Structural and luminescence characteristics of CuAlxIn1−xSe2 (0 < x ≤ 0.30) chalcopyrite solid solutions

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Synthesis,crystal structure,and electronic structure of Li2PbSiS4: a quaternary thiosilicate with a compressed chalcopyrite‐like structure

The new quaternary thiosilicate, Li₂PbSiS₄ (dilithium lead silicon tetrasulfide), was prepared in an evacuated fused‐silica tube via high‐temperature, solid‐state synthesis at 800 °C, followed by slow cooling. The crystal structure was solved and refined using single‐crystal X‐ray diffraction data. By strict definition, the title compound crystallizes in the stannite structure type; however, this type of structure can also be described as a compressed chalcopyrite‐like structure. The Li⁺ cation lies on a crystallographic fourfold rotoinversion axis, while the Pb²⁺ and Si⁴⁺ cations reside at the intersection of the fourfold rotoinversion axis with a twofold axis and a mirror plane. The Li⁺ and Si⁴⁺ cations in this structure are tetrahedrally coordinated, while the larger Pb²⁺ cation adopts a distorted eight‐coordinate dodecahedral coordination. These units join together via corner‐ and edge‐sharing to create a dense, three‐dimensional structure. Powder X‐ray diffraction indicates that the title compound is the major phase of the reaction product. Electronic structure calculations, performed using the full potential linearized augmented plane wave method within density functional theory (DFT), indicate that Li₂PbSiS₄ is a semiconductor with an indirect bandgap of 2.22 eV, which compares well with the measured optical bandgap of 2.51 eV. The noncentrosymmetric crystal structure and relatively wide bandgap designate this compound to be of interest for IR nonlinear optics.     

Mn掺杂后三元黄铜矿结构半导体CuInTe2的缺陷特征与热电性能

三元黄铜矿结构(也称类金刚石结构)半导体是一类具有热电转换潜力的新型热电材料. 本次工作中采用电负性更小的Mn元素替换CuInTe₂黄铜矿结构半导体中的Cu元素, 设计制备贫Cu化合物Cu_1-xInMn_xTe₂. 研究表明, 当Mn含量较低时, Mn优先占位在In 位置产生受主缺陷Mn_In^-. 因此随着Mn含量的增大, 载流子浓度和电导率均得到改善. 但当Mn含量进一步增大后, Mn可同时占位在In位置和Cu位置, 除产生受主缺陷Mn_In^-外, 还能产生施主缺陷Mn_Cu⁺. 由于两类极性相反的缺陷之间的湮灭现象, 使得缺陷浓度及载流子浓度开始降低, 晶格结构畸变有变小趋势, 因此在高温下晶格热导率仅略有提高. 研究结果表明, 在某一特定的Mn含量(x=0.05)时, 材料具有最优的热电性能(ZT=0.84@810.0 K), 这一性能约是未掺杂CuInTe₂的2倍.     

A convenient synthesis of nanocrystalline chalcopyrite,CuFeS2 using single‐source precursors

Nanocrystalline chalcopyrite (CuFeS₂) have been synthesized using single‐source precursors, CuL₂ and Cu(LH)₂Cl₂ (where LH = monoacetylferrocene thiosemicarbazone) by pyrolysis and solvothermal decomposition methods. The nanocrystals were characterized by UV–visible spectroscopy, X‐ray powder diffraction, transmission electron microscopy and energy dispersive X‐ray analysis. The magnetic character was determined by the hysteresis loop. CuFeS₂ nanocrystallites prepared by the pyrolysis of CuL₂ and Cu(LH)₂Cl₂ have a cubic phase and rod‐like morphology with diameters of about 18 and 15 nm, respectively, and lengths of about 195–390 and 100–145 nm, respectively. However, CuFeS₂ nanoparticles obtained by solvothermal route from CuL₂ and Cu(LH)₂Cl₂, which are capped with ethylene glycol, possess a nearly spherical shape with an average grain size of 16 and 11 nm, respectively. Copyright © 2009 John Wiley & Sons, Ltd.     

Structural and Electronic Properties Study of Colombian Aurifer Soils by Mössbauer Spectroscopy and X-ray Diffraction

In this work a study on gold mineral samples is reported, using optical microscopy, X-ray diffraction (XRD) and Mössbauer spectroscopy (MS). The auriferous samples are from the El Diamante mine, located in Guachavez-Nariño (Colombia) and were prepared by means of polished thin sections. The petrography analysis registered the presence, in different percentages that depend on the sample, of pyrite, quartz, arsenopyirite, sphalerite, chalcopyrite and galena. The XRD analysis confirmed these findings through the calculated cell parameters. One typical Rietveld analysis showed the following weight percent of phases: 85.0% quartz, 14.5% pyrite and 0.5% sphalerite. In this sample, MS demonstrated the presence of two types of pyrite whose hyperfine parameters are δ ₁ = 0.280 ± 0.002 mm/s and Δ ₁ = 0.642 ± 0.002 mm/s, δ ₂ = 0.379 ± 0.002 mm/s and Δ ₂ = 0.613 ± 0.002 mm/s.     

Electronic and structural properties of A Al2Se4 (A=Ag, Cu, Cd, Zn) chalcopyrite semiconductors

We have studied the structural and electronic properties of defect chalcopyrite semiconductors A Al₂Se₄ (A=Ag, Cu, Cd, Zn) using density functional theory (DFT) based first principle technique within tight binding linear muffin-tin orbital (TB-LMTO) method. Our calculated structural parameters such as lattice constants a and c, tetragonal distortion (η=c/2a) are in good agreement with experimental work. Anion displacement parameters, bond lengths and bulk modulus are also calculated. Our band structure calculation suggests that these compounds are direct band gap semiconductors having band gaps 2.40, 2.50, 2.46 and 2.82 eV for A Al₂Se₄ (A=Ag, Cu, Cd, Zn) respectively. Calculated band gaps are in good agreement with other experimental and theoretical works within LDA limitation. We have made a quantitative estimation of the effect of p-d hybridization and structural distortion on the electronic properties. The reduction in band gap due to p-d hybridization is 19.47%, 21.29%, 0% and 0.7% for A Al₂Se₄ (A=Ag, Cu, Cd, Zn) respectively. Increment of the band gap due to structural distortion is 11.62%, 2.45%, 2.92% and 9.30% in case of AgAl₂Se₄, CuAl₂Se₄, CdAl₂Se₄ and ZnAl₂Se₄ respectively. We have also discussed the bond nature of all four compounds.     

The effect of temperature on the photoluminescence ofp-CuGaSe2 single crystals

We studied the temperature dependences of spectral bands and of the outer quantum yield of the edge photoluminescence (PhL) of p-CuGaSe₂ single crystals obtained by the method of chemical transport reactions. We determined the activation energies of acceptor levels and showed that the temperature dependence of the intensity of PhL is determined by an acceptor level of 35 meV below the Debye temperature and of 150 meV above the Debye temperature. The spectra of the edge PhL at 300 and 80 K are determined mainly by band-band optical transitions. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 4, pp. 590–593, July–August, 1998.     

Electrical and photo-electrical properties of a chalcopyrite semiconductor AgInSe2

In this paper we report the electrical and photoelectrical properties of AgInSe₂. Nyquist plots for AgInSe₂, obtained at different temperatures, are perfect arcs of a semicircle with their centres lying below the abscissa at an angleα. Finite values ofα (the distribution parameter) clearly indicate a multirelaxation behaviour. Transient and steady state photoconductivity of AgInSe₂ has been studied at different temperatures and illumination levels. The lnI _ph vs lnF curves at different temperatures follow the empirical relation:I _ph ∝F ^γ. Values of γ are close to 0.5 at all the temperatures, suggesting a bimolecular recombination. Decay of the photocurrent, when the illumination is switched off, shows that during decay, photocurrent has two components, i.e. a fast decay in the beginning and a slow decay thereafter. Decay time constant for slow decay process decreases with increasing temperature, suggesting that recombination is a thermally activated process in the temperature range studied.     

Synthesis,structure, optical,and electric properties of Ce-doped CuInTe_2 compound

Ce-doped Cu In Te2（CICT） semiconducting compounds are successfully synthesized. The phase structures, optical,and electric properties are investigated using powder X-ray diffraction（XRD）, field emission scanning electron microscopy（FESEM）, X-ray photoelectron spectrometer（XPS）, Raman spectrometer, ultraviolet and visible spectrophotometer（UVVis）, and a standard four-probe method. Cu In1-xCex Te2 crystallizes into a tetragonal structure with predominant orientation along the [112] direction. The lattice parameters are a = 6.190（6） A–6.193（0） A and c = 12.406（5） A–12.409（5） A. Ce prefers to occupy the 4b crystal position. According to the analysis of XPS spectra, Ce shows the mixture of valences 4＋and 3＋. Raman spectra reveal that the photon vibrating model in the CICT follows A1 mode in a wavenumber range of123 cm^-1–128 cm^-1. UV-Vis spectra show that the band gap Eg values before and after 0.1 mole Ce doped into Cu In Te2 are 1.28 e V and 1.16 e V, respectively. It might be due to the mixture of valences for Ce. Ce doped into Cu In Te2 still shows the semiconductor characteristics.     

直流三极溅射法制备CuInS2 薄膜

采用直流三极溅射装置制备获得了CuInS₂薄膜, 其中溅射靶采用一定面积比的[Cu]/[In]混合靶,反应气体采用CS₂气体. 本文中主要研究了0.02 Pa分压反应气体条件下不同面积比的[Cu]/[In]混合靶和沉积基板温度对CuInS₂薄膜结构和成分的影响, 其中CuInS₂薄膜制备所用时间为2 h生长的厚度为1—2 μm. 通过对CuInS₂薄膜的EPMA, X射线衍射测试分析表明, 最佳的CuInS₂薄膜可在面积比[Cu]/[In]混合靶为1.4:1和可控温度(150, 250和350 ℃)的条件下制备获得, 并且其结构被确认为黄铜矿结构. 通过实验结果计算出CuInS₂薄膜层有约为8.9%的C杂质含量.