Electronic properties of chalcopyrite CuAlX2(X=S,Se,Te) compounds

We present results of the band structure and density of states for the chalcopyrite compounds CuAlX₂ (X=S,Se,Te) using the state-of-the-art full potential linear augmented plane wave (FP-LAPW) method. Our calculations show that these compounds are direct band gap semiconductors. The energy gap decreases when S is replaced by Se and Se replaced by Te in agreement with the experimental data. The values of our calculated energy gaps are closer to the experimental data than the previous calculations. The electronic structure of the upper valence band is dominated by the Cu-d and X-p interactions. The existence of Cu-d states in the upper valence band has significant effect on the optical band gap.     

First principles calculations of Cd and Zn chalcogenides with modified Becke–Johnson density potential

In this work, we present first principles calculations based on a full potential linear augmented plane-wave method (FP-LAPW) to calculate structural and electronic properties of CdX and ZnX (X = S, Se, Te) based II–VI chalcogenides. First principles calculations using the local density approximation (LDA) and the related generalized gradient approximation (GGA) lead to a severe underestimate of the band gap. The proposed model uses various exchange–correlation potentials (LSDA, GGA and MBJLDA) to determine band gaps and structural properties of semiconductors. We show that using modified Becke–Johnson (MBJLDA) density potential leads to a better agreement with experimental data for band gaps of Cd and Zn based semiconductors.     

氢化二维过渡金属硫化物的稳定性和电子特性:第一性原理研究

用氢对单层二维过渡金属硫化物(TMDs)进行功能化是调节单层TMDs电子性质的既有效又经济的方法.采用密度泛函理论,对单层TMDs (MX_2 (M=Mo, W; X=S, Se, Te))的稳定性和电子性质进行理论研究,发现在单层MX_2 的层间有一个比其表面更稳定的氢吸附位点.当同阳离子时,随着阴离子原子序数的增加, H原子与MX_2 层的结合越强,氢化单层MX_2 结构越稳定;相反,同阴离子时,随着阳离子原子序数的增加, H原子与MX_2 层的结合越弱.氢原子从MoS_2的表面经层间穿越到另一表面的扩散势垒约为0.9 eV.氢化对单层MX_2 的电子特性也会产生极大的影响,主要表现在氢化实现了MX_2 体系从无磁性到磁性体系的过渡.表面氢化会使MX_2 层的带隙急剧减小,而层间氢化使MX_2 的电子结构从半导体转变为金属能带.     

First-principles study of electronic and optical properties of BaS,BaSe and BaTe

The optimized crystal structure, energy band structures, density of states (DOS) and optical properties of BaX (X=S, Se and Te) were investigated by the full potential linearized augmented plane wave plus local orbitals method (FP-LAPW+lo). The exchange-correlation potential was treated using the generalized gradient approximation (GGA). We have used also Engel and Vosko GGA (EV-GGA) formalism to improve the band gap results. The calculated results such as band gaps, dielectric constants and reflectivity spectra showed good agreement with the experimental data. The effect of the spin-orbit coupling (SOC) on the optical properties was also studied and found to be very small, especially in the low-energy region.     

NiAs、PbO型FeX(X=S,Se,Te)结构的稳定性与电子特征

利用基于密度泛函理论的第一性原理方法,Ni As与Pb O型Fe X(X=S,Se,Te)结构的稳定性与电子特征得到了研究.计算结果显示Fe的内聚能与X-Fe元素之间的相互作用是影响Fe X结构稳定性的重要因素.当X原子半径较小、电负性较大时(X=S),Fe X趋向于形成Fe-X相互作用较强、密度较大的Ni As型结构;当X原子半径较大、电负性较小时(X=Se,Te),Fe X趋向于形成Fe-Fe相互作用较强、密度较小的Pb O型结构.此外,压强使得Pb O型Fe X结构的稳定性降低.当压强分别大于5、9 GPa时,Fe Te、Fe Se趋向于形成Ni As型结构.Pb O型Fe Se中Fe原子周围的电子密度随压强的增大而增大.     

纳米半导体中多重激子效应研究进展

多重激子效应是指纳米半导体吸收一个高能光子后产生两个甚至多个电子-空穴对的物理过程,不仅具有重要的基础研究意义,而且在新型太阳电池及高性能光电子器件领域具有潜在应用价值.综述了多重激子效应的发展历程;总结了纳米半导体的材料组分、体系结构甚至表面质量对多重激子效应的影响;介绍了多重激子效应的实验测试分析方法以及解释多重激子效应的理论方法;概括了目前多重激子效应在器件中的应用并对其应用前景进行展望.     

新型硫族化合物在中红外非线性光学晶体方面研究进展

利用红外非线性光学晶体材料对已有的成熟的激光光源进行频率转换是获得3~5μm和8~12μm"大气窗口"红外激光的主要方法。传统的红外非线性光学晶体存在缺陷,不能满足应用要求,需要探索新型的红外材料。综述了以硫族化合物为研究对象,寻找新型中红外非线性光学晶体材料的研究进展。介绍了Li MQ2(M=Ga,In;Q=S,Se,Te),BaGa4S7,BaGa4Se7,BaGa2MQ6(M=Si,Ge;Q=S,Se)及Li2In2MQ6(M=Si,Ge;Q=S,Se)的研究进展。     

Electronic structure patterns of isoelectronic compounds

X-ray photoelectron spectra of the valence levels of AO₄^x? anions (A = P, S, Cl, As, Se), AO₃^x? anions (A = S, Cl, I, Se, Te, Br) and AF₆^x? anions (A = Al, Si, As) have been studied. The spectra are interpreted and the electronic structures are considered for the isoelectronic and isovalent compounds.     

Band gap anomaly and topological properties in lead chalcogenides

Band gap anomaly is a well-known issue in lead chalcogenides Pb X(X = S, Se, Te, Po). Combining ab initio calculations and tight-binding(TB) method, we have studied the band evolution in Pb X, and found that the band gap anomaly in Pb Te is mainly related to the high on-site energy of Te 5s orbital and the large s–p hopping originated from the irregular extended distribution of Te 5s electrons. Furthermore, our calculations show that Pb Po is an indirect band gap(6.5 me V) semiconductor with band inversion at L point, which clearly indicates that Pb Po is a topological crystalline insulator(TCI). The calculated mirror Chern number and surface states double confirm this conclusion.     

Map of Two-Dimensional Tungsten Chalcogenide Compounds (W–S,W–Se,W–Te) Based on USPEX Evolutionary Search

JETP Letters - New two-dimensional nanostructures of W–X composition (X = S, Se, Te) are predicted using the evolutionary algorithm implemented in the USPEX software package. Based on the...     

Theoretical Prediction for Structural Stabilities and Optical Properties of SrS, SrSe and SrTe under High Pressure

An investigation on the structural stabilities and electronic properties of SrX （X =S, Se and Te） under high pressure is conducted using the first-principles calculation based on density functional theory （DFT） with the plane wave basis set as implemented in the CASTEP code. Our results demonstrate that the sequence of the pressure-induced phase transition of the three compounds is the NaCl-type （B1） structure （Fm3rn） to the CsC1- type （B2） structure （Pm3m）. The phase transition and the metallization pressures are determined theoretically. The pressure effect on the optical properties is discussed. The results are compared with the previous calculations and experimental data.     

A First-Principles Study of TiX2 (X = S,Se, and Te) Compounds Optical Properties under the Effect of Externally Applied Electric Field and Strain

Physics of the Solid State - Optical properties of titanium dichalcogenide compounds, TiX2 (X = S, Se, and Te) have been calculated by first-principles calculations using density functional theory...     

Electronic structure and structural phase stability of CuAlX2 (X=S, Se, Te) under pressure

The electronic and structural properties of chalcopyrite compounds CuAlX₂ (X=S, Se, Te) have been studied using the first principle self-consistent Tight Binding Linear Muffin-Tin Orbital (TBLMTO) method within the local density approximation. The present study deals with the ground state properties, structural phase transition, equations of state and pressure dependence of band gap of CuAlX₂ (S, Se, Te) compounds.Electronic structure and hence total energies of these compounds have been computed as a function of reduced volume. The calculated lattice parameters are in good agreement with the available experimental results. At high pressures, structural phase transition from bct structure (chalcopyrite) to cubic structure (rock salt) is observed. The pressure induced structural phase transitions for CuAlS₂, CuAlSe₂, and CuAlTe₂ are observed at 18.01, 14.4 and 8.29 GPa, respectively. Band structures at normal as well as for high-pressure phases have been calculated. The energy band gaps for the above compounds have been calculated as a function of pressure, which indicates the metallic character of these compounds at high-pressure fcc phase. There is a large downshift in band gaps due to hybridatization of the noble-metal d levels with p levels of the other atoms.     

CaAl2X2(X=C,Si,Ge)的稳定性、电子结构和力学性质研究

由于AB2X2类型的材料在储能、催化、超导、发光等领域都有着潜在应用价值,因此得到了广泛关注。本文通过第一原理方法计算分析了CaAl2X2(X=C,Si,Ge)的材料声子谱、电子结构、力学性质和硬度,其主要结果为：材料晶格常数的计算结果和实验值都与理论结构符合的很好;CaAl2C2和CaAl2Si2材料的声子谱没有出现虚频,表明这两种材料在热力学及动力学上是稳定的;计算的材料的能带结构表明,CaAl2Si2和 CaAl2Ge2具有金属特性, CaAl2C2具有较小带隙的间接半导体材料。这类材料的金属特性,热稳定性及力学各项异性特征对于其作为二次电池活性电极有着重要影响,因此本文的研究结果可为相关领域的研究提供较好的理论依据及参考。     

Magnetic and electronic properties of NiAs-type chromium chalcogenides

We have computed spin-dependent energy bands, spin moments and density of states of NiAs-type CrX (X=S, Se and Te) chalcogenides using linear combination of atomic orbitals method within density functional theory as well as full potential augmented plane wave method. In addition, magnetic properties have also been computed using spin polarized relativistic Korringa-Kohn-Rostoker method. We have also obtained the first ever theoretical electron momentum densities of CrX compounds considering linear combination of atomic orbitals and compared the results with the isotropic Compton profiles measured using 20 Ci ¹³⁷Cs Compton spectrometer. The Fermi surface topology and magnetic properties are discussed in terms of majority and minority energy bands and density of states. In addition, to highlight the role of Cr (3d) electrons in such type of chalcogenides, we have also reported the magnetic Compton profile of CrTe using the Korringa-Kohn-Rostoker method.     

Atomistic tight-binding computations of the structural and optical properties of CdTe/CdX (X=S and Se)/ZnS core/shell/shell nanocrystals

A study of CdTe/CdX (X=S and Se)/ZnS core/shell/shell nanocrystals is carried out using atomistic tight-binding theory and the configuration interaction method to provide information for applications in bioimaging, biolabeling, display devices and near-infrared electronic instruments. The calculations yield the dependences of the internal and external passivated shells on the natural behaviours of CdTe/CdX (X=S and Se)/ZnS core/shell/shell nanocrystals. The reduction of the optical band gaps is observed with increasing numbers of monolayers in the external ZnS shell due to quantum confinement. Interestingly, the optical band gaps of CdTe/CdS/ZnS core/shell/shell nanocrystals are greater than those of CdTe/CdSe/ZnS core/shell/shell nanocrystals. In the presence of an external ZnS-coated shell, electron–hole wave function overlaps, oscillation strengths, ground-state exchange energies and Stokes shift are improved, whereas ground-state coulomb energies and fine-structure splitting are reduced. The oscillation strengths, Stokes shift and fine-structure splitting are reduced with the increase in external ZnS shell thickness. The oscillation strengths, Stokes shift and fine-structure splitting of CdTe/CdS/ZnS core/shell/shell nanocrystals are larger than those of CdTe/CdSe/ZnS core/shell/shell nanocrystals. Reduction of the atomistic electron–hole interactions is observed with increasing external ZnS shell size. The strong electron–hole interactions are more probed in CdTe/CdS/ZnS core/shell/shell nanocrystals than in CdTe/CdSe/ZnS core/shell/shell nanocrystals.     

High pressure phase transition and elastic properties of thorium chalcogenides

The structural and elastic properties of thorium chalcogenides at high pressure, have been investigated using a suitable inter-ionic potential. The calculated equation of state, phase transition pressures for B1-B2 transition and bulk moduli for ThX (X=S,Se,Te) compounds agree well with the experimental results. ThTe, which crystallizes in the CsCl structure, does not show any structural transition up to 48 GPa. The present analysis does not show any anomalous features in elastic properties arising from ‘f’ electrons.     

Study of methyl chalcogen compounds with ultraviolet photoelectron spectroscopy

Dimethyl sulfide, dimethyl selenide, dimethyl telluride, dimethyl disulfide, dimethyl diselenide and dimethyl trisulfide have been studied by ultraviolet photoelectron spectroscopy. For the first time, the high resolution He(I) spectrum of dimethyl trisulfide is reported. However, the main thrust of this work is to examine trends among related compounds. We report the results of correlations of the first three ionization energies of (CH₃)₂X, X = O, S, Se, and Te and of the correlations of the first five ionization energies of (CH₃)₂X₂, X = O, S, and Se with the ionization energies of oxygen, sulfur, selenium, and tellurium. Where possible, orbital trends of isoelectronic molecules were also examined. Finally, we report the results of correlations of the FWHM of the first three bands of CH₃(S)_nCH₃ with the number of sulfur atoms and investigate convergence of the first two orbital bandwidths to the bandwidths of the two highest occupied bands in μ-sulfur.     

Uniaxial strain-modulated electronic structures of CdX (X = S,Se, Te) from first-principles calculations:A comparison between bulk and nanowires

Using first-principles calculations based on density functional theory, we systematically study the structural deformation and electronic properties of wurtzite CdX(X = S, Se, Te) bulk and nanowires(NWs) under uniaxial [0001] strain. Due to the intrinsic shrinking strain induced by surface contraction, large NWs with {10ˉ10} facets have heavy hole(HH)-like valence band maximum(VBM) states, while NWs with {11ˉ20} facets have crystal hole(CH)-like VBM states. The external uniaxial strain induces an HH–CH band crossing at a critical strain for both bulk and NWs, resulting in nonlinear variations in band gap and hole effective mass at VBM. Unlike the bulk phase, the critical strain of NWs highly depends on the character of the VBM state in the unstrained case, which is closely related to the size and facet of NWs. The critical strain of bulk is at compressive range, while the critical strain of NWs with HH-like and CH-like VBM appears at compressive and tensile strain, respectively. Due to the HH–CH band crossing, the charge distribution of the VBM state in NWs can also be tuned by the external uniaxial strain. Despite the complication of the VBM state, the electron effective mass at conduction band minimum(CBM) of NWs shows a linear relation with the CBM–HH energy difference, the same as the bulk material.     

Studies on the local structures and the spin Hamiltonian parameters for Fe3+ in CdX (X = S,Se, Te)

The improved perturbation formulas of the spin Hamiltonian parameters (zero-field splitting D and g factors) for a 3d⁵ ion in trigonally distorted tetrahedra are constructed from the cluster approach by including both the crystal-field and charge-transfer contributions. These formulas are applied to the studies of the local structures and the electron paramagnetic resonance (EPR) spectra for Fe³⁺ in CdX (X = S, Se, Te). The impurity Fe³⁺ is found not to occupy exactly the host Cd²⁺ sites but to experience the small outward shifts 0.014 and 0.006 Å away from the ligand triangles along the C₃ axis in CdS and CdSe, respectively. The charge-transfer contributions to the spin Hamiltonian parameters are important and increase significantly with increasing atomic number of the ligand (i.e., S^2? < Se^2? < Te^2?) arising from the decreases of charge-transfer energy levels and the increases of ligand spin–orbit coupling coefficients. The results are discussed.