Superconducting thin films of MxMo6S8 type

Thin films of M_xMo₆S₈, where M=Pb, Sn, Sn-Al and Cu, known as the Chevrel phases have been prepared by d.c. getter sputtering method and the optimal conditions of their preparation have been determined. The transition temperatures reached: 10.16, 13.66, 11.74 and 12.86 K for thin films with M=Cu, Sn, Sn-Al and Pb respectively. The highest critical fields H_c²(0) of 428 kG were obtained for Pb compounds.     

Synthesis of earth-abundant Cu2SnS3 powder using solid state reaction

Cu₂SnS₃ (CTS) powder has been synthesized at 200 °C by solid state reaction of pastes consisting of Cu and Sn salts and different sulphur compounds in air. The compositions of the products is elucidated from XRD and only thiourea is found to yield CTS without any unwanted CuS_x or SnS_y. Rietveld analysis of Cu₂SnS₃ is carried out to determine the structure parameters. XPS shows that Cu and Sn are in oxidation states +1 and +4, respectively. Morphology of powder as revealed by SEM shows the powder to be polycrystalline with porous structure. The band gap of CTS powder is found to be 1.1 eV from diffuse reflectance spectroscopy. Cu₂SnS₃ pellets are p-type with electrical conductivity of 10⁻² S/cm. The thermal degradation and metal–ligand coordination in CTS precursor are studied with TGA/DSC and FT-IR, respectively, and a probable mechanism of formation of CTS has been suggested.     

Cu(In,Sn)Se2 thin films for absorption of energy from infrared radiation

In this study, we sought to lower the bandgap of thin film solar cells by replacing the Ga used in the absorber layer of Cu(In,Ga)Se₂ with Sn (bandgap of 0.07?eV) to form Cu(In,Sn)Se₂. The proposed scheme was shown to reduce the bandgap of the absorber layer from 1.0?eV to 0.88?eV. Sn films of various thicknesses were deposited using precursors of Sn–In–Cu metal in order to study the effects of Sn/(In?+?Sn) ratio (SIR) on the structure of the material and photoelectrical characteristics of the Cu(In,Sn)Se₂ absorber layer. Experiment results revealed that a higher SIR following selenization increased the grain size and surface roughness of the absorber layer. It increased the quantity of secondary phases of SnSe₂ and Cu₂SnSe₃ and improved the distribution of Cu and In in the absorber layer. A higher SIR was also shown to increase electron mobility while decreasing carrier concentration and conductivity. When SIR≧0.25, the replacement of In³⁺ with Sn⁴⁺in the Cu⁺ vacancies decreased the electron strength of In. We speculate that an increase in SIR caused a relative increase in the quantity of Sn²⁺ compared to Sn⁴⁺, thereby increasing the electron strength of Sn and switching the absorber layer from a p-type to an n-type semiconductor.     

YBa2Cu3Oy中对Y位与Cu(Ⅰ)位取代导致的空穴浓度变化

本文研究Co对Cu(I)和Ca对Y作取代时,YBa₂Cu₃O_y系统中的空穴浓度、晶体结构和超导临界温度随掺杂量的变化关系及其起源。结果表明,上述取代对体系中的Cu-O平面上的空穴浓度P_sh都有重要影响,但其作用和方式是不同的。前一种取代主要是通过对空穴的复合和增强对空穴的局域化而使P_sh下降:后者则具有明显的退局域化作用,从而使得P_sh上升。当两种取代同时进行时,局域化作用不 关键词：     

Bi2Sr2CaCu2-xSnxO8+δ系列 超导体的XRD和XPS研究

实验研究了Bi₂Sr₂CaCu_2-xSn_xO_8+δ 的X射线衍射(XRD)和光电子能谱(XPS).实验发现随着掺杂(Sn)量的增加,晶格参数a 和c都有所变化,O1s和Cu2p芯能级谱也发生了变化.实验结果表明： 在低掺杂量时,Sn主要 呈二价态;而在高掺杂浓度时呈四价态;掺Sn对超导电性的影响与其他元素的掺杂不同.这 些实验结果支持化学环境在高温超导样品的电子结构中起着重要作用的结论. 关键词： Bi系超导体 掺杂 X射线衍射 光电子能谱     

Preparing Cu2ZnSnS4 films using the co-electro-deposition method with ionic liquids

Cu2ZnSnS4（CZTS） films are successfully prepared by co-electrodeposition in aqueous ionic solution and sulfurized in elemental sulfur vapor ambient at 400 C for 30 min using nitrogen as the protective gas.It is found that the CZTS film synthesized at Cu/（Zn＋Sn）=0.71 has a kesterite structure,a bandgap of about 1.51 eV,and an absorption coefficient of the order of 10 4 cm 1.This indicates that the co-electrodeposition method with aqueous ionic solution is a viable process for the growth of CZTS films for application in photovoltaic devices.     

深过冷Cu60Sn30Pb10偏晶合金的快速凝固

实现了大体积Cu₆₀Sn₃₀Pb₁₀偏晶合金的深过冷与快速凝固. 实验获得的最大过冷度为173 K(0.17T_L). 凝固组织发生了明显的宏观偏析,XRD分析表明,试样上部是由固溶体(Sn),(Pb)相和金属间化合物ε(Cu₃Sn)相组成的三相区,下部为富(Pb)相区. 在小过冷条件下,三相区中ε(Cu₃Sn)相的凝固组织为粗大的枝晶,随着过冷度的增大,ε(Cu₃Sn)相细化成层片状组织,且层片间距随过冷度的增大而减小,而(Sn),(Pb)两相始终以离异共晶的方式存在. 富(Pb)相区中分布有少量的ε(Cu₃Sn)枝晶,枝晶长度随过冷度的增大而增大,且在大过冷条件下发生碎断. (Sn)相在ε(Cu₃Sn)相表面形核、长大,其形态类似于包晶凝固组织. 关键词： 深过冷 快速凝固 偏晶合金 层片组织     

使用金属掺杂SnO2(110)作为表面催化剂的电催化CO2还原反应：通过调控Sn:O原子比例来控制产物

电催化CO₂还原反应可以产生HCOOH和CO,目前该反应是将可再生电力转化为化学能存储在燃料中的最有前景的方法之一. SnO₂作为将CO₂转换为HCOOH和CO的良好催化剂,其反应发生的晶面可以是不同的. 其中(110)面的SnO₂非常稳定,易于合成. 通过改变SnO₂(110)的Sn:O原子比例,得到了两种典型的SnO₂薄膜：完全氧化型(符合化学计量)和部分还原型. 本文研究了不同金属(Fe、Co、Ni、Cu、Ru、Rh、Pd、Ag、Os、Ir、Pt和Au)掺杂的SnO₂(110),发现在CO₂还原反应中这些材料的催化活性和选择性是不同的. 所有这些变化都可以通过调控(110)表面中Sn:O原子的比例来控制. 结果表明,化学计量型和部分还原型Cu/Ag掺杂的SnO₂(110)对CO₂还原反应具有不同的选择性. 具体而言,化学计量型的Cu/Ag掺杂的SnO₂(110)倾向于产生CO(g),而部分还原型的表面倾向于产生HCOOH(g). 此外,本文还考虑了CO₂还原的竞争析氢反应. 其中Ru、Rh、Pd、Os、Ir和Pt掺杂的SnO₂(110)催化剂对析氢反应具有较高的活性,其他催化剂对CO₂还原反应具有良好的催化作用.     

The crystal structure of SnYb3Rh4Sn12, a new ternary superconducting stannide

The crystal structure of superconducting SnYb₃Rh₄Sn₁₂ has been determined from single-crystal X-ray diffraction data. This compound is cubic, space group Pm3n, $\text{a}{}_{\mathrm{o}}\text{= 9.676}\text{A}\text{?}$ (1) and has two formulae per unit cell. The structure was solved from Patterson and subsequent Fourier synthesis. The least squares refinement was based on 375 independent reflections. The final R and wR factors were 0.015 and 0.014, respectively. The two Sn(1) atoms occupy the 2a (000) positions, the six Yb atoms the 6d ($\text{1}\text{4}$$\text{1}\text{2}$ 0) positions, the eight Rh atoms the 8e ($\text{1}\text{4}$$\text{1}\text{4}$$\text{1}\text{4}$) positions and the twenty-four Sn(2) atoms the 24k (Oyz) positions (y ～ 0.31, z ～ 0.15). The Sn(2) atoms form a tridimensional array of corner-sharing trigonal prisms whose centers are occupied by the rhodium atoms. The Sn(1) and the Yb atoms occupy the icosahedral and cuboctahedral holes of this array, respectively. They form a sublattice which has the arrangement found in the structure of the A15 compounds. The structure of SnYb₃Rh₄Sn₁₂ can be described as containing two interpenetrated structures, namely Yb₃Sn and RhSn₃, or as having an A15 arrangement of clusters of atoms such as (SnSn₁₂) and (YbSn₁₂). These clusters are bound together by face-sharing among them; and by the rhodium atoms. An analogy is drawn between SnYb₃Rh₄Sn₁₂ and the perovskite-like ternary oxides A′A″₃B₄O₁₂.     

Magnetic order in palladium-based Heusler alloys Part I: Pd2MnIn1−xSnx and Pd2MnSn1−xSbx

Magnetization, susceptibility, X-ray and neutron diffraction measurements have been made on the two series of alloys Pd₂MnIn_1?xSn_x and Pd₂MnSn_1?xSb_x, for 0 ? x ? 1. All were single phase and were chemically ordered intermetallic compounds with the Heusler L2₁ structure in which the Mn atoms occupy an f.c.c. sub-lattice. At all compositions the alloys were magnetically ordered with a moment of ～4.3 μ_B located at the Mn sites. At the In-rich end the magnetic order is antiferromagnetic f.c.c. type 2. As Sn is increasingly substituted for In there is a change in magnetic order first to antiferromagnetic f.c.c. type 3A and then to ferromagnetism. All the alloys in the Sn/Sb series are ferromagnetic and in both series there is an increase in the ferromagnetic exchange interactions with increasing electron concentration.     

Elastic, electronic, and optical properties of hypothetical SnNNi3 and CuNNi3 in comparison with superconducting ZnNNi3

The elastic, electronic, and optical properties of MNNi₃ (M=Zn, Sn, and Cu) have been calculated using the plane-wave ultrasoft pseudopotential technique, which is based on the first-principle density functional theory (DFT) with generalized gradient approximation (GGA). The optimized lattice parameters, independent elastic constants (C₁₁, C₁₂, and C₄₄), bulk modulus B, compressibility K, shear modulus G, and Poisson's ratio υ, as well as the band structures, total and atom projected densities of states and finally the optical properties of MNNi₃ have been evaluated and discussed. The electronic band structures of the two hypothetical compounds show metallic behavior just like the superconducting ZnNNi₃. Using band structures, the origin of features that appear in different optical properties of all the three compounds has been discussed. The large reflectivity of the predicted compounds in the low energy region might be useful in good candidate materials for coating to avoid solar heating.     

Effect of substitution elements on magnetization of monodispersed MFe2O4 particles

The monodispersed hydrophilic magnetic fluids with nanometric M_xFe_3−xO₄ (M = Cu, Co, Ca and Ni) particles were prepared by sonochemical method. The substituted M amounts were analyzed with different x values by ICP-AES quantitatively. The excellent substitutability and magnetic property for Co, Ni was observed compared to those for Cu and Ca relatively. In particular, the applicability of Co was confirmed for novel radiotherapy.     

Gd替代YBa2Cu3O7－δ超导体的相结构与局域电子结构的研究

利用正电子湮没实验，结合x射线衍射(XRD)结构分析，研究了具有混合稀土特征的(Y_{1 -x}Gd_x)Ba₂Cu₃O_7-δ系列样品. XRD 实验结果表明，半径较大的Gd离子Y位替代使得样品晶胞参数和晶胞体积增大，但所有样品 仍保持与YBa₂Cu₃O_7-δ(YBCO)样品相同的单相正交结 构. 正电子湮没实验表明，正电子各寿命参数表现出很强的Gd替代依赖关系. 从正电子实验 结果出发，计算了Cu-O链区局域电子密度n_e的变化. 结果表明，局域电子密度n _e随Gd含量x的增加而减小，而超导转变温度T_c随局域电子密度ne的减小而增加，这种局域电子密度n_e与超导电性的关联是与铜位替代 完全不同的，且可能是近年来人们关于混合稀土铜氧化物体系具有较高临界电流密度的原因 之一. 该研究结果为铜氧化物超导体的应用和机理研究提供了相应的正电子实验资料. 关键词： 超导电性 正电子湮没 相结构 局域电子密度     

Exchange interaction and spin dynamics in pentanuclear clusters, Cu3Ln2(ClCH2COO)12(H2O)8 (Ln = Nd3+, Sm3+, Pr3+)

New compounds, [Cu₃Ln₂(ClCH₂COO)₁₂(H₂O)₈]·2H₂O with Ln = Nd³⁺ (I), Sm³⁺ (II), Pr³⁺ (III), built up of pentanuclear clusters were synthesized and studied by means of X-ray analysis and electron paramagnetic resonance (EPR). X-ray data show that all compounds are isostructural and the pentanuclear clusteres may be considered as a linear system with alternating Cu(II) and Ln(III) ions: Cu(2)-L¹-Ln-L²-Cu(1)-L²-Ln-L²-Cu(2) with L¹ and L² being bridging fragments and Cu(1) and Cu(2) being structurally nonequivalent copper complexes. EPR studies demonstrate that in the temperature range of 100–293 K the signals due to only one type of the copper complexes are observed in the spectra of I–III. AtT<100 K the spectral temperature dependence is nontrivial. AtT<30 K new signals are detected in the spectra of I and II. The temperature dependence of the EPR spectra is interpreted under the assumption that the parameter of the exchange interaction Cu(2)-Ln considerably exceeds the parameter of the interaction Cu(1)-Ln. EPR spectra are calculated for the fragments of five paramagnetic centers in the frames of the model taking into account the nonequivalence of two copper complexes, short longitudinal and transverse paramagnetic relaxation times of the rare-earth ions at room temperature and the change of the relaxation rates when the temperature decreases. The results of the calculations show that it is possible to obtain information about the interactions in the system on the basis of the analysis of the temperature dependence of the EPR spectra of the central copper complex. The parameter of the isotropic part of the exchange interaction between copper and neodymium ions (for the interaction Cu(2)-Nd) is estimated as about 15 cm⁻¹. A considerable rearrangement of the spin states when the temperature changes is found for all complexes.     

在工频外磁场下高温超导体的交流损耗

在工频外磁场条件下,研究了不同工艺的Bi-2223/Ag带和Cu位元素替代的YBa₂Cu_3-xSn_xO_y超导体的交流损耗.实验结果表明：在单芯Bi-2223/Ag带中,热处理时间、温度及超导芯厚度的增加都将增加Bi-2223相的含量,因而导致磁滞损耗增加.将单芯带细分成19芯Bi-2223/Ag带能减少磁滞损耗,但另一方面,超导芯间的耦合增加了银基体的涡流损耗,因此19芯带的损耗只比单芯带减少20%左右.在YBa关键词：     

Nonmagnetic impurities induced magnetism in SnO2

A density functional study is performed to investigate the magnetism induced by the nonmagnetic impurity substitution for the cation in SnO₂. The calculated results show that the K impurity substitution leads to a robust magnetism in SnO₂, and the induced magnetic moments are mainly attributed to the first shell of oxygen atoms surrounding the impurity atom. Meanwhile, no magnetism is observed in SnO₂ doped with Ca which implies a decreasing tendency of induced magnetic moments for Sn substituted by vacancy, K, and Ca. It is also demonstrated that the magnetic coupling constant oscillates as a function of K-K separation distance, and the Curie temperature above room temperature can be obtained in K-doped SnO₂.     

First-principle study of extrinsic defects in CuScO2 and CuYO2

Using first-principles methods, we studied the extrinsic defects doping in transparent conducting oxides CuMO₂ (MSc, Y). We chose Be, Mg, Ca, Si, Ge, Sn as extrinsic defects to substitute for M and Cu atoms. By systematically calculating the impurity formation energy and transition energy level, we find that BeCu is the most prominent extrinsic donor and CaM is the prominent extrinsic acceptor. In addition, we find that Mg atom substituting for Sc is the most prominent extrinsic acceptor in CuScO₂. Our calculation results are expected to be a guide for preparing n-type and p-type materials through extrinsic doping in CuMO₂ (MSc,Y).     

Magnetic measurements on Heusler alloys Ni2(Ti,Mn)Sn and Co2(Ti,Mn)Sn

Magnetic measurements (temperature and field dependence) on Heusler alloys Ni₂(Ti, Mn)Sn and Co₂(Ti, Mn)Sn were performed in the ferro- and para-magnetic region. In both systems the composition range was from x = 0 to x = 1. All the Co₂(Ti, Mn)Sn samples are ferromagnetic; in the system Ni₂Ti_1?xMn_xSn for x ? 0.2. Our interpretation of the magnetic data differs from that of previous authors.     

The effect of Cu substitution on the A1g mode of La0.7Sr0.3MnO3 manganites

We report on the first Raman data of Cu substituted La_1−ySr_yMn_1−xCu_xO₃ (0≤x≤0.10 and 0.17≤y≤0.3, accordingly in order to have the same Mn⁴⁺/[Mn⁴⁺+Mn³⁺] ratio), collected in the frequency range 100-900 cm⁻¹ and at room temperature, with parallel (e_i∥e_s) and crossed (e_i⊥e_s) polarizations of the incident (e_i) and scattered (e_s) light. Spectra were fitted with a Drude-Lorentz model, and peaks at 190-220 and 430 cm⁻¹, together with two broad structures centered at near 500 and 670 cm⁻¹, have been found. We also have observed that the A_1g mode is substantially shifted with increasing Cu substitution. The A_1g phonon shift is a linear function of the tolerance factor t and the rhombohedral angle α_r, thus following the structural changes of the MnO₆ octahedra in the system.     

Optical constants of Cu(In0.7Ga0.3)5Se8 and Cu(In0.4Ga0.6)5Se8 crystals

Variable angle spectroscopic ellipsometry has been applied to characterize the optical constants of bulk Cu(In_0.7Ga_0.3)₅Se₈ and Cu(In_0.4Ga_0.6)₅Se₈ crystals grown by the Bridgman method. The spectra were measured at room temperature over the energy range 0.8-4.4 eV. Adachi’s model was used to calculate the dielectric functions as well as the spectral dependence of complex refractive index, absorption coefficient, and normal-incidence reflectivity. The calculated data are in good agreement with the experimental ones over the entire range of photon energies. The parameters such as strength, threshold energy, and broadening, corresponding to the E₀, E_1A, and E_1B interband transitions, have been determined using the simulated annealing algorithm.