Depth profile of the lattice constant of the Cu-poor surface layer in (Cu2Se)1−x(In2Se3)x evidenced by grazing incidence X-ray diffraction

The surface of CuInSe₂ or related compounds is an essential part of heterojunctions for photovoltaic applications. It is generally accepted that the reconstruction of the surface of slightly Cu-deficient film results in a Cu-depleted defect layer. Since this surface layer generally exhibits a CuIn₃Se₅ stoichiometry the existence of a defect chalcopyrite phase CuIn₃Se₅ has also been proposed. Although efforts have been made to identify this phase structurally by means of grazing incidence X-ray-diffraction (GIXRD), it has not been detected so far. However, the existence of a Cu-depleted surface layer fits well in the existing theory, which models the functioning of photovoltaic devices. In this contribution we present for the first time evidence for a Cu-depleted surface layer measured by X-ray diffraction. A careful analysis of GIXRD-data at incident angles from 0.3 to 10° by comparing the measured shape and width with simulated spectra confirms structural changes in the surface layer. The thickness of this layer varies from 5 to 60 nm with the integral Cu-content of the film. Hence GIXRD provides a unique means for non-destructive depth profiling.     

Optical properties of ternary ZnS x Se1−x polycrystalline thin films

Ternary ZnS_xSe_1–x polycrystalline thin films were prepared by evaporation in vacuum of 10^–5 Torr. The molecular fractionx varied in the region ox1. The optical constants (the refractive indexn, the absorption indexk, and the absorption coefficient) were determined in the wavelength range 300–1600nm. A plot representing ₂=f(hv) shows that the ZnS_xSe_1–x polycrystalline thin films of different compositions have two direct transitions corresponding to the energy gapsE andE+. The variation in eitherE orE+ withx indicates that this system belongs to the amalgamation type. Such variation follows a quadratic equation. The bowing parameter was found to be 0.456 eV, roughly equal to the calculated value 0.60 eV using the empirical pseudopotential method based on the virtual-crystal approximation, in which the disorder effect has not been taken into account.     

LDA’+DMFT investigation of electronic structure of K1 − x Fe2 − y Se2 superconductor

We investigate electronic structure of the new iron chalcogenide high temperature superconductor K_1?x Fe_2?y Se₂ (hole doped case with x = 0.24, y = 0.28) in the normal phase using the novel LDA’+DMFT computational approach. We show that this iron chalcogenide is more correlated in a sense of bandwidth renormalization (energy scale compression by factor about 5 in the interval ±1.5 eV), than typical iron pnictides (compression factor about 2), though the Coulomb interaction strength is almost the same in both families. Our results for spectral densities are in general agreement with recent ARPES data on this system. It is found that all Fe-3d(t _2g ) bands crossing the Fermi level have equal renormalization, in contrast to some previous interpretations. Electronic states at the Fermi level are of predominantly xy symmetry. Also we show that LDA’+DMFT results are in better agreement with experimental spectral function maps, than the results of conventional LDA+DMFT. Finally we make predictions for photoemission spectra lineshape for K_0.76Fe_1.72Se₂.     

Influence of Covalence on the Metal-Insulator Temperature in the CuIr 2 (S 1− x Se x ) 4 Spinels

Influence of the covalence on the metal-insulator (M-I) temperature in the CuIr 2 (S 1 m x Se x ) 4 spinel series is considered. For this purpose a vacancy model and the effective number of valence electrons per molecule are used. Calculations of the vacancy model parameters, i.e., the ion packing coefficients, the filling coefficient of the unit cell, the difference of the Pauling electronegativities and the vacancy parameter suggest that the covalence increases with increasing selenium concentration x , leading to a decrease of the metal-insulator temperature. It was observed that the metal-insulator temperature is related to the effective number of valence electrons per molecule, suggesting that with increasing covalence, less and less valence electrons take part in the metal-insulator transition. These effects are explained within the framework of the mixed valence of the iridium ions including structural defects.     

Helimagnetism of CuxZn1−xCr2Se4 (for 0.0 ≤ × ≤ 0.1)

Abstract

The magnetization, the susceptibility and the magnetic anisotropy field of Cu _x Zn_1?xCr₂Se₄ compounds have been studied at low temperatures (down to 2.9 K) in: high magnetic stationary fields (up to 14 T), high pulsed magnetic fields (up to 25 T), medium magnetic stationary fields (up to 0.6 T). The magnetic structure of these spinels was studied by neutron powder diffraction.

The magnetic properties of Cu_xZn_1?xCr₂Se₄ are explained in terms of the molecular field approximation assuming the existence of 90° exchange interactions, ferromagnetic for Cr-Se-Cr between the nearest Cr ions and antiferromagnetic for Cr-Se-Se-Cr between the second-nearest Cr ions. The exchange parameters and integrals for the whole series under consideration are calculated. Taking into account the three magnetic phase transitions observed in these spinels (Juszczyk, Krok, Okońska-Koz?owska, Broda, Warczewski, Byszewski, 1981) and the neutron diffraction studies a modification of the simple spin spiral forced by a strong magnetic field is described.     

Band gap tunable and improved microstructure characteristics of Cu2ZnSn(S1−x,Sex)4 thin films by annealing under atmosphere containing S and Se

Cu₂ZnSn(S_xS_1?x)₄ (CZTSSe) thin films were prepared by annealing a stacked precursor prepared on Mo coated glass substrates by the sputtering technique. The stacked precursor thin films were prepared from Cu, SnS₂, and ZnS targets at room temperature with stacking orders of Cu/SnS₂/ZnS. The stacked precursor thin films were annealed using a tubular two zone furnace system under a mixed N₂ (95%) + H₂S (5%) + Se vaporization atmosphere at 580 °C for 2 h. The effects of different Se vaporization temperature from 250 °C to 500 °C on the structural, morphological, chemical, and optical properties of the CZTSSe thin films were investigated. X-ray diffraction patterns, Raman spectroscopy, and X-ray photoelectron spectroscopy results showed that the annealed thin films had a single kesterite crystal structure without a secondary phase. The 2θ angle position for the peaks from the (112) plane in the annealed thin films decreased with increasing Se vaporization temperature. Energy dispersive X-ray results showed that the presence of Se in annealed thin films increased from 0 at% to 42.7 at% with increasing Se vaporization temperatures. UV–VIS spectroscopy results showed that the absorption coefficient of all the annealed thin films was over 10⁴ cm^?1 and that the optical band gap energy decreased from 1.5 eV to 1.05 eV with increasing Se vaporization temperature.     

电沉积Cu(In,Ga)Se_2预置层硫化退火制备Cu(In,Ga)(Se,S)_2薄膜及表征

在550℃下的H2S气氛中退火处理电沉积制备的Cu(In,Ga)Se2(CIGS)预置层,制备了太阳电池光吸收层Cu(In,Ga)(Se,S)2(CIGSS)薄膜.采用X射线能量色散谱、俄歇电子能谱、扫描电镜、X射线衍射和拉曼光谱对退火前后的薄膜进行表征.结果表明,H2S气氛下退火能够实现薄膜中O的去除和S的掺入,同时使得各元素的纵向分布更加均匀并可消除Cu-Se微相.此外,H2S退火还可改善薄膜的结晶性能,并使S和Ga进入黄铜矿结构,薄膜晶格参数变小.     

Low-temperature phase transitions and dynamics of ammonium in (NH4)3H(SO4)2 and [(NH4)1−x Rbx]3H(SO4)2 crystals

The (NH₄)₃H(SO₄)₂ and [(NH₄)_0.82Rb_0.18]₃H(SO₄)₂ crystals are investigated by dielectric spectroscopy, inelastic incoherent neutron scattering (IINS), and neutron powder diffraction. A comparative analysis of the data obtained is given. It is shown that the phase transitions II ? III, III ? IV, IV ? V, and V ? VII in the (NH₄)₃H(SO₄)₂ crystal are accompanied by changes in the orientation ordering of the NH ₄ ⁺ ions. In the [(NH₄)_0.82Rb_0.18]₃H(SO₄)₂ crystal, these phase transitions are completely suppressed and the long-range order inherent in the II phase is retained over the entire temperature range covered (6–300 K). It is revealed that this crystal at the temperature T _g≈70 K undergoes a transition to the dipole glass phase, which is attended by “freezing” the orientation disordering of the ammonium ions.     

衬底对Cu(In,Ga)Se2薄膜织构的影响

分别在苏打石灰玻璃、Mo箔、无择优取向的Mo薄膜以及(110)择优取向的Mo薄膜四种不同衬底上,采用共蒸发工艺沉积约2μm厚的Cu(In,Ga)Se2薄膜,用X射线衍射仪测量薄膜的织构,研究衬底对Cu(In,Ga)Se2薄膜织构的影响.在以上四种衬底上沉积的Cu(In,Ga)Se2薄膜的(112)衍射峰强度依次逐渐减弱,(220/204)衍射峰从无到有且强度逐渐增强.在苏打石灰玻璃和Mo箔衬底上的Cu(In,Ga)Se2薄膜具有明显的(112)择优生长,而在(110)取向的Mo薄膜衬底上,Cu(In,Ga)Se2薄膜的织构为(220/204)取向.研究结果表明,只有(110)择优取向的Mo薄膜衬底对Cu(In,Ga)Se2薄膜(220/204)织构的形成有重要影响.     

Thermodynamic properties of the ferromagnetic spinel ZnpCd1−pCr2Se4

The magnetic properties of the B-spinel ferromagnetic Zn_pCd_1−pCr₂Se₄ compound are studied via a cluster series expansion approximation with nearest and next-nearest exchange integrals J₁ and J₂, respectively. Using the minimization of the free-energy expressions, the magnetization, the magnetic susceptibility, the two-spin correlation functions and the specific heat are obtained and computed numerically as a function of temperature and for each composition of the system. The magnetization curves are used to determine the critical temperatures T_c. Using the power laws in the vicinity of the critical regions the critical exponents β, γ and α associated, respectively, with the magnetization, the magnetic susceptibility and the specific heat are numerically calculated. The critical temperatures T_c obtained are in very good agreement with those predicted by the magnetic measurements and the values of the critical exponents may be compared with other theoretical results based on the 3D Heisenberg model.     

Laser Raman spectra of mixed crystals of [(NH4)1−x Kx]2 SO4

The Raman spectra of mixed crystals of [(NH₄)_1?x K _x ]₂ SO₄ in the region 50–3400 cm^?1 at 293 K and below 223 K have been reported. At room temperature 293 K, as the concentration of K⁺ ion increases in the crystal up to 50%, the frequencies of the totally symmetric vibrations of SO ₄ ^2? and NH ₄ ⁺ ions increase and thereafter the frequency of SO ₄ ^2? vibration decreases and attains the value in K₂SO₄. This change in frequency up to 50% of potassium concentration is due to the breaking of hydrogen bonds of the type N-H...O. The behaviour of Raman intensities of A _g (v ₁) mode of SO ₄ ^2? for various concentrations (x=0, 0·03, 0·11, 0·5, 0·85) suggest that the phase transition changes from first order type to one of second order. The phase transition in mixed crystals of [(NH₄)_1?x K _x ]₂ SO₄ can be a cooperative phenomenon arising from a coupling between (NH₄)⁺ ions through hydrogen bonds with the distorted SO ₄ ^2? ions in the low temperature phase.     

Infrared Reflection Spectra of (FeIn2S4)x∙(In2S3)1–x Solid Solutions

Journal of Applied Spectroscopy - IR reflectance spectroscopy at 50–450 cm–1 was used to study homogeneous monocrystals of (FeIn2S3)x?(In2S3)1–x grown by the method of...     

Photovoltaic structures using AgSb(S x Se1−x )2 thin films as absorber

Photovoltaic structures were prepared using AgSb(S _x Se_1?x )₂ as absorber and CdS as window layer at various conditions via a hybrid technique of chemical bath deposition and thermal evaporation followed by heat treatments. Silver antimony sulfo selenide thin films [AgSb(S _x Se_1?x )₂] were prepared by heating multilayers of sequentially deposited Sb₂S₃/Ag dipped in Na₂SeSO₃ solution, glass/Sb₂S₃/Ag/Se. For this, Sb₂S₃ thin films were deposited from a chemical bath containing SbCl₃ and Na₂S₂O₃. Then, Ag thin films were thermally evaporated on glass/Sb₂S₃, followed by selenization by dipping in an acidic solution of Na₂SeSO₃. The duration of dipping was varied as 3, 4 and 5 h. Two different heat treatments, one at 350 °C for 20 min in vacuum followed by a post-heat treatment at 325 °C for 2 h in Ar, and the other at 350 °C for 1 h in Ar, were applied to the multilayers of different configurations. X-ray diffraction results showed the formation of AgSb(S _x Se_1?x )₂ thin films as the primary phase and AgSb(S,Se)₂ and Sb₂S₃ as secondary phases. Morphology and elemental detection were done by scanning electron microscopy and energy dispersive X-ray analysis. X-ray photoelectron spectroscopic studies showed the depthwise composition of the films. Optical properties were determined by UV–vis–IR transmittance and reflection spectral analysis. AgSb(S _x Se_1?x )₂ formed at different conditions was incorporated in PV structures glass/FTO/CdS/AgSb(S _x Se_1?x )₂/C/Ag. Chemically deposited post-annealed CdS thin films of various thicknesses were used as window layer. J–V characteristics of the cells were measured under dark and AM1.5 illumination. Analysis of the J–V characteristics resulted in the best solar cell parameters of V _oc = 520 mV, J _sc = 9.70 mA cm^?2, FF = 0.50 and η = 2.7 %.     

Birefringence of CuGa(S1−x Sex)2 single crystals

The magnitude and dispersion of birefringence of single crystals of CuGa(S_1?x Se_x)₂ solid solutions is studied in the spectral region of 0.5–2.5 μ at T=300 K. The effect of the substitution of selenium for sulfur on special features of birefringence dispersion is analyzed within the framework of the single-oscillator model.     

Preparation and superconductivity of (B1−xCx)(Sr1−yBay)2Ca2Cu3Oz

Preparation of (B_1−xC_x)(Sr_1−yBa_y)₂Ca₂Cu₃O_z has been studied using high-pressure synthesis technique to improve sample quality. Samples were prepared from various starting compositions of 0.2≤x≤0.8 and 0≤y≤1. Nearly single-phased samples were obtained for (B_0.6C_0.4)(Sr_1−yBa_y)₂Ca₂Cu₃O_z (0≤y≤0.75) and (B_1−xC_x)-(Sr_0.25Ba_0.75)₂Ca₂Cu₃O_z (0.3≤x≤0.6). We have found that the partial substitution of Ba is effective to improve the sample quality as well as to enhance the T_c. The C substitution was also demonstrated to affect the sample preparation and the physical properties. Based on the substitution study, a maximum T_c of 120 K was observed for the sample with a starting composition of (B_0.65C_0.35)(Sr_0.3Ba_0.7)₂Ca₂Cu₃O_9+δ. Critical current density (J_c) and irreversibility field (H_irr) were estimated from magnetization measurements. The J_c at 77 K in a field of 1 T was about 1.1×10⁴ A/cm³ and the H_irr at 77 K was about 2.5 T. The H_irr was well-described by H_irr=a(1−T/T_c)ⁿ with a=39.1 and n=2.38.     

Features of the plasma sputtering of polycrystalline Pb1 − x Sn x S films

The processes of the sputtering and modification of surfaces of polycrystalline films of the ternary solid solution Pb_{1 ? x} Sn _x S (x = 0.9–1.0) in a high-density Ar plasma of high-frequency low-pressure inductive discharge are studied. Films with thicknesses of 1–4 μm are grown on glass substrates using the “hot-wall” method and consist of plate-like crystallites. It is established that the sputtering rate for lead-tin sulfide films does not exceed 2.0 nm/s, which is determined by the presence of oxygen-containing compounds on the surfaces. In the case of plate-like crystallites with nanodimensional thicknesses, the effect of smoothing of the developed surfaces of the polycrystalline Pb_{1 ? x} Sn _x S layers during plasma treatment is observed; this is important for fabricating multilayer device structures.     

Doping dependence of correlation effects in K1 − x Fe2 − y Se2 superconductors: LDA’ + DMFT investigation

We present a detailed LDA’ + DMFT investigation of the doping dependence of correlation effects in the novel K_{1 ? x} Fe_{2 ? y} Se₂ superconductor. Calculations are performed at four different hole doping levels, starting from a hypothetical stoichiometric composition with the total number of electrons equal to 29 per unit cell through 28 and 27.2 electrons toward the case of 26.52, which corresponds to the chemical composition K_0.76Fe_1.72Se₂ studied in recent ARPES experiments. In the general case, the increase in hole doping leads to quasiparticle bands in a wide energy window ±2 eV around the Fermi level becoming more broadened by lifetime effects, while correlation-induced compression of Fe-3d LDA’ bandwidths stays almost the same, of the order of 1.3 for all hole concentrations. However, close to the Fermi level, the situation is more complicated. In the energy interval from ?1.0 eV to 0.4 eV, the bare Fe-3d LDA’ bands are compressed by significantly larger renormalization factors up to 5 with increased hole doping, while the value of Coulomb interaction remains the same. This fact manifests the increase in correlation effects with hole doping in the K_{1 ? x} Fe_{2 ? y} Se₂ system. Moreover, in contrast to typical pnictides, K_{1 ? x} Fe_{2 ? y} Se₂ does not have well-defined quasiparticle bands on the Fermi levels, but has a “pseudogap”-like dark region instead. We also find that with the growth of hole doping, Fe-3d orbitals of various symmetries are affected by correlations differently in different parts of the Brillouin zone. To illustrate this, we determine the quasiparticle mass renormalization factors and energy shifts that transform the bare Fe-3d LDA’ bands of various symmetries into LDA’ + DMFT quasiparticle bands. These renormalization factors effectively mimic more complicated energy-dependent self-energy effects and can be used to analyze the available ARPES data.