solid-state electrolytes.The MD method is usually the choice for studying the materials involving complex multiple diffusion paths or having disordered structures.However,it relies on simulations at temperatures much higher than working temperature.This paper studies the reliability of the MD method using the system of Na diffusion in MgO as a benchmark.We carefully study the convergence behavior of the MD method and demonstrate that total effective simulation time of 12 ns can converge the calculated diffusion barrier to about 0.01 eV.The calculated diffusion barrier is 0.31 eV from both methods.The diffusion coefficients at room temperature are 4.3×10^(-9) cm^(2)⋅s^(−1) and 2.2×10^(-9) cm^(2)⋅s^(−1),respectively,from the NEB and MD methods.Our results justify the reliability of the MD method,even though high temperature simulations have to be employed to overcome the limitation on simulation time.展开更多
Materials for deep-ultraviolet(DUV)light emission are extremely rare,significantly limiting the development of efficient DUV light-emitting diodes.Here we report CsMg(I_(1−x)Br_(x))_(3) alloys as potential DUV light e...Materials for deep-ultraviolet(DUV)light emission are extremely rare,significantly limiting the development of efficient DUV light-emitting diodes.Here we report CsMg(I_(1−x)Br_(x))_(3) alloys as potential DUV light emitters.Based on rigorous first-principles hybrid functional calculations,we find that CsMgI_(3) has an indirect bandgap,while CsMgBr_(3) has a direct bandgap.Further,we employ a band unfolding technique for alloy supercell calculations to investigate the critical Br concentration in CsMg(I_(1−x)Br_(x))_(3) associated with the crossover from an indirect to a direct bandgap,which is found to be∼0.36.Thus,CsMg(I_(1−x)Br_(x))_(3) alloys with 0.366≤6≤1 cover a wide range of direct bandgap(4.38–5.37 eV;284–231 nm),falling well into the DUV regime.Our study will guide the development of efficient DUV light emitters.展开更多
The choices of proper dopants and doping sites significantly influence the doping efficiency.In this work,using doping in Al N as an example,we discuss how to choose dopants and doping sites in semiconductors to creat...The choices of proper dopants and doping sites significantly influence the doping efficiency.In this work,using doping in Al N as an example,we discuss how to choose dopants and doping sites in semiconductors to create shallow defect levels.By comparing the defect properties of C_(N),O_(N),Mg_(Al),and Si_(Al)in AlN and analyzing the pros and cons of different doping approaches from the aspects of size mismatch between dopant and host elements,electronegativity difference and perturbation to the band edge states after the substitution,we propose that Mg_(Al)and Si_(Al)should be the best dopants and doping sites for p-type and n-type doping,respectively.Further first-principles calculations verify our predictions as these defects present lower formation energies and shallower defect levels.The defect charge distributions also show that the band edge states,which mainly consist of N-s and p orbitals,are less perturbed when Al is substituted,therefore,the derived defect states turn out to be delocalized,opposite to the situation when N is substituted.This approach of analyzing the band structure of the host material and choosing dopants and doping sites to minimize the perturbation on the host band structure is general and can provide reliable estimations for finding shallow defect levels in semiconductors.展开更多
From the recent experimentally observed conduction band offset and previously reported band gaps,one may deduce that the valence band offset between rutile SnO2 and TiO2 is around 1 eV,with TiO2 having a higher valenc...From the recent experimentally observed conduction band offset and previously reported band gaps,one may deduce that the valence band offset between rutile SnO2 and TiO2 is around 1 eV,with TiO2 having a higher valence band maximum.This implication sharply contradicts the fact that the two compounds have the same rutile structure and the Γ3^+ VBM state is mostly an oxygen p state with a small amount of cation d character,thus one would expect that SnO2 and TiO2 should have small valence band offset.If the valence band offset between SnO2 and TiO2 is indeed small,one may question the correctness of the previously reported band gaps of SnO2 and TiO2.In this paper,using first-principles calculations with different levels of computational methods and functionals within the density functional theory,we reinvestigate the long-standing band gap problem for SnO2.Our analysis suggests that the fundamental band gap of SnO2 should be similar to that of TiO2,i.e.,around 3.0 eV.This value is significantly smaller than the previously reported value of about 3.6 eV,which can be attributed as the optical band gap of this material.Similar to what has been found in In2O3,the discrepancy between the fundamental and optical gaps of SnO2 can be ascribed to the inversion symmetry of its crystal structure and the resultant dipole-forbidden transitions between its band edges.Our results are consistent with most of the optical and electrical measurements of the band gaps and band offset between SnO2 and TiO2,thus provide new understanding of the band structure and optical properties of SnO2.Experimental tests of our predictions are called for.展开更多
Utilizing first-principles band structure method, we studied the trends of electronic structures and band offsets of the common-anion heterojunctions GaX/ZnGeX_2(X = N, P, As, Sb). Here, ZnGeX_2 can be derived by atom...Utilizing first-principles band structure method, we studied the trends of electronic structures and band offsets of the common-anion heterojunctions GaX/ZnGeX_2(X = N, P, As, Sb). Here, ZnGeX_2 can be derived by atomic transmutation of two Ga atoms in GaX into one Zn atom and one Ge atom. The calculated results show that the valence band maximums(VBMs) of GaX are always lower in energy than that of ZnGeX_2, and the band offset decreases when the anion atomic number increases. The conduction band minimums(CBMs) of ZnGeX_2 are lower than that of GaX for X = P, As, and Sb, as expected. However, surprisingly, for ZnGeN2, its CBM is higher than GaN. We found that the coupling between anion p and cation d states plays a decisive role in determining the position of the valence band maximum, and the increased electronegativity of Ge relative to Ga explains the lower CBMs of ZnGeX_2 for X = P, As, and Sb. Meanwhile, due to the high ionicity, the strong coulomb interaction is the origin of the anomalous behavior for nitrides.展开更多
Enhancing the dopability of semiconductors via strain engineering is critical to improving their functionalities,which is,however,largely hindered by the lack of basic rules.In this study,for the first time,we develop...Enhancing the dopability of semiconductors via strain engineering is critical to improving their functionalities,which is,however,largely hindered by the lack of basic rules.In this study,for the first time,we develop a universal theory to understand the total energy changes of point defects(or dopants)with different charge states under strains,which can exhibit either parabolic or superlinear behaviors,determined by the size of defect-induced local volume change(ΔV).In general,ΔV increases(decreases)when an electron is added(removed)to(from)the defect site.Consequently,in terms of this universal theory,three basic rules can be obtained to further understand or predict the diverse strain-dependent doping behaviors,i.e.,defect formation energies,charge-state transition levels,and Fermi pinning levels,in semiconductors.These three basic rules could be generally applied to improve the doping performance or overcome the doping bottlenecks in various semiconductors.展开更多
Topological phase transition in a single material usually refers to transitions between a trivial band insulator and a topological Dirac phase, and the transition may also occur between different classes of topologica...Topological phase transition in a single material usually refers to transitions between a trivial band insulator and a topological Dirac phase, and the transition may also occur between different classes of topological Dirac phases.It is a fundamental challenge to realize quantum transition between Z_2 nontrivial topological insulator（TI） and topological crystalline insulator（TCI） in one material because Z_2 TI and TCI have different requirements on the number of band inversions. The Z_2 TIs must have an odd number of band inversions over all the time-reversal invariant momenta, whereas the newly discovered TCIs, as a distinct class of the topological Dirac materials protected by the underlying crystalline symmetry, owns an even number of band inversions. Taking PbSnTe_2 alloy as an example, here we demonstrate that the atomic-ordering is an effective way to tune the symmetry of the alloy so that we can electrically switch between TCI phase and Z_2 TI phase in a single material. Our results suggest that the atomic-ordering provides a new platform towards the realization of reversibly switching between different topological phases to explore novel applications.展开更多
CdTe is one of the leading materials for low cost,high efficiency thin-film solar cells with a nearly ideal band gap of 1.48 eV.However,its solar to electricity power conversion efficiency(PCE)is hindered by the relat...CdTe is one of the leading materials for low cost,high efficiency thin-film solar cells with a nearly ideal band gap of 1.48 eV.However,its solar to electricity power conversion efficiency(PCE)is hindered by the relatively low open circuit voltage(VOC)due to intrinsic defect related issues.Here,we propose that alloying CdTe with CdSe could possibly improve the solar cell performance by reducing the"ideal"band gap of CdTe to gain more short-circuit current from long-wavelength absorption without sacrificing much VOC.Using the hybrid functional calculation,we find that the minimum band gap of the CdTe1-xSex alloy can be reduced from 1.48 eV at x=0 to 1.39 eV at x=0.32,and most of the change come from the lowering of the conduction band minimum.We also show that the formation of the alloy can improve the p-type doping of CuCdimpurity based on the reduced effective formation energy and nearly constant effective transition energy level,thus possibly enhance VOC,thus PCE.展开更多
Metal oxides play an essential role in modern optoelectronic devices because they have many unique physical properties such as structure diversity, superb stability in solution, good catalytic activity, and simultaneo...Metal oxides play an essential role in modern optoelectronic devices because they have many unique physical properties such as structure diversity, superb stability in solution, good catalytic activity, and simultaneous high electron conductivity and optical transmission. Therefore, they are widely used in energy-related optoelectronic applications such as photovoltaics and photoelectrochemical（PEC） fuel generation. In this review, we mainly discuss the structure engineering and defect control of oxides for energy applications, especially for transparent conducting oxides（TCOs） and oxide catalysts used for water splitting. We will review our current understanding with an emphasis on the contributions of our previous theoretical modeling, primarily based on density functional theory. In particular, we highlight our previous work：（i） the fundamental principles governing the crystal structures and the electrical and optical behaviors of TCOs;（ii） band structures and defect properties for n-type TCOs;（iii） why p-type TCOs are difficult to achieve;（iv） how to modify the band structure to achieve p-type TCOs or even bipolarly dopable TCOs;（v） the origin of the high-performance of amorphous TCOs; and（vi） band structure engineering of bulk and nano oxides for PEC water splitting. Based on the understanding above, we hope to clarify the key issues and the challenges facing the rational design of novel oxides and propose new and feasible strategies or models to improve the performance of existing oxides or design new oxides that are critical for the development of next-generation energy-related applications.展开更多
The solar cell based on organic-inorganic hybrid halide perovskite is progressing amazingly fast in last decade owing to the robust experimental and theoretical investigations. First-principles calculation is one of t...The solar cell based on organic-inorganic hybrid halide perovskite is progressing amazingly fast in last decade owing to the robust experimental and theoretical investigations. First-principles calculation is one of the crucial ways to understand the nature of the materials and is practically helpful to the development and application of perovskite solar cells. Here, we briefly review the progress of theoretical studies we made in the last few years on the modification of electronic structures of perovskites by varying the composition, configuration, and structure, and the new understandings into the defect properties of halide perovskites for solar cell and optoelectronic applications. These understandings are foundations and new starting points for future investigations. We hope the experience and inspiration gained from these studies encourage more theoretical explorations for new functional perovskite-based materials.展开更多
First-principles approaches have recently been developed to replace the phenomenological modeling approaches with adjustable parameters for calculating carrier mobilities in semiconductors.However,in addition to the h...First-principles approaches have recently been developed to replace the phenomenological modeling approaches with adjustable parameters for calculating carrier mobilities in semiconductors.However,in addition to the high computational cost,it is still a challenge to obtain accurate mobility for carriers with a complex band structure,e.g.,hole mobility in common semiconductors.Here,we present a computationally efficient approach using isotropic and parabolic bands to approximate the anisotropy valence bands for evaluating group velocities in the first-principles calculations.This treatment greatly reduces the computational cost in two ways:relieves the requirement of an extremely denseκmesh to obtain a smooth change in group velocity,and reduces the 5-dimensional integral to 3-dimensional integral.Taking Si and SiC as two examples,we find that this simplified approach reproduces the full first-principles calculation for mobility.If we use experimental effective masses to evaluate the group velocity,we can obtain hole mobility in excellent agreement with experimental data over a wide temperature range.These findings shed light on how to improve the first-principles calculations towards predictive carrier mobility in high accuracy.展开更多
The growing worldwide energy needs call for developing novel materials for energy applications.Ab initio density functional theory(DFT)calculations allow the understanding and prediction of material properties at the ...The growing worldwide energy needs call for developing novel materials for energy applications.Ab initio density functional theory(DFT)calculations allow the understanding and prediction of material properties at the atomic scale,thus,play an important role in energy materials design.Due to the fast progress of computer power and development of calculation methodologies,DFT-based calculations have greatly improved their predictive power,and are now leading to a paradigm shift towards theory-driven materials design.The aim of this perspective is to introduce the advances in DFT calculations which accelerate energy materials design.We first present state-of-the-art DFT methods for accurate simulation of various key properties of energy materials.Then we show examples of how these advances lead to the discovery of new energy materials for photovoltaic,photocatalytic,thermoelectric,and battery applications.The challenges and future research directions in computational design of energy materials are highlighted at the end.展开更多
Ferroelectricity of group-Ⅳ chalcogenides MX(M = Ge,Sn;X = Se,S) monolayers has been extensively investigated.However,how the ferroelectricity evolves in their one-dimensional nanotubes remains largely unclear.Employ...Ferroelectricity of group-Ⅳ chalcogenides MX(M = Ge,Sn;X = Se,S) monolayers has been extensively investigated.However,how the ferroelectricity evolves in their one-dimensional nanotubes remains largely unclear.Employing an accurate deep-learning interatomic potential of first-principles precision,we uncover a general stepwise mechanism for polarization switching in zigzag and chiral Ge S nanotubes,which has an energy barrier that is substantially lower than the one associated with the conventional one-step switching mechanism.The switching barrier(per atom) gradually decreases with increasing the number of intermediate steps and converges to a value that is almost independent of the tube diameter.In the chiral Ge S nanotubes,the switching path of polarization with chirality coupling is preferred at less intermediate steps.This study unveils novel ferroelectric switching behaviors in one-dimensional nanotubes,which is critical to coupling ferroelectricity and chirality.展开更多
The coupling between electric ordering and magnetic ordering in two-dimensional(2D)materials is important for both fundamental research of 2D multiferroics and future development of magnetism-based information storage...The coupling between electric ordering and magnetic ordering in two-dimensional(2D)materials is important for both fundamental research of 2D multiferroics and future development of magnetism-based information storage and operation.Here,we introduce a scheme for realizing a magnetic phase transition through the transition of electric ordering.We take CuMoP_(2)S_(6) monolayer as an example,which is a member of the large 2D transition-metal chalcogen-phosphates family.Based on first-principles calculations,we find that it is a multiferroic with unprecedented characters,namely,it exhibits two different phases:an antiferroelectric-antiferromagnetic phase and a ferroelectric-ferromagnetic phase,in which the electric and magnetic orderings are strongly coupled.Importantly,the electric polarization is out-of-plane,so the magnetism can be readily switched by using the gate electric field.Our finding reveals a series of 2D multiferroics with special magnetoelectric coupling,which hold great promise for experimental realization and practical applications.展开更多
Many issues concerning the origin of high-temperature superconductivity(HTS)are still under debate.For example,how the magnetic order varies with doping and its relationship with the superconducting temperature(Tc);an...Many issues concerning the origin of high-temperature superconductivity(HTS)are still under debate.For example,how the magnetic order varies with doping and its relationship with the superconducting temperature(Tc);and why Tcalways peaks near the quantum critical point.In this paper,taking hole-doped La_(2)CuO_(4)as a classical example,we employ the first-principles band structure and total energy calculations with Monte Carlo simulations to explore how the symmetry-breaking magnetic ground state evolves with hole doping and the origin of a dome-shaped superconductivity region in the phase diagram.We demonstrate that the local antiferromagnetic order and doping play key roles in determining the electron-phonon coupling,thus Tc.Initially,the La_(2)CuO_(4)possesses a checkerboard local antiferromagnetic ground state.As the hole doping increases,Tcincreases with the enhanced electron-phonon coupling strength.But as the doping increases further,the strength of the antiferromagnetic interaction weakens and spin fluctuation increases.At the critical doping level,a magnetic phase transition occurs that reduces the local antiferromagnetism-assisted electron-phonon coupling,thus diminishing the Tc.The superconductivity disappears in the heavily overdoped region when the ferromagnetic order dominates.These observations could account for why cuprates have a dome-shaped superconductivity region in the phase diagram.Our study,thus,contributes to a fundamental understanding of the correlation between doping,local magnetic order,and superconductivity of HTS.展开更多
Wide-bandgap two-dimensional (2D) β-TeO_(2) has been reported as a high-mobility p-type transparent semiconductor [Nat. Electron. 4 277 (2021)], attracting significant attention. This "breakthrough" not onl...Wide-bandgap two-dimensional (2D) β-TeO_(2) has been reported as a high-mobility p-type transparent semiconductor [Nat. Electron. 4 277 (2021)], attracting significant attention. This "breakthrough" not only challenges the conventional characterization of TeO_(2) as an insulator but also conflicts with the anticipated difficulty in hole doping of TeO_(2) by established chemical trends. Notably, the reported Fermi level of 0.9 eV above the valence band maximum actually suggests that the material is an insulator, contradicting the high hole density obtained by Hall effect measurement. Furthermore, the detected residual Se and the possible reduced elemental Te in the 2D β-TeO_(2) samples introduces complexity, considering that elemental Se, Te, and Te_(1−x)Se_(x) themselves are high-mobility p-type semiconductors. Therefore, doubts regarding the true cause of the p-type conductivity observed in the 2D β-TeO_(2) samples arise. In this Letter, we employ density functional theory calculations to illustrate that TeO_(2), whether in its bulk forms of α-, β-, or γ-TeO_(2), or in the 2D β-TeO_(2) nanosheets, inherently exhibits insulating properties and poses challenges in carrier doping due to its shallow conduction band minimum and deep valence band maximum. Our findings shed light on the insulating properties and doping difficulty of TeO_(2), contrasting with the claimed p-type conductivity in the 2D β-TeO_(2) samples, prompting inquiries into the true origin of the p-type conductivity.展开更多
Anisotropic materials are of considerable interest because of their unique combination of polarization- or direction-dependent electrical, optical, and thermoelectric properties. Low-symmetry two-dimensional （2D） ma...Anisotropic materials are of considerable interest because of their unique combination of polarization- or direction-dependent electrical, optical, and thermoelectric properties. Low-symmetry two-dimensional （2D） materials formed by van der Waals stacking of covalently bonded atomic layers are inherently anisotropic. Layered SnSe exhibits a low degree of lattice symmetry, with a distorted NaC1 structure and an in-plane anisotropy. Here we report a systematic study of the in-plane anisotropic properties in layered SnSe, using angle-resolved Raman scattering, optical absorption, and electrical transport studies. The optical and electrical characterization was direction-dependent, and successfully identified the crystalline orientation in the layered SnSe. Furthermore, the dependence of Raman-intensity anisotropy on the SnSe flake thickness and the excitation wavelength were investigated by both experiments and theoretical calculations. Finally, the electrical transport studies demonstrated that few-layer SnSe field- effect transistors （FETs） have a large anisotropic ratio of carrier mobility （N 5.8） bet- ween the armchair and zigzag directions, which is a record high value reported for 2D anisotropic materials. The highly-anisotropic properties of layered SnSe indicate considerable promise for anisotropic optics, electronics, and optoelectronics.展开更多
Realization of half-metallicity in low dimensional materials is a fundamental challenge for nano spintronics,which is a critical component for next-generation information technology.Using the method of generalized Blo...Realization of half-metallicity in low dimensional materials is a fundamental challenge for nano spintronics,which is a critical component for next-generation information technology.Using the method of generalized Bloch theorem,we show that an in-plane bending can induce inhomogeneous strains,which in turn lead to spin-splitting in zigzag graphene nanoribbons and results in the highly desired half-metallic state.Unlike the previously proposed scheme that requires unrealistically strong external electric fields,the obtained half-metallicity with sizeable half-metallic gap and high energetic stability of magnetic order of edge states requires only relatively low-level strain in the in-plane bending.Given the superior structural flexibility of graphene and the recent experimental advances in controllable synthesis of graphene nanoribbons,our design provides a hitherto most practical approach to the realization of half-metallicity in low dimensional systems.This work,thus paves a way towards the design of nanoscale spintronic devices through strain engineering.展开更多
Using first-principles calculations,the structural,electronic,and defect properties of AgInSe_(2)(AIS),AgGaSe_(2)(AGS),and their alloys(AIGS)are systematically studied and compared with their Cu counterparts as potent...Using first-principles calculations,the structural,electronic,and defect properties of AgInSe_(2)(AIS),AgGaSe_(2)(AGS),and their alloys(AIGS)are systematically studied and compared with their Cu counterparts as potential candidates for thin-film solar cell absorbers.The bandgap energies of AIS(1.24 eV)and AGS(1.84 eV)are larger than their Cu counterparts,despite their larger lattice parameters.According to the Shockley-Queisser theory,AIS or AIGS could be more suitable for solar-cell-absorber materials than their Cu counterparts.However,after investigating the band structures and intrinsic defect properties of AIS and AGS,we find that,(i)AIS and AGS have large negative crystal field splitting,thus low density of states near the valence band maximum(VBM);(ii)similar to the Cu counterparts,Ag vacancy(V_(Ag))is the main hole-carrier provider,while In_(Ag)(or Ga_(Ag))serves as the hole-carrier killer in p-type AIS(or AGS).However,because the positions of theVBM and conduction band minimum of AIS(or AGS)are lower than those of Cu In Se_(2)(CIS)[or Cu Ga Se_(2)(CGS)],the compensation of the p-type doping in AIS(or AGS)is more severe.Thus,the p-type doping of AIS(or AIGS)is more difficult than that of CIS(or CIGS),which is consistent with the doping limit rule.To improve the p-type doping of the AIS(or AIGS)as the solar-cell absorber,thus,improve the power conversion efficiency(PCE),the Ag-rich/(In,Ga)-poor/Se-rich growth condition is preferred.Alloy engineering of AIS with AGS can enhance the PCE because it can tune the bandgap energy of the absorber and band alignment at the absorber/buffer interface.More importantly,we suggest that for AIS(or AIGS)solar cell,the traditional buffer material of Cd S is not suitable anymore due to the large conduction band offset between AIS and Cd S.A new buffer layer material with a lower conduction band edge is necessary for better electron transport in AIS(or AIGS)solar cell.展开更多
A solar cell is a photovoltaic device that converts solar radiation energy to electrical energy, which plays a leading role in alleviating global energy shortages and decreasing air pollution levels typical of convent...A solar cell is a photovoltaic device that converts solar radiation energy to electrical energy, which plays a leading role in alleviating global energy shortages and decreasing air pollution levels typical of conventional fossil fuels. To render solar cells more efficient, high visible-light absorption rates and excellent carrier transport properties are required to generate high carrier levels and high output voltage. Hence, the core material, i.e., the absorption layer, should have an appropriate direct band gap and be effectively doped by both p-and n-types with minimal carrier traps and recombination centers. Consequently, defect properties of absorbers are critical in determining solar cell efficiency. In this work, we review recent first-principles studies of defect properties and engineering in four representative thin-film solar cells, namely CdTe, Cu(In,Ga)Se2, Cu2ZnSnS4, and halide perovskites. The focal points include basic electronic and defect properties, existing problems, and possible solutions in engineering defect properties of those materials to optimize solar cell efficiency.展开更多
基金supported by the National Natural Science Foundation of China (Grant Nos.12164019,11991060,12088101,and U1930402)the Natural Science Foundation of Jiangxi Province of China (Grant No.20212BAB201017).
文摘Considerable efforts are being made to transition current lithium-ion and sodium-ion batteries towards the use of solid-state electrolytes.Computational methods,specifically nudged elastic band(NEB)and molecular dynamics(MD)methods,provide powerful tools for the design of solid-state electrolytes.The MD method is usually the choice for studying the materials involving complex multiple diffusion paths or having disordered structures.However,it relies on simulations at temperatures much higher than working temperature.This paper studies the reliability of the MD method using the system of Na diffusion in MgO as a benchmark.We carefully study the convergence behavior of the MD method and demonstrate that total effective simulation time of 12 ns can converge the calculated diffusion barrier to about 0.01 eV.The calculated diffusion barrier is 0.31 eV from both methods.The diffusion coefficients at room temperature are 4.3×10^(-9) cm^(2)⋅s^(−1) and 2.2×10^(-9) cm^(2)⋅s^(−1),respectively,from the NEB and MD methods.Our results justify the reliability of the MD method,even though high temperature simulations have to be employed to overcome the limitation on simulation time.
基金supported by the National Natural Science Foundation of China(Grant Nos.52172136,12088101,11991060,and U2230402)。
文摘Materials for deep-ultraviolet(DUV)light emission are extremely rare,significantly limiting the development of efficient DUV light-emitting diodes.Here we report CsMg(I_(1−x)Br_(x))_(3) alloys as potential DUV light emitters.Based on rigorous first-principles hybrid functional calculations,we find that CsMgI_(3) has an indirect bandgap,while CsMgBr_(3) has a direct bandgap.Further,we employ a band unfolding technique for alloy supercell calculations to investigate the critical Br concentration in CsMg(I_(1−x)Br_(x))_(3) associated with the crossover from an indirect to a direct bandgap,which is found to be∼0.36.Thus,CsMg(I_(1−x)Br_(x))_(3) alloys with 0.366≤6≤1 cover a wide range of direct bandgap(4.38–5.37 eV;284–231 nm),falling well into the DUV regime.Our study will guide the development of efficient DUV light emitters.
基金supported by the National Natural Science Foundation of China(Grants No.11991060,No.12088101,No.U2230402,and No.12304006)the Natural Science Foundation of WIUCAS(Grants No.WIUCASQD2023004)。
文摘The choices of proper dopants and doping sites significantly influence the doping efficiency.In this work,using doping in Al N as an example,we discuss how to choose dopants and doping sites in semiconductors to create shallow defect levels.By comparing the defect properties of C_(N),O_(N),Mg_(Al),and Si_(Al)in AlN and analyzing the pros and cons of different doping approaches from the aspects of size mismatch between dopant and host elements,electronegativity difference and perturbation to the band edge states after the substitution,we propose that Mg_(Al)and Si_(Al)should be the best dopants and doping sites for p-type and n-type doping,respectively.Further first-principles calculations verify our predictions as these defects present lower formation energies and shallower defect levels.The defect charge distributions also show that the band edge states,which mainly consist of N-s and p orbitals,are less perturbed when Al is substituted,therefore,the derived defect states turn out to be delocalized,opposite to the situation when N is substituted.This approach of analyzing the band structure of the host material and choosing dopants and doping sites to minimize the perturbation on the host band structure is general and can provide reliable estimations for finding shallow defect levels in semiconductors.
基金support from the Beijing Computational Science Research Center (CSRC)supported by the Science Challenge Project (No.TZ2016003)+1 种基金the National Key Research and Development Program of China (No.2016YFB0700700)the Nature Science Foundation of China (No.11634003,51672023,U1930402 )
文摘From the recent experimentally observed conduction band offset and previously reported band gaps,one may deduce that the valence band offset between rutile SnO2 and TiO2 is around 1 eV,with TiO2 having a higher valence band maximum.This implication sharply contradicts the fact that the two compounds have the same rutile structure and the Γ3^+ VBM state is mostly an oxygen p state with a small amount of cation d character,thus one would expect that SnO2 and TiO2 should have small valence band offset.If the valence band offset between SnO2 and TiO2 is indeed small,one may question the correctness of the previously reported band gaps of SnO2 and TiO2.In this paper,using first-principles calculations with different levels of computational methods and functionals within the density functional theory,we reinvestigate the long-standing band gap problem for SnO2.Our analysis suggests that the fundamental band gap of SnO2 should be similar to that of TiO2,i.e.,around 3.0 eV.This value is significantly smaller than the previously reported value of about 3.6 eV,which can be attributed as the optical band gap of this material.Similar to what has been found in In2O3,the discrepancy between the fundamental and optical gaps of SnO2 can be ascribed to the inversion symmetry of its crystal structure and the resultant dipole-forbidden transitions between its band edges.Our results are consistent with most of the optical and electrical measurements of the band gaps and band offset between SnO2 and TiO2,thus provide new understanding of the band structure and optical properties of SnO2.Experimental tests of our predictions are called for.
基金financially supported by the Major State Basic Research Development Program of China under Grant No2016YFB0700700the National Natural Science Foundation of China(NSFC)under Grants Nos.11634003,11474273,61121491 and U153040+2 种基金the Science Challenge Project,under Grant No.TZ20160003supported by the National Young 1000 Talents Plansupported by the Youth Innovation Promotion Association of CAS(No.2017154)
文摘Utilizing first-principles band structure method, we studied the trends of electronic structures and band offsets of the common-anion heterojunctions GaX/ZnGeX_2(X = N, P, As, Sb). Here, ZnGeX_2 can be derived by atomic transmutation of two Ga atoms in GaX into one Zn atom and one Ge atom. The calculated results show that the valence band maximums(VBMs) of GaX are always lower in energy than that of ZnGeX_2, and the band offset decreases when the anion atomic number increases. The conduction band minimums(CBMs) of ZnGeX_2 are lower than that of GaX for X = P, As, and Sb, as expected. However, surprisingly, for ZnGeN2, its CBM is higher than GaN. We found that the coupling between anion p and cation d states plays a decisive role in determining the position of the valence band maximum, and the increased electronegativity of Ge relative to Ga explains the lower CBMs of ZnGeX_2 for X = P, As, and Sb. Meanwhile, due to the high ionicity, the strong coulomb interaction is the origin of the anomalous behavior for nitrides.
基金the National Natural Science Foundation of China(Grant Nos.11634003,11991060,and 12088101)NSAF(Grant No.U1930402)。
文摘Enhancing the dopability of semiconductors via strain engineering is critical to improving their functionalities,which is,however,largely hindered by the lack of basic rules.In this study,for the first time,we develop a universal theory to understand the total energy changes of point defects(or dopants)with different charge states under strains,which can exhibit either parabolic or superlinear behaviors,determined by the size of defect-induced local volume change(ΔV).In general,ΔV increases(decreases)when an electron is added(removed)to(from)the defect site.Consequently,in terms of this universal theory,three basic rules can be obtained to further understand or predict the diverse strain-dependent doping behaviors,i.e.,defect formation energies,charge-state transition levels,and Fermi pinning levels,in semiconductors.These three basic rules could be generally applied to improve the doping performance or overcome the doping bottlenecks in various semiconductors.
基金Supported by the Major State Basic Research Development Program of China under Grant No 2016YFB0700700the National Natural Science Foundation of China(NSFC)under Grants Nos 11634003,11474273,61121491 and U1530401+1 种基金supported by the National Young 1000 Talents Plansupported by the Youth Innovation Promotion Association of CAS(2017154)
文摘Topological phase transition in a single material usually refers to transitions between a trivial band insulator and a topological Dirac phase, and the transition may also occur between different classes of topological Dirac phases.It is a fundamental challenge to realize quantum transition between Z_2 nontrivial topological insulator（TI） and topological crystalline insulator（TCI） in one material because Z_2 TI and TCI have different requirements on the number of band inversions. The Z_2 TIs must have an odd number of band inversions over all the time-reversal invariant momenta, whereas the newly discovered TCIs, as a distinct class of the topological Dirac materials protected by the underlying crystalline symmetry, owns an even number of band inversions. Taking PbSnTe_2 alloy as an example, here we demonstrate that the atomic-ordering is an effective way to tune the symmetry of the alloy so that we can electrically switch between TCI phase and Z_2 TI phase in a single material. Our results suggest that the atomic-ordering provides a new platform towards the realization of reversibly switching between different topological phases to explore novel applications.
基金Project supported by the National Key Research and Development Program of China(Grant No.2016YFB0700700)the National Natural Science Foundation of China(Grant Nos.51672023,11847043,11634003,and U1530401)the Science Challenge Project(Grant Nos.TZ2016003 and TZ2018004)
文摘CdTe is one of the leading materials for low cost,high efficiency thin-film solar cells with a nearly ideal band gap of 1.48 eV.However,its solar to electricity power conversion efficiency(PCE)is hindered by the relatively low open circuit voltage(VOC)due to intrinsic defect related issues.Here,we propose that alloying CdTe with CdSe could possibly improve the solar cell performance by reducing the"ideal"band gap of CdTe to gain more short-circuit current from long-wavelength absorption without sacrificing much VOC.Using the hybrid functional calculation,we find that the minimum band gap of the CdTe1-xSex alloy can be reduced from 1.48 eV at x=0 to 1.39 eV at x=0.32,and most of the change come from the lowering of the conduction band minimum.We also show that the formation of the alloy can improve the p-type doping of CuCdimpurity based on the reduced effective formation energy and nearly constant effective transition energy level,thus possibly enhance VOC,thus PCE.
基金Project supported by the National Key Research and Development Program of China(Grant No.2016YFB0700700)the Science Challenge Project,China(Grant No.TZ20160003)+1 种基金the National Natural Science Foundation of China(Grant Nos.51672023,11474273,11634003,and U1530401)supported by the Youth Innovation Promotion Association of Chinese Academy of Sciences(Grant No.2017154)
文摘Metal oxides play an essential role in modern optoelectronic devices because they have many unique physical properties such as structure diversity, superb stability in solution, good catalytic activity, and simultaneous high electron conductivity and optical transmission. Therefore, they are widely used in energy-related optoelectronic applications such as photovoltaics and photoelectrochemical（PEC） fuel generation. In this review, we mainly discuss the structure engineering and defect control of oxides for energy applications, especially for transparent conducting oxides（TCOs） and oxide catalysts used for water splitting. We will review our current understanding with an emphasis on the contributions of our previous theoretical modeling, primarily based on density functional theory. In particular, we highlight our previous work：（i） the fundamental principles governing the crystal structures and the electrical and optical behaviors of TCOs;（ii） band structures and defect properties for n-type TCOs;（iii） why p-type TCOs are difficult to achieve;（iv） how to modify the band structure to achieve p-type TCOs or even bipolarly dopable TCOs;（v） the origin of the high-performance of amorphous TCOs; and（vi） band structure engineering of bulk and nano oxides for PEC water splitting. Based on the understanding above, we hope to clarify the key issues and the challenges facing the rational design of novel oxides and propose new and feasible strategies or models to improve the performance of existing oxides or design new oxides that are critical for the development of next-generation energy-related applications.
基金Project supported by the National Key Research and Development Program of China (Grant No. 2016YFB0700700)the National Natural Science Foundation of China (Grant Nos. 51672023, 11634003, and U1930402)the Creative Talents Plan in CPSF, China (Grant No. BX2018033).
文摘The solar cell based on organic-inorganic hybrid halide perovskite is progressing amazingly fast in last decade owing to the robust experimental and theoretical investigations. First-principles calculation is one of the crucial ways to understand the nature of the materials and is practically helpful to the development and application of perovskite solar cells. Here, we briefly review the progress of theoretical studies we made in the last few years on the modification of electronic structures of perovskites by varying the composition, configuration, and structure, and the new understandings into the defect properties of halide perovskites for solar cell and optoelectronic applications. These understandings are foundations and new starting points for future investigations. We hope the experience and inspiration gained from these studies encourage more theoretical explorations for new functional perovskite-based materials.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11925407 and 61927901)the Key Research Program of Frontier Sciences,Chinese Academy of Sciences(Grant No.ZDBS-LY-JSC019).
文摘First-principles approaches have recently been developed to replace the phenomenological modeling approaches with adjustable parameters for calculating carrier mobilities in semiconductors.However,in addition to the high computational cost,it is still a challenge to obtain accurate mobility for carriers with a complex band structure,e.g.,hole mobility in common semiconductors.Here,we present a computationally efficient approach using isotropic and parabolic bands to approximate the anisotropy valence bands for evaluating group velocities in the first-principles calculations.This treatment greatly reduces the computational cost in two ways:relieves the requirement of an extremely denseκmesh to obtain a smooth change in group velocity,and reduces the 5-dimensional integral to 3-dimensional integral.Taking Si and SiC as two examples,we find that this simplified approach reproduces the full first-principles calculation for mobility.If we use experimental effective masses to evaluate the group velocity,we can obtain hole mobility in excellent agreement with experimental data over a wide temperature range.These findings shed light on how to improve the first-principles calculations towards predictive carrier mobility in high accuracy.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.12088101,11991060,12074029,52172136,and U1930402)。
文摘The growing worldwide energy needs call for developing novel materials for energy applications.Ab initio density functional theory(DFT)calculations allow the understanding and prediction of material properties at the atomic scale,thus,play an important role in energy materials design.Due to the fast progress of computer power and development of calculation methodologies,DFT-based calculations have greatly improved their predictive power,and are now leading to a paradigm shift towards theory-driven materials design.The aim of this perspective is to introduce the advances in DFT calculations which accelerate energy materials design.We first present state-of-the-art DFT methods for accurate simulation of various key properties of energy materials.Then we show examples of how these advances lead to the discovery of new energy materials for photovoltaic,photocatalytic,thermoelectric,and battery applications.The challenges and future research directions in computational design of energy materials are highlighted at the end.
基金supported by the National Natural Science Foundation of China (Grant Nos.52172136,11991060,12088101,and U2230402)。
文摘Ferroelectricity of group-Ⅳ chalcogenides MX(M = Ge,Sn;X = Se,S) monolayers has been extensively investigated.However,how the ferroelectricity evolves in their one-dimensional nanotubes remains largely unclear.Employing an accurate deep-learning interatomic potential of first-principles precision,we uncover a general stepwise mechanism for polarization switching in zigzag and chiral Ge S nanotubes,which has an energy barrier that is substantially lower than the one associated with the conventional one-step switching mechanism.The switching barrier(per atom) gradually decreases with increasing the number of intermediate steps and converges to a value that is almost independent of the tube diameter.In the chiral Ge S nanotubes,the switching path of polarization with chirality coupling is preferred at less intermediate steps.This study unveils novel ferroelectric switching behaviors in one-dimensional nanotubes,which is critical to coupling ferroelectricity and chirality.
基金Supported by the National Key R&D Program of China(Grant No.2019YFE0112000)the Zhejiang Provincial Natural Science Foundation of China(Grant No.LR21A040001)the National Natural Science Foundation of China(Grant No.11974307,12088101,11991060,and U1930402).
文摘The coupling between electric ordering and magnetic ordering in two-dimensional(2D)materials is important for both fundamental research of 2D multiferroics and future development of magnetism-based information storage and operation.Here,we introduce a scheme for realizing a magnetic phase transition through the transition of electric ordering.We take CuMoP_(2)S_(6) monolayer as an example,which is a member of the large 2D transition-metal chalcogen-phosphates family.Based on first-principles calculations,we find that it is a multiferroic with unprecedented characters,namely,it exhibits two different phases:an antiferroelectric-antiferromagnetic phase and a ferroelectric-ferromagnetic phase,in which the electric and magnetic orderings are strongly coupled.Importantly,the electric polarization is out-of-plane,so the magnetism can be readily switched by using the gate electric field.Our finding reveals a series of 2D multiferroics with special magnetoelectric coupling,which hold great promise for experimental realization and practical applications.
基金supported by the National Natural Science Foundation of China(Grant Nos.61922077,11874347,11991060,12088101,61927901U2230402)+3 种基金the National Key Research and Development Program of China(Grant Nos.2018YFB2200100,and 2020YFB1506400)the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB0460000)the CAS Project for Young Scientists in Basic Research(Grant No.YSBR-026)supported by the Youth Innovation Promotion Association of Chinese Academy of Sciences(Grant No.Y2021042)。
文摘Many issues concerning the origin of high-temperature superconductivity(HTS)are still under debate.For example,how the magnetic order varies with doping and its relationship with the superconducting temperature(Tc);and why Tcalways peaks near the quantum critical point.In this paper,taking hole-doped La_(2)CuO_(4)as a classical example,we employ the first-principles band structure and total energy calculations with Monte Carlo simulations to explore how the symmetry-breaking magnetic ground state evolves with hole doping and the origin of a dome-shaped superconductivity region in the phase diagram.We demonstrate that the local antiferromagnetic order and doping play key roles in determining the electron-phonon coupling,thus Tc.Initially,the La_(2)CuO_(4)possesses a checkerboard local antiferromagnetic ground state.As the hole doping increases,Tcincreases with the enhanced electron-phonon coupling strength.But as the doping increases further,the strength of the antiferromagnetic interaction weakens and spin fluctuation increases.At the critical doping level,a magnetic phase transition occurs that reduces the local antiferromagnetism-assisted electron-phonon coupling,thus diminishing the Tc.The superconductivity disappears in the heavily overdoped region when the ferromagnetic order dominates.These observations could account for why cuprates have a dome-shaped superconductivity region in the phase diagram.Our study,thus,contributes to a fundamental understanding of the correlation between doping,local magnetic order,and superconductivity of HTS.
基金supported by the National Natural Science Foundation of China(Grant Nos.52372150,12088101,and 11991060)the National Key R&D Program of China(Grant No.2022YFB4200305)。
文摘Wide-bandgap two-dimensional (2D) β-TeO_(2) has been reported as a high-mobility p-type transparent semiconductor [Nat. Electron. 4 277 (2021)], attracting significant attention. This "breakthrough" not only challenges the conventional characterization of TeO_(2) as an insulator but also conflicts with the anticipated difficulty in hole doping of TeO_(2) by established chemical trends. Notably, the reported Fermi level of 0.9 eV above the valence band maximum actually suggests that the material is an insulator, contradicting the high hole density obtained by Hall effect measurement. Furthermore, the detected residual Se and the possible reduced elemental Te in the 2D β-TeO_(2) samples introduces complexity, considering that elemental Se, Te, and Te_(1−x)Se_(x) themselves are high-mobility p-type semiconductors. Therefore, doubts regarding the true cause of the p-type conductivity observed in the 2D β-TeO_(2) samples arise. In this Letter, we employ density functional theory calculations to illustrate that TeO_(2), whether in its bulk forms of α-, β-, or γ-TeO_(2), or in the 2D β-TeO_(2) nanosheets, inherently exhibits insulating properties and poses challenges in carrier doping due to its shallow conduction band minimum and deep valence band maximum. Our findings shed light on the insulating properties and doping difficulty of TeO_(2), contrasting with the claimed p-type conductivity in the 2D β-TeO_(2) samples, prompting inquiries into the true origin of the p-type conductivity.
文摘Anisotropic materials are of considerable interest because of their unique combination of polarization- or direction-dependent electrical, optical, and thermoelectric properties. Low-symmetry two-dimensional （2D） materials formed by van der Waals stacking of covalently bonded atomic layers are inherently anisotropic. Layered SnSe exhibits a low degree of lattice symmetry, with a distorted NaC1 structure and an in-plane anisotropy. Here we report a systematic study of the in-plane anisotropic properties in layered SnSe, using angle-resolved Raman scattering, optical absorption, and electrical transport studies. The optical and electrical characterization was direction-dependent, and successfully identified the crystalline orientation in the layered SnSe. Furthermore, the dependence of Raman-intensity anisotropy on the SnSe flake thickness and the excitation wavelength were investigated by both experiments and theoretical calculations. Finally, the electrical transport studies demonstrated that few-layer SnSe field- effect transistors （FETs） have a large anisotropic ratio of carrier mobility （N 5.8） bet- ween the armchair and zigzag directions, which is a record high value reported for 2D anisotropic materials. The highly-anisotropic properties of layered SnSe indicate considerable promise for anisotropic optics, electronics, and optoelectronics.
基金supported by the National Natural Science Foundation of China(NSFC)under Grants No.U1530401,and No.11674022.
文摘Realization of half-metallicity in low dimensional materials is a fundamental challenge for nano spintronics,which is a critical component for next-generation information technology.Using the method of generalized Bloch theorem,we show that an in-plane bending can induce inhomogeneous strains,which in turn lead to spin-splitting in zigzag graphene nanoribbons and results in the highly desired half-metallic state.Unlike the previously proposed scheme that requires unrealistically strong external electric fields,the obtained half-metallicity with sizeable half-metallic gap and high energetic stability of magnetic order of edge states requires only relatively low-level strain in the in-plane bending.Given the superior structural flexibility of graphene and the recent experimental advances in controllable synthesis of graphene nanoribbons,our design provides a hitherto most practical approach to the realization of half-metallicity in low dimensional systems.This work,thus paves a way towards the design of nanoscale spintronic devices through strain engineering.
基金supported by the National Natural Science Foundation of China(Grant Nos.11991060,12088101,and U1930402)National Supercomputer Center in Tianjin is acknowledged for computational support。
文摘Using first-principles calculations,the structural,electronic,and defect properties of AgInSe_(2)(AIS),AgGaSe_(2)(AGS),and their alloys(AIGS)are systematically studied and compared with their Cu counterparts as potential candidates for thin-film solar cell absorbers.The bandgap energies of AIS(1.24 eV)and AGS(1.84 eV)are larger than their Cu counterparts,despite their larger lattice parameters.According to the Shockley-Queisser theory,AIS or AIGS could be more suitable for solar-cell-absorber materials than their Cu counterparts.However,after investigating the band structures and intrinsic defect properties of AIS and AGS,we find that,(i)AIS and AGS have large negative crystal field splitting,thus low density of states near the valence band maximum(VBM);(ii)similar to the Cu counterparts,Ag vacancy(V_(Ag))is the main hole-carrier provider,while In_(Ag)(or Ga_(Ag))serves as the hole-carrier killer in p-type AIS(or AGS).However,because the positions of theVBM and conduction band minimum of AIS(or AGS)are lower than those of Cu In Se_(2)(CIS)[or Cu Ga Se_(2)(CGS)],the compensation of the p-type doping in AIS(or AGS)is more severe.Thus,the p-type doping of AIS(or AIGS)is more difficult than that of CIS(or CIGS),which is consistent with the doping limit rule.To improve the p-type doping of the AIS(or AIGS)as the solar-cell absorber,thus,improve the power conversion efficiency(PCE),the Ag-rich/(In,Ga)-poor/Se-rich growth condition is preferred.Alloy engineering of AIS with AGS can enhance the PCE because it can tune the bandgap energy of the absorber and band alignment at the absorber/buffer interface.More importantly,we suggest that for AIS(or AIGS)solar cell,the traditional buffer material of Cd S is not suitable anymore due to the large conduction band offset between AIS and Cd S.A new buffer layer material with a lower conduction band edge is necessary for better electron transport in AIS(or AIGS)solar cell.
基金supported by the National Natural Science Foundation of China (Grant Nos. 61922077, 11874347, 51672023, 11634003, and U1930402)the National Key Research and Development Program of China (Grant Nos. 2016YFB0700700, and 2018YFB2200100)+1 种基金the Key Research & Development Program of Beijing (Grant No. Z181100005118003)supported by the Youth Innovation Promotion Association of Chinese Academy of Sciences (Grant No. 2017154)。
文摘A solar cell is a photovoltaic device that converts solar radiation energy to electrical energy, which plays a leading role in alleviating global energy shortages and decreasing air pollution levels typical of conventional fossil fuels. To render solar cells more efficient, high visible-light absorption rates and excellent carrier transport properties are required to generate high carrier levels and high output voltage. Hence, the core material, i.e., the absorption layer, should have an appropriate direct band gap and be effectively doped by both p-and n-types with minimal carrier traps and recombination centers. Consequently, defect properties of absorbers are critical in determining solar cell efficiency. In this work, we review recent first-principles studies of defect properties and engineering in four representative thin-film solar cells, namely CdTe, Cu(In,Ga)Se2, Cu2ZnSnS4, and halide perovskites. The focal points include basic electronic and defect properties, existing problems, and possible solutions in engineering defect properties of those materials to optimize solar cell efficiency.
