Electrical properties and electronic structure of Cu1−xZnxInSe2 and Cu1−xZnxInS2 single crystals

Temperature dependence of the electrical conductivity of CuInS₂–ZnIn₂S₄ and CuInSe₂–ZnIn₂Se₄ solid solutions possessing n-type conductivity has been studied. It has been established that when the temperature decreases down to ~100 to 27 K, the hopping mechanism of electrical conductivity with a variable jumping length between localized states positioned in a narrow energy band near the Fermi level becomes dominant. The main parameters of the hopping conductivity have been determined. At higher temperatures (150–300 K), in the CuInSe₂–ZnIn₂Se₄ single crystals containing 15 and 20 mol% ZnIn₂Se₄ the thermally activated conductivity with activation energy of 0.018 and 0.04 eV, respectively, is detected. Among the CuInSe₂–ZnIn₂Se₄ single crystals, samples with 5 and 10 mol% ZnIn₂Se₄ were found to be close to degenerate semiconductors. Temperature dependences of the electrical conductivity of CuInS₂–ZnIn₂S₄ single crystals are described by a more complicated function that may indicate a competition of several conduction mechanisms in these compounds. For the CuInS₂–ZnIn₂S₄ solid solutions, X-ray photoelectron core-level and valence-band spectra have been measured for both pristine and Ar⁺ ion-bombarded surfaces. Our results indicate that the Cu_1−xZn_xInS₂ single-crystal surfaces are sensitive to Ar⁺ ion-bombardment. Additionally, for the Cu_1−xZn_xInS₂ crystal with the highest ZnIn₂S₄ content, namely 12 mol% ZnIn₂S₄, the X-ray emission bands representing the energy distribution of the Cu 3d, Zn 3d and S 3p states have been measured and compared on a common energy scale with the X-ray photoelectron valence-band spectrum.     

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.     

Mössbauer study of Cu1−xZnxFe2O4 catalytic materials

In the present work, we have synthesized and characterized magnetic nanoparticles of maghemite γ-Fe₂O₃ to study their structural and magnetic properties. For the preparation, magnetite precursor, were oxidized by adjusting the pH = 3.5 at about 80 °C in an acid medium, The mean size of the maghemite particles calculated from the X-ray diffractogram was around 5.7 nm. Mössbauer spectroscopy measurements at room temperature show their superparamagnetic behavior. Furhermore, Mössbauer measurements were carried out at 77 K and 4.2 K in order to find the typical hyperfine fields of the maghemite. Magnetite phase was not found. FC and ZFC magnetization curves measured at 500 Oe indicate a blocking temperature of 105.3 K. The magnetization measurements also show almost zero coercivity at RT. TEM images show nanoparticles with diameter smaller than 10 nm, which are in good agreement with the X-ray pattern and the fitting of the magnetization data.     

Tunneling conductance of a Bi2−xPbxSr2Ca2Cu3O10−y-SnO2 junction

Fine structures were observed in the tunneling conductance of a sintered Bi 2223-SnO₂ junction. The structures are weaker than those of a single crystalline Bi2212. They correspond to the Raman spectrum of Bi2223 and approximately to the phonon density of states of Bi2212. The structures must therefore be phonon structures, and phonons may contribute substantially to highT _c superconductivity. Multiphonon structures are scarcely discernible. Hence we propose a new model, in place of the prior multiphonon model, to explain the rapid increase inT _c with the CuO₂ layer number. 2 (21 K)=68±4 meV inT _c=98±5 K. 2 (0)/k _B T _c is 8.1±0.9. The temperature dependence of the gap was also observed and discussed.     

Seebeck-effect in the mixed state of Y−Ba−Cu−O

We report on measurements of the Seebeck-effect, the Nernst-effect, and the magnetoresistance in the mixed state of ac-axis oriented expitaxial film of Y–Ba–Cu–O. In contrast to conventional superconductors we find a large Seebeck-coefficientS, which is comparable in magnitude to the Nernst-effect. The broadening of the super-conducting transitions of magnetoresistance and Seebeck-effect are rather similar with respect to (1) the temperature dependence, (2) the dependence on the direction between magnetic field and crystal axis and (3) the dependence on the direction between magnetic field and driving forces. The large Seebeck-effect has to be attributed to dissipation due to normal quasiparticle-excitations, since the vortex-contribution to the Seebeck-effect is by far too small to account for the observed magnitude ofS. It is argued that such a quasiparticle contribution to the dissipation is large in the high-T _c superconductors because of the small coherence lengths and thus the small vortex cores. Another possibility is that granularity leads to dissipation proportional to the normal state transport properties. The Seebeck-voltage depends on all dissipative processes other than vortex motion, whereas the Nernst-effect depends only on the vortex motion. Therefore by measurements of thermomagnetic effects the various dissipative properties may be separated.     

A Mössbauer study of YBa2(Cu1−x)Fex3O7−σ

⁵⁷Fe Mössbauer spectra of a sample of YBa₂(Cu_0.985Fe_0.015)₃O_7−σ for which T_c≈59 K show that long-range magnetic order is established below ∼ K. A model in which the Fe spins are aligned with the crystallographic c-axis provides satisfactory agreement with the observed relaxation spectra. This result is discussed with reference to current theoretical models of high-T_c superconductivity which involve magnetic coupling mechanisms.     

Preparation and properties of Y1−xHoxBa2Cu3O7−δ thin films by TFA-MOD method

Y_1?xHo_xBa₂Cu₃O_7?δ (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) thin films were prepared on LaAlO₃ (0 0 1) substrates by trifluoroacetate metal organic deposition (TFA-MOD) without change of the processing parameters. The highest J_c was attributed to the sample of Y_0.6Ho_0.4Ba₂Cu₃O_7?δ thin film, whose critical current density is about 1.6 times as compared to that of YBa₂Cu₃O_7?δ thin film at 77 K and self field. The flux pinning type was not varied with Ho substitution and can be attributed to δl pinning model, which is attributed to the close ionic radius between the Y³⁺ and Ho³⁺ ions. The improvement of J_c by Ho substitution without change of the processing parameters will provide an effective route to enhance the J_c of YBCO-based thin films using TFA-MOD method.     

Thermoelectric properties of Cr1−xMoxSi2

The thermoelectric properties of Mo-substituted CrSi₂ were studied. Dense polycrystalline samples of Mo-substituted hexagonal C40 phase Cr_1−xMo_xSi₂ (x=0–0.30) were fabricated by arc melting followed by spark plasma sintering. Mo substitution substantially increases the carrier concentration. The lattice thermal conductivity of CrSi₂ at room temperature was reduced from 9.0 to 4.5 W m⁻¹ K⁻¹ by Mo substitution due to enhanced phonon–impurity scattering. The thermoelectric figure of merit, ZT, increases with increasing Mo content because of the reduced lattice thermal conductivity. The maximum ZT value obtained in the present study was 0.23 at 800 K, which was observed for the sample with x=0.30. This value is significantly greater than that of undoped CrSi₂ (ZT=0.13).     

Infrared spectra of superconducting La2−xSrxCuO4 and YBa2Cu3O7−δ

Abstract

Abstract Infrared spectra of La_2?xSr_xCuO₄ and YBa₂Cu₃O_7?δ are discussed, specially with respect to the disappearance of the high-frequency (～650 cm) band of the superconducting compositions at 300K. Some of the bands persist at 300K eventhough the materials are fairly conducting. YBa₂Cu₃O_7?δ does not show evidence in the far IR spectrum for the presence of an optical gap.     

Magnetic properties of Nd3+ in Nd−Ba−Cu−O-compounds

Neutron diffraction, neutron spectroscopy and magnetization measurements have been employed to study the structural, electronic, and magnetic behavior of eleven compounds with the general formula Nd_1+y Ca _v Ba_2–y–v Cu₃O _x (0y0.5; 0v0.25; 6x7). The structure turned out to react to oxygen reduction similar as other 123-compounds, yielding discontinuities close to the metal-insulator-transition and the well-known relations of bond lengths as a function ofT _c. The crystalline electric field (CEF) interaction, splitting the 10-fold degenerate ground-state J-multiplet of the Nd³⁺-ions into five doublet states, was investigated by neutron spectroscopy. The derived CEF parameters have been used to determine changes in the electronic surroundings of the Nd³⁺ ions. In addition, with the help of the CEF parameters the thermodynamic magnetic properties of these compounds were calculated which turn out to be in good agreement with the experimental data.     

Local electronic structure of Cu2O,CuO and YBa2Cu3O7−δ

Cu 3d and O 2p electronic states of Cu₂O, CuO, and the highT _c compound YBa₂Cu₃O_7– have been probed by means of high resolution x-ray emission spectroscopy (XES). The CuL and OK XES bands are compared in detail with recently reported x-ray photoelectron and ultraviolet photoelectron spectroscopy (XPS and UPS) measurements and densities of states obtained by local density functional (LDF) theory. The XES data show that the hybridization between Cu 3d and O 2p states is completely modified in CuO and YBa₂Cu₃O_7–, whered-d correlation energy is large, as compared to LDF predictions. Such is not the case for Cu₂O where agreement between theory and experiment is good.The Cu 3d states are found to be highly localized in YBa₂Cu₃O_7– (though less so than in CuO). The O 2p states lie at lower binding energies than in the simpler oxides and are mainly situated above the Cu 3d states. The respective positions of the centre of gravity of the OK emission bands on an x-ray energy scale indicate that the oxygen sites are less well screened by the O 2p states in the highT _c compound. This provides indirect evidence for the presence ofd-like states at the oxygen sites.     

Normal state resistivity of YBa2Cu3O7−x

A systematic study has been carried out on the normal state resistivity of YBa₂Cu₃O_7–x . Samples were cut from the same well-annealed material and were quenched from different temperatures (T _Q ). The resistivity is metallic whenT _Q 500 °C and becomes semiconductor-like whenT _Q 600 °C. The data on the latter was interpreted in terms of the three-dimensional localization model proposed by Mott.The work at USCD was supported by the California MICRO program     

Magnetic properties of superconducting EuBa2Cu3O7−x

The magnetic properties of superconducting EuBa₂Cu₃O_7–x with resistiveT _c 96.5 K are measured. The normal state magnetic susceptibility is analyzed within the framework of the Van Vleck-Frank theory, leading to the conclusion that the strong moments of the Eu³⁺ ions are uncorrelated, and do not affect the superconducting state.     

Growth of Cu0.5Tl0.5Ba2Ca3Cu4−yZnyO12−δ superconductor with optimum carriers

We have tried to vary the carriers concentration in Cu_0.5Tl_0.5Ba₂Ca₃Cu_4?yZn_yO_12?δ (y = 0, 1, 1.5, 2, 2.5) superconductor with the help of post-annealing experiments carried out in nitrogen, oxygen and air and to investigate its effects on the superconductivity parameters. The zero resistivity critical temperature [T_c(R = 0)], the magnitude of diamagnetism and critical current [I_c(H = 0)] are found to increase in Zn free samples after post-annealing in oxygen and air, while these superconducting properties have been suppressed after post-annealing in nitrogen at 550 °C for 6 h. The post-annealing of Zn-doped samples in air has marginally increased the superconducting properties, while these properties have been suppressed after post-annealing in nitrogen and oxygen. These studies have led us to the definite conclusion that the Zn-doped material has grown with optimum carriers concentration.     

Hall effect of noncrystalline Zr−Cu films

Quench condensed Zr _x Cu_1–x films offer a wide concentration range (0.1x0.9) for measurements of the Hall coefficientR _H of amorphous Zr–Cu alloys.R _H changes sign as a function of composition, from negative to positive, as the Zr concentration is increased. The sign change is observed in a narrow concentration range at aboutx=0.22, without any peculiarity of the conductivity at this crossover concentration. The Hall coefficient of the unannealed Zr-rich films is nearly independent of temperature. However, both, the values ofR _H and of the temperature dependence ofR _H change with a heat treatment well below the crystallization temperature. This is most obvious for the films with a composition close to the cross-over concentration.Dedicated to B. Mühlschlegel on the occasion of his 60th birthday     

Optical Properties of Films of Cu x Ag1−x InSe2 Solid Solutions Obtained by Laser Evaporation

The structure and optical properties of the films of ternary compounds AgInSe₂, CuInSe₂ and Cu _x Ag_1–x InSe₂ solid solutions obtained by pulsed laser evaporation are investigated. It has been established that the films like bulk crystals have the structure of chalcopyrite. By the transmission and reflection spectra near the edge of natural absorption the refractive index and coefficient of optical absorption are calculated and the energies of interband transitions and the crystalline and spinorbit splitting are determined.     

Optical properties of Li1−xNb1−xEu2xO3 solid solutions

Abstract

The effects of europium substitution on crystalline solubility, structural changes and optical properties of LiNbO₃ is reported. Li_1?xNb_1?xEu_2xO₃ solid solutions exist over a very limited range of europium concentrations (x ≤ 0.01). The solid solutions were characterized by X-ray powder diffraction and density measurements. Within the range of compositions of the solid solutions, the optical properties (emission and excitation spectra) of the Eu³⁺ ions have been characterized. The obtained optical data indicate that two equally abundant europium luminescent species exist in the stoichiometric speciments; these correspond to the Eu³⁺ ions occupying the Li⁺ and Nb⁵⁺ sites, in agreement with the replacement mechanism which is inferred from density measurements. Other Eu³⁺ luminescent species which appear to be closely related with lithium deficiency were found to exist in nonstoichiometric samples, in addition to those which are present in the stoichiometric materials.     

Effect of K-doping to the weak link behaviour of (Cu0.5Tl0.5−xKx)Ba2Ca2Cu3O10−δ superconductors

A systematic study of the weak link behaviour for (Cu_0.5Tl_0.5?xK_x)Ba₂Ca₂Cu₃O_10?δ (x = 0, 0.25) superconductors samples has been carried out using electrical resistivity and AC-susceptibility techniques. The K-doped (Cu_0.5Tl_0.5?xK_x)Ba₂Ca₂Cu₃O_10?δ samples were synthesized by solid-state reaction method. In magnetic susceptibility measurements, the real (χ′) and imaginary (χ″) parts of the magnetic susceptibility of (Cu_0.5Tl_0.5?xK_x)Ba₂Ca₂Cu₃O_10?δ (x = 0, 0.25) samples were measured as a function of temperature under various DC-magnetic fields up to 172 Oe. It is observed from these studies that the magnitude of the diamagnetism is substantially enhanced by K-doping. The possible reasons for the enhanced magnitude of diamagnetism have been investigated. It is observed from in-field magnetic measurements that the inter-grain coupling is improved with the K-doping. It is concluded from these studies that potassium atoms appearing at the crystal boundaries enhance inter-grain coupling and pinning mechanism in K-doped (Cu_0.5Tl_0.25K_0.25)Ba₂Ca₂Cu₃O_10?δ superconductors.