Structural,optoelectronic and thermoelectric properties of antiperovskite compounds Ae3PbS (Ae = Ca,Sr and Ba): A first principles study

In the last years, alkaline-earth based antiperovskite compounds with small semiconductor band gap have been proven to be promising candidate for optoelectronic and thermoelectric applications. In this work, the structural, electronic, optical and thermoelectric properties of Ae₃PbS (Ae = Ca, Sr and Ba) compounds have been predicted using first principles calculations based on the full-potential linearized augmented plane-wave (FP-LAPW) method and semiclassical Boltzmann transport theory. Exchange-correlation effect is treated with the generalized gradient approximation with Perdew–Burke–Ernzerhof scheme (GGA-PBE) and Tran–Blaha modified Becke–Johnson exchange potential. The lattice constant of considered materials increases as Ae goes in order from Ca to Ba and the hardness slightly decreases in this order. Ca₃PbS and Sr₃PbS are semiconductor with direct band gap of 0.199 eV and 0.116 eV, respectively, while Ba₃PbS is nearly metallic. Important optical responses of studied antiperovskites are found in the visible and ultraviolet energy range. Finally, the thermoelectric properties including Seebeck coefficient, electrical conductivity, thermal conductivity, power factor and figure of merit are calculated. Obtained results show that Ca₃PbS and Sr₃PbS could be candidate for applications in thermoelectric generators at low and moderate temperatures due to their high figure of merit values.     

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 study of the optical properties of PbFX (X = Cl,Br, I) compounds in its matlockite-type structure

We present the results of the ab initio theoretical study of the optical properties for PbFX (X = Cl, Br, I) compounds in its matlockite-type structure using the full potential linearized augmented plane wave (FP-LAPW) method as implemented in the WIEN2K code. We employed generalized gradient approximation (GGA), which is based on exchange-correlation energy optimization to calculate the total energy. Also we have used the Engel-Vosko GGA formalism, which optimizes the corresponding potential for band structure calculations. Our calculations show that the valence band maximum (VBM) and conduction band minimum (CBM) are located at Z resulting in a direct energy gap. We present calculations of the frequency-dependent complex dielectric function ε( ω) and its zero-frequency limit ε₁ ( 0 ). We find that the values of ε₁ ( 0 ) increases with decreasing the energy gap. The reflectivity spectra and absorption coefficient has been calculated and compared with the available experimental data. The optical properties are analyzed and the origin of some of the peaks in the spectra is discussed in terms of the calculated electronic structure.     

Contribution of carriers to optical conductivity spectra of lanthanum manganites

To study the band structure and carriers in lanthanum manganites, measurements have been made of the reflectance spectra of single crystals and polycrystals in the 0.04–1.6-eV range and of the optical conductivity σ _opt calculated by the Kramers-Kronig method as functions of the concentration and species of divalent ions in the paramagnetic (PM) and ferromagnetic (FM) regions. The optical gap for single-crystal La_0.9Sr_0.1MnO₃ is ∼0.17 eV, and the polaronband energy is 0.12 eV. In the PM region, σ _opt spectra do not indicate a band-carrier contribution, and conduction is dominated by polaron hopping and activation to the mobility edge. In the FM region, the variation in the σ _opt and absorption spectra of La_0.7Sr_0.3MnO₃ epitaxial films indicate the appearance of band carriers and a red shift of the absorption edge. The two band-carrier contributions, with weak and strong dependences on photon energy, are related to conduction in the antiferromagnetic matrix and the ferromagnetic regions. Fiz. Tverd. Tela (St. Petersburg) 41, 475–482 (March 1999)     

Structural,electronic, and optical properties of ZnO:ZnSnN2 compounds for optoelectronics and photocatalyst applications

Semiconductors with suitable band gap are highly desirable for the applications in optoelectronic and energy conversion devices. In this work, using the recently developed strongly constrained and appropriately normed (SCAN) density functional calculations in conjunction with hybrid functional, we investigate the structural, electronic, and optical properties of earth abundant element based ZnO:ZnSnN₂ compounds formed through alloying. The proposed ZnO:ZnSnN₂ compounds in the low energy configurations possess band gaps of 2.28 eV-2.52 eV. The decrease in band gap compared to ZnO is mainly attributed to the p-d repulsion between N 2p+O 2p and Zn 3d electrons that lifts the top of valence band. For the ZnO:ZnSnN₂ compounds studied the band edges straddle the water redox potentials and the absorption onsets lie in the visible light range. Our studies are helpful for ZnO:ZnSnN₂ compounds' experimental synthesis and future application in optoelectronics and photocatalyst.     

Structural,elastic, electronic,optical and thermoelectric properties of the Zintl-phase Ae3AlAs3 (Ae = Sr,Ba)

First-principles calculations were performed to investigate the structural, elastic, electronic, optical and thermoelectric properties of the Zintl-phase Ae₃AlAs₃ (Ae = Sr, Ba) using two complementary approaches based on density functional theory. The pseudopotential plane-wave method was used to explore the structural and elastic properties whereas the full-potential linearised augmented plane wave approach was used to study the structural, electronic, optical and thermoelectric properties. The calculated structural parameters are in good consistency with the corresponding measured ones. The single-crystal and polycrystalline elastic constants and related properties were examined in details. The electronic properties, including energy band dispersions, density of states and charge-carrier effective masses, were computed using Tran-Blaha modified Becke-Johnson functional for the exchange-correlation potential. It is found that both studied compounds are direct band gap semiconductors. Frequency-dependence of the linear optical functions were predicted for a wide photon energy range up to 15 eV. Charge carrier concentration and temperature dependences of the basic parameters of the thermoelectric properties were explored using the semi-classical Boltzmann transport model. Our calculations unveil that the studied compounds are characterised by a high thermopower for both carriers, especially the p-type conduction is more favourable.     

Mechanical stability and optoelectronic behavior of BeXP2 (X=Si and Ge) chalcopyrite

We have conducted a first-principles study on the structural, electronic, optical and elastic properties of BeSiP₂ and BeGeP₂ chalcopyrite compounds. Using the density functional theory (DFT), implemented in both full potential linear muffin-tin orbital (FP-LMTO) and Vienna Ab initio simulation (VASP) packages. The FP-LMTO is used for the determination of the structural, electronic and optical properties, while the VASP is used to determine the elastic constants that give indications about the material stability. The obtained equilibrium structural parameters are in good agreement with available results. An investigation of the band gap indicates that our compounds possess a semiconductor behavior with direct band gap for BeSiP₂ and with an indirect band gap for BeGeP₂. The energy band gaps decreased by changing Be atoms from Si to Ge. We have calculated the dielectric function ε(ω). The obtained results show that these materials are promising semiconductors for photovoltaic applications. For the elastic properties, the single-crystal elastic constants C_ij, shear anisotropic factors A, as well as polycrystalline bulk, shear and Young's modulus (B, G and E) and Poisson's ratio v have been predicted. The generalized elastic stability criteria for a tetragonal crystal are well satisfied, indicating that BeSiP₂ and BeGeP₂ are mechanically stable in the chalcopyrite structure.     

立方(Ba0.5Sr0.5)TiO3高压诱导带隙变化的第一性原理研究

采用基于密度泛函理论(DFT)的第一性原理计算研究了 (Ba_0.5Sr_0.5)TiO₃ (BST) 晶体在高压下的电子结构及能带变化行为. 研究结果发现,随着压强的增加,BST能带间隙先增加,在压强为55 GPa时达到最大值,然后减小,这些有趣的结果将有助于开发与设计新的BST铁电器件. 进一步地,通过电子态密度和密度分布图的研究分析可知:在低压区域(055 GPa),则是出现的离域现象占主导(电子的离域作用超过键态的作用),从而使带隙减小. 关键词： 钛酸锶钡 第一性原理 高压 能带间隙     

Optical,structural characterization and dielectric relaxation of [C2H5NH3]2ZnCl4 compound

ABSTRACT

The new organic-inorganic compound [C₂H₅NH₃]₂ZnCl₄ has been grown by the slow evaporation at room temperature. The zero-dimensional (0-D) structure for this compound was determined by the single X-ray diffraction. It crystallizes at room temperature in the non-centrosymmetric space group Pna2₁ and consists of ethylammonium cations [C₂H₅NH₃]⁺ and [ZnCl₄]^2? tetrahedra anions. That is interconnected by means of hydrogen bonding contacts N-H···Cl. The molecular geometry and vibrational frequencies of [ZnCl₄]^2? and [C₂H₅NH₃]⁺ in the ground state was calculated using density functional method (B3LYP) with 6–31G(d) and 6–311G (d,p) basis set. The optimized geometric bond lengths and bond angles, obtained by using B3LYP/6–311G (d,p), show the best agreement with the experimental data. The optical absorbance was measured in order to deduce the absorption coefficient α, optical band gap E_g. The optical band gap is determined by extrapolating the plotted graph of (αhυ)^1/2 vs. (hυ). The large value of indirect optical band gap energy indicates the insulating nature of this material. Moreover, the extinction coefficient, refractive index and the dielectric permittivity of [C₂H₅NH₃]₂ZnCl₄ compound were calculated and the results are discussed. The evolution of the dielectric loss as a function of frequency revealed a distribution of relaxation times, probably ascribed to the reorientational dynamics of alkyl chains in this compound, and then analyzed with the Cole–Cole formalism.     

Kramers-Kronig analysis of the reflectance spectra of Pb-doped Bi-4334 type glass and the corresponding glass-ceramic superconductor

The room temperature reflectance spectra in UV-VIS-NIR region (energy range of 0.6 to 6.2 eV) for glassy, partially crystalline and its fully crystalline superconducting ceramic phases of Bi_3.9Pb_0.1Sr₃Ca₃Cu₄O _x have been studied by Kramers-Kronig (KK) analysis. A comparative study of the energy loss function [− Im (1/ε)] and the absorption coefficient [α(E)] has been done. Excitions in the superconducting phase hitherto evidenced by the authors are located in the polarizable layers of the superconducting cuprate and their implications for superconductivity have been pointed out. An estimate of the optical band gap energy (E _g) has also been made from the linear fit ofα ² vs.E curve for the superconducting phase. Jezierski’s method ofR-extrapolations in the higher energy has been used to show that both methods yield results that agree quantitatively and can be relied upon.     

Ba0.5Sr0.5TiO3电子结构和光学性质的第一性原理研究

利用第一性原理研究了Ba_0.5Sr_0.5TiO₃的能带结构和光学性质.结果表明,导带和价带都来源于钛原子3d轨道和氧原子2p轨道的杂化.导带主要由钛原子的3d轨道贡献,价带主要由氧原子的2p轨道贡献.吸收系数为10⁵ cm^-1量级,且吸收主要集中在低能区.折射率为n（0）=2.1,结果与实验符合. 关键词： 第一性原理 能带结构 光学性质     

Structural,electronic and optical properties of Ca3Bi2: First-principles investigation

In this work by applying first principles calculations structural, electronic and optical properties of Ca₃Bi₂ compound in hexagonal and cubic phases are studied within the framework of the density functional theory using the full potential linearized augmented plane wave (FP-LAPW) approach. According to our study band gap for Ca₃Bi₂ in hexagonal phase are 0.47, 0.96 and 1?eV within the PBE-GGA, EV-GGA and mBJ-GGA, respectively. The corresponding values for cubic phase are 1.24, 2.08 and 2.14?eV, respectively. The effects of hydrostatic pressure on the behavior of the electronic properties such as band gap, valence bandwidths and anti-symmetry gap are investigated. It is found that the hydrostatic pressure increases the band widths of all bands below the Fermi energy while it decreases the band gap and the anti-symmetry gap. In our calculations, the dielectric tensor is derived within the random phase approximation (RPA). The first absorption peak in imaginary part of dielectric function for both phases is located in the energy range 2.0–2.5?eV which are beneficial to practical applications in optoelectronic devices in the visible spectral range. For instance, hexagonal phase of Ca₃Bi₂ with a band gap around 1?eV can be applied for photovoltaic application and cubic phase with a band gap of 2?eV can be used for water splitting application. Moreover, we found the optical spectra of hexagonal phase are anisotropic along E||x and E||z.     

Structural,elastic, electronic and optical properties of the cubic perovskites CaXO3 (X=Hf and Sn)

The structural, elastic, electronic and optical properties of CaXO₃ compounds with the cubic perovskites structure have been investigated, by employing a first principles method, using the plane wave pseudo potential calculations (PP-PW), based on the density functional theory (DFT), within the local density approximation (LDA). The elastic constants and their pressure dependence are calculated using the static finite strain technique. We derived the bulk, shear and Young’s moduli for ideal monocrystalline and for polycrystalline CaXO₃ aggregates which we have classified as ductile in nature. Band structures reveal that these compounds are indirect energy band gap (R-G) semiconductors; the analysis of the site and momentum projected densities, valence charge density bond length, bond population and Milliken charges, shows that bonding is of covalent–ionic nature. We have found that the elastic constants C₁₁, C₁₂, C₄₄ are in good correlation with the bonding properties. The optical constants, including the dielectric function, optical reflectivity, refractive index and electron energy loss, are calculated for radiation up to 20 eV.     

Laser-induced changes on optical band gap of amorphous and crystallized thin films of Se75S25−xAGx

Optical band gap of amorphous, crystallized, laser induced amorphous and laser induced crystallized films of Se₇₅S_25−xAg_x (x=4, 6 and 8) glassy alloys was studied from absorption spectra. The amorphous and crystallized films were induced by pulse laser for 10 min. After laser irradiation on amorphous and crystalline films, optical band gap was measured. It has been found that the mechanism of the optical absorption follows the rule of indirect transition. The amorphous thin films show an increase in the optical band gap, while the crystallized (thermally annealed) thin films show a decrease in the optical band gap by inducing laser irradiation. Crystallization and amorphization of chalcogenide films were accompanied with the change in the optical band gap. The change in optical energy gap could be determined by identification of the transformed phase. These results are interpreted in terms of concentration of localized states due to shift in Fermi level.     

The under-pressure behaviour of mechanical,electronic and optical properties of calcium titanate and its ground state thermoelectric response

Abstract

In this study, the elastic, electronic, optical and thermoelectric properties of CaTiO₃ perovskite oxide have been investigated using first-principles calculations. The generalised gradient approximation (GGA) has been employed for evaluating structural and elastic properties, while the modified Becke Johnson functional is used for studying the optical response of this compound. In addition to ground state physical properties, we also investigate the effects of pressure (0, 30, 60, 90 and 120 GPa) on the electronic structure of CaTiO₃. The application of pressure from 0 to 90 GPa shows that the indirect band gap (Γ-M) of CaTiO₃ increases with increasing pressure and at 120 GPa it spontaneously decreases transforming cubic CaTiO₃ to a direct (Γ-Γ) band gap material. The complex dielectric function and some optical parameters are also investigated under the application of pressures. All the calculated optical properties have been found to exhibit a shift to the higher energies with the increase of applied pressure suggesting potential optoelectronic device applications of CaTiO₃. The thermoelectric properties of CaTiO₃ have been computed at 0 GPa in terms of electrical conductivity, thermal conductivity and Seebeck coefficient.     

Optical,thermal and polaron energy levels in α-Al2O3

Calculations of the thermal band gap, ionisation energy and O(2p) valence band width are reported based on defect lattice methods. From these it is estimated that the large polaron is the preferred hole state in α-Al₂O₃ by about 0.4 eV. Theoretical values for the optical and thermal energy levels of Ti³⁺ in α-Al₂O₃ are also reported.     

Gigantic stimulated Raman scattering in one-dimensional Mott-Hubbard insulators: A possible THz source

One-dimensional Mott-Hubbard insulators like Sr₂CuO₃, halogen-bridged Nickel chain compounds have orders-of-magnitude nonlinear optical properties compared to other one-dimensional organic or inorganic compounds. We show theoretically, that the stimulated Raman scattering susceptibility for such insulators could be order(s)-of-magnitude larger even compared to other nonlinear optical susceptibilities. The lowest two-photon state is at lower energy than the lowest one-photon state in some of these insulators. This leads to a potential for strong Stokes generation in the THz regime from these compounds. Our results and conclusions are based on exact numerical solution of finite size two-band extended Hubbard model.     

Structural, electronic and optical properties of orthorhombic distorted perovskite TbMnO3

This paper calculates the structural parameters, electronic and optical properties of orthorhombic distorted perovskite-type TbMnO3 by first principles using density functional theory within the generalised gradient approximation. The calculated equilibrium lattice constants are in a reasonable agreement with theoretical and experimental data. The energy band structure, density of states and partial density of states of elements are obtained. Band structures show that TbMnO3 is an indirect band gap between the O 2p states and Mn 3d states, and the band gap is of 0.48 eV agreeing with experimental result. Furthermore, the optical properties, including the dielectric function, absorption coefficient, optical reflectivity, refractive index and energy loss spectrum are calculated and analysed, showing that the TbMnO3 is a promising dielectric material.     

Mechanical,electronic and optical properties of SeZnO3: a GGA+U study

ABSTRACT

Based on first principles computations, the structural, mechanical, electronic band structure, and optical properties of SeZnO₃ compound have been predicted. The dependence of selected observables of SeZnO₃ compound on the effective U (the Hubbard on-site Coulomb repulsion) parameter has been investigated in detail. The elastic constant, Young’s modulus, bulk modulus, shear modulus, Poisson ratio, anisotropic factor, acoustic velocity, and Debye temperature have been computed. The calculated electronic band structure and density of states indicate that SeZnO₃ is a semiconductor material and has indirect band gap. The computations of the optical spectra, as a function of the incident photon radiation in 0–35?eV energy range has also been performed and the interband transitions are examined. The results indicate that Hubbard parameter plays a crucial role in explaining mechanical, electronic, and optical properties of SeZnO₃.