Growth and Accurate Characterization of Bi2Sr2?xLaxCuO6+δ Single Crystals

High-quality and various doped Bi₂Sr_2−x La _x CuO_6+δ (x=0–0.90) single crystals were obtained by floating-zone method. Analysis of the thermal behavior indicated an incongruent melt for all the doped compounds. The segregation coefficient of La related to Sr was estimated to be ∼1.02. Chemical compositions including the La doping in the crystals were accurately determined to study the effect of doping on the structural, chemical and superconducting property of the compounds. Raman spectra were performed to show the high-frequency modes 627 cm⁻¹ softened with increasing the doping level of La. Implications of the doping effect on crystals for understanding the superconductivity are discussed.     

Characterization of epitaxial Bi2Sr2CaCu2O8+δ thin films

We report a dc sputtering method for the fullin situ preparation of Bi₂Sr₂CaCu₂O₈₊ thin films on SrTiO₃ and LaAlO₃.T _c values of more than 90 K can be achieved by oxidizing annealing below the melting point, followed by a reducing anneal at 500°C. The structural properties of the films are revealed by X-ray diffraction in Bragg-Brentano geometry (strongc-axis orientation with FWHM (0 0 10)=0.3) and also by scans (epitaxy within the substrate plane). Rutherford backscattering and channeling confirmed the correct composition of the cations while the minimum yield, _min, is 23%. Depth profiles by SNMS show a very homogeneous distribution of the cations with no detectable loss of bismuth near the surface. The surface morphology of the films was studied by SEM and by STM. Patterning of the films in lateral geometry can be performed by photolithographic techniques without degradation ofT _c .     

Anomaly in the Complex Conductivity of Overdoped Y1?xCaxBa2Cu3O7?δ Thin Films from THz Spectroscopy

We measured the complex conductivity of Ca-doped YBCO thin films in the THz frequency range. The films were measured using both Time domain and Frequency domain methods for THz spectroscopy. We show that a subgap exists in the overdoped samples of 5% and 10% Ca doping. The subgap appears as a sharp decrease in the real part of conductivity at frequencies equivalent to gap energy of 1 meV and is more prominent with increased doping. We suggest that this decrease in conductivity is related to a d_x²-y²d_{x^{2}-y^{2}}-wave pairing symmetry with an imaginary part of is or id _xy . The imaginary part of the conductivity shows the well-known 1/ω behavior, but its ωσ ₂ product shows a dip in the spectrum at about ∼1 meV.     

Phase Separation in La2CuO4+δ by electrical transport measurements

The dc conductivity and the high-frequency capacitance of a La₂CuO₄₊ single crystal are determined by impedance spectroscopy in the frequency range 20 Hz to 1 MHz at liquid helium temperature. Using isochronal annealing, the effect of the phase separation on these quantitites is studied for E parallel and perpendicular to the CuO₂ planes as well as for different oxygen doping levels,, of the sample. The results are consistent with the model of a diffusion-controlled formation of a metallic—and belowT _c superconducting—percolation network in an insulating background.     

Growth of untwinned Bi2Sr2Can?1CunO2n+4+δ thin films on Nd : YAlO3 substrates

Thin film growth of Bi₂Sr₂Ca _n–1Cu _n O_2n+4+ by molecular beam epitaxy is performed on Nd : YAlO₃ (001) substrates. It was revealed that the orthorhombicity of the Nd:YAlO₃ substrate is quite effective to the growth of untwinned Bi₂Sr₂Ca _n–1Cu _n O_2n+4+ thin films. In all phases withn=13, the incommensurate structural modulation lies parallel to the Nd : YAlO₃ [100] direction, and this relation holds even in the case of superlattices. The origin of the epitaxial relation is discussed from the viewpoint of the lattice misfit. The orthorhombicity of the substrate competes with the step edges on a vicinally polished substrate for determining the in-plane growth direction. The rotation of the modulation direction was observed when the off angles are varied.     

Room-temperature oxidation of La2?xSrxCuO4

A series of oxidized La_2–x Sr _x CuO_4+y compounds has been prepared by treating the starting materials with a solution of Br₂ in NaOH at room temperature. The structural modifications due to the oxidation of the materials have been studied by X-ray diffraction. Some of the observed changes are: (i) a large increase in the long parameter of the unit cell for samples with Sr content and (ii) a slight decrease in a along the whole range ofx. Interesting features have been observed regarding the critical temperatures of these materials: transition temperatures are higher for those containing lower Sr amounts (some of them were even nonsuperconducting before the oxidation treatment) in contrast to materials with x0.15, whoseT _c's do not change very much. The influence of both oxygen and strontium contents on the structural modifications and the superconducting properties of the oxidized materials will be discussed.     

Magnetic penetration depth of Tl2Ba2CuO6+δ:Tc～σ0 in the overdoped region

We report transverse-field muon-spin-rotation experiments carried out on Tl₂Ba₂CuO₆₊ . This system spans the whole overdoped regime, andT _c is reduced by excess oxygen doping, which increases the normal-state carrier concentration. In the heavily overdoped regime(0) is found to scale linearly with the superconducting critical temperatureT _c , similar to the behavior previously observed for other cuprates in the underdoped regime. However, for the overdoped region one has to explain the reduction of ₀, thus the increase of the magnetic penetration depth, in spite of an increasing normal-state carrier concentration. We discuss some possible explanations for this behavior.     

Experimental determination of the spatial distribution of electron defects in La2 ? xSrxCuO4 and Nd2 ? xCexCuO4 crystal lattices

The data of M?ssbauer emission spectroscopy on ⁶⁷Cu(⁶⁷Zn) and ⁶⁷Ga(⁶⁷Zn) isotopes show that holes appearing as a result of the Sr²⁺ substitution for La³⁺ in the La_{2 − x} Sr _x CuO₄ crystal lattice are localized predominantly at oxygen atoms occurring in the same atomic plane as the copper atoms. In contrast, electrons appearing as a result of the Ce⁴⁺ substitution for Nd³⁺ in the Nd_{2 − x} Ce _x CuO₄ crystal lattice are localized in the copper sublattice. These results are consistent with the model assuming that a mechanism responsible for the high-temperature superconductivity in La_{2 − x} Sr _x CuO₄ and Nd_{2 − x} Ce _x CuO₄ crystal lattices is based on the interaction of electrons with two-site two-electron centers possessing negative correlation energies (negative-U centers).     

Normal-state Conduction Mechanisms in GdBa2Cu3?xRuxO7?δ Superconducting Phase

Bulk superconducting samples of type GdBa₂Cu_3−x Ru _x O_7−δ , Gd-123, with x=0.0–0.3 were prepared by the conventional solid-state reaction technique. X-ray powder diffraction (XRD), scanning electron microscope (SEM), electron dispersive X-ray (EDX) and electrical-resistivity measurements were performed in order to investigate the effect of Ru⁴⁺ ions substitution on Gd-123 phase. Enhancement of both phase formation and the superconducting transition temperature T _c for GdBa₂Cu_3−x Ru _x O_7−δ phase up to x=0.05 was observed from XRD and electrical-resistivity measurement, respectively. This enhancement was confirmed with the calculated relative volume fraction. For x>0.05, suppression of both phase formation and T _c was obtained and the superconductivity was completely destroyed around x=0.3. The normal-state electrical resistivity was analyzed by the two- and three-dimensional variable range hopping (2D-VRH and 3D-VRH) and Coulomb gap CG. The results showed that the dominant mechanism was CG for x≤0.075, while was 3D-VRH for x≥0.15.     

Magnetic order and evolution of the electronic state aroundx=0.12 in La2?xBaxCuO4 and La2?xSrxCuO4

Muon spin rotation ( ⁺SR) measurement provides clear evidence of the antiferromagnetic order of Cu moments below 35 K for La_2–x Ba _x CuO₄ and below 15 K for La_2–x Sr _x CuO₄ in the narrow range ofx where the high-T _c superconductivity (SC) is suppressed remarkably. The results suggest that the change of the electronic state coupled with the lattice instability is relevant to the local suppression of SC and freezing of spin fluctuations of the Cu moment.     

Thermoelectric Power of Deoxygenated Bi1.6Pb0.4Sr2Ca2Cu3O10 + δ Sintered Superconducting Pellets

The thermal variation of the electrical resistivity and thermoelectric power of Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_{10 +} pellets subjected to various degrees of deoxygenation is reported. The temperature dependence of the electrical resistivities of deoxygenated samples displays gradual transformation from metallic-like to semiconductor-like features in the normal state. All the samples however, show superconducting transition, but increasing deoxygenation depresses T _C0 from 102 to 45 K. Gross features of the temperature variation of thermoelectric power observed in properly oxygenated (Bi, Pb)-2223 cuprates are retained in all the deoxygenated samples. Our results on electrical resistivity and thermoelectric power in the normal state have been found to be consistent with a two-band model.     

Synthesis and Structure of Hg1?xCrxSr2CuO4+δ Mercurocuprates

We report preliminary results concerning the synthesis and structural characterisation of the chromium stabilised 1201 phases: Hg_1–xCr_xSr₂CuO₄₊. A systematic study of the formation of phases in this system has been undertaken, together with a combined powder neutron and synchrotron x-ray diffraction study, to address the issue of chromium clustering and ordering in this system.     

Investigation of the quasi-ternary system LaMnO3–LaCoO3–“LaCuO3”. II: The series LaMn0.25?xCo0.75?xCu2xO3?δ and LaMn0.75?xCo0.25?xCu2xO3?δ

This paper investigates the crystal structure, thermal expansion, and electrical conductivity of two series of perovskites (LaMn_0.25−x Co_0.75−x Cu_2x O_3−δ and LaMn_0.75−x Co_0.25−x Cu_2x O_3−δ with x = 0, 0.025, 0.05, 0.1, 0.15, 0.2, and 0.25) in the quasi-ternary system LaMnO₃–LaCoO₃–“LaCuO₃”. The Mn/Co ratio was found to have a stronger influence on these properties than the Cu content. In comparison to the Co-rich series (LaMn_0.25−x Co_0.75−x Cu_2x O_3−δ), the Mn-rich series (LaMn_0.75−x Co_0.25−x Cu_2x O_3−δ) showed a much higher Cu solubility. All compositions in this series were single-phase materials after calcination at 1100 °C. The Co-rich series showed higher thermal expansion coefficients (α_max = 19.6 × 10⁻⁶ K⁻¹) and electrical conductivity (σ_max = 730 S/cm at 800 °C) than the Mn-rich series (α_max = 10.6 × 10⁻⁶ K⁻¹, σ_max = 94 S/cm at 800 °C). Irregularities in the thermal expansion curves indicated phase transitions at 150–350 °C for the Mn-rich series, while partial melting occurred at 980–1000 °C for the Co-rich series with x > 0.15. I. Arul Raj—on leave from Central Electrochemical Research Institute, Karaikudi, 630006 India.     

The Effect of Silver Substitution in Bi1.7Pb0.3Sr2Ca2?xAgxCu3Oy

The effect of Ag substitution on the properties of high-temperature superconductor Bi_1.7Pb_0.3Sr₂Ca_2−x Ag _x Cu₃O _y system have been investigated. The electrical and structural properties of the samples, prepared by the conventional solid-state reaction method, have been characterized by X-ray diffraction (XRD), electrical resistance and scanning electron microscopy (SEM) studies. XRD analysis reveals a multiphase structure of the samples, whereas SEM micrographs indicate some morphological changes induced by silver addition. It was found that an increase of the amount of Ag₂O addition leads to an enhancement of the critical temperature and the percentage of Bi-2223 phase in the phase mixture.     

A Study of the Magnetic Properties of?Bi1.64?xPb0.36CdxSr2Ca2Cu3Oy Superconductor

The flux pinning energy and magnetic properties of Bi_1.64−x Pb_0.36Cd _x Sr₂Ca₂Cu₃O _y (BPCSCCO) with x=0.0, 0.02, 0.04 and 0.06 were studied. A series of Bi-2223 superconductor samples with a nominal composition of BPCSCCO was synthesized and the effect of Cd substitution for Bi was investigated. As a result, Cd addition has been found to improve the superconducting properties of the Bi-Pb-Sr-Ca-Cu-O system. The effects of the annealing time and the amount of Cd doping on the structure, AC magnetic susceptibility, ρ–T curves and flux pinning energy were investigated. Also, for all samples the relation between the current and voltage in the mixed state was found to follow the model relationship V=α I ^β . The maximum value of β is 22.30, which is obtained for the sample with an annealing time of 270 h and a Cd content of 0.04.     

Normal state and superconductivity of ErBa2(Cu1?xCrx)O7?δ(x=0–0.1)

The effects of Cr in ErBa₂(Cu_1–x Cr _x )O_7– (x=0–0.1) superconductor have been investigated. The critical temperature, which was determined by DC electrical resistance measurements, showed no suppression of the onset temperature (T _{c onset}) within the substitution range. The transition width (T _c ) broadened as the Cr content is increased. The normal state changes from the metal-like to semimetal/semiconductor-like for x0.03. Micrographs from the scanning electron microscope, X-ray diffraction pattern, and energy dispersive X-ray analysis results are used to describe the superconducting properties of these materials. The orthorhombic structure was preserved throughout the substitution range. Some possible roles of Cr in the system are discussed.     

Extraordinary behaviour of the Y1?xPrxBa2Cu3O7?δ system

Investigations of Y_1–x M _x Ba₂Cu₃O_7– (M=Ce, Th)c-axis oriented thin film specimens show that the rate of depression ofT _c withx is larger for M=Th, than for M=Ce and Pr, and suggest that Ce, like Th, is tetravalent in this compound. Hall effect measurements on Y_1–x Pr _x Ba₂Cu₃O_7– single crystals reveal aT ² dependence of the cotangent of the Hall angle in the normal state and a negative Hall anomaly belowT _c in the superconducting state, in agreement with recent reports. Our research shows that the depth, , of the negative Hall signal scales withT/T _c and that the maximum value of decreases linearly withx and vanishes atx0.24. Magnetoresistance measurements on Y_1–x Pr _x Ba₂Cu₃O_7– single crystals indicate that the irreversibility lineH(T ^*) obeys a universal scaling relation characterized by anm=3/2 power law nearT _c, with a crossover to a more rapid temperature dependence of belowT/T _c 0.6, similar to that observed for polycrystalline specimens.     

AC Response of Cu0.5Tl0.5Ba2Ca2Cu3?xSnxO10?δ Superconductor

We have studied the ac response of Sn doped Cu_0.5Tl_0.5Ba₂Ca₂Cu_3−x Sn _x O_10−δ superconductor samples from their ac-susceptibility measurements under different magnitudes of ac magnetic fields; H _ac=0.4, 4, 16 A/m. The samples with x=0.5 and 1.0 have shown strong flux pinning and intergrain coupling. However, the sample with Sn doping of x=1.5 has shown very poor flux pinning characteristics.     

Optimum Synthesis Temperature of (Cu1?xTlx)Ba2Ca3Cu4O12?δ Superconductor

The effect of synthesis temperature on the superconducting properties of (Cu_1−x Tl _x )Ba₂Ca₃Cu₄O_12−δ (CuTl-1234) samples has been explored. Almost all the superconducting parameters studied in this research work are observed to be suppressed with the increase of synthesis temperature beyond 880 °C, which may be due to impurities caused by the volatility of some constituents such as thallium and oxygen deficiencies as well in the final compound. The Fluctuation Induced Conductivity (FIC) analysis has shown a decrease in the cross-over temperature (T ₀) and the shift of three-dimensional (3D) Aslamasov–Larkin (AL) regions to the lower temperature with the increase of synthesis temperature beyond 880 °C. A direct correlation between the cross-over temperature (T ₀), the zero temperature coherence length {ξ _c (0)}, the zero resistivity critical temperature {T _c (R=0)} as well as carrier concentration has also been observed.     

Effect of Pb Doping on the Superconducting Properties of?(Cu0.5?xPbxTl0.5)Ba2Ca2Cu3O10?δ

The effect of Pb doping on the superconducting properties of (Cu_0.5−x Pb _x Tl_0.5)Ba₂Ca₂Cu₃O_10−δ (x=0.0, 0.15, 0.25, 0.35) samples has been investigated. Lead is doped in Cu_0.5Tl_0.5Ba₂O_4−δ charge reservoir layer and at the CuO₂ planar sites. A multiphase material is achieved with the doping of Pb at the CuO₂ planar sites; however, a predominant single-phase (Cu_0.5−x Pb _x Tl_0.5)Ba₂Ca₂Cu₃O_10−δ (x=0.0, 0.15, 0.25, 0.35) material is synthesized with the doping of Pb at the charge reservoir layers. Formation of multiphase material with the doping of lead at the planar sites showed that its substitution at the planar site is not possible and the formation of PbO₂ planes is less likely. In the samples doped at the charge reservoir layer, the zero critical temperature [T _c (R=0)] is systematically depressed with the increased concentration of lead. The T _c (R=0) and magnitude of the diamagnetism are enhanced after post-annealing the samples in oxygen atmosphere. An apical oxygen mode is observed around 438 cm⁻¹ in undoped samples, which is shifted to 457–461 cm⁻¹ in the Pb-doped samples. This shift in the peak position is most likely associated with the connectivity of apical oxygen atoms with Pb atoms of (Cu_0.5−x Pb _x Tl_0.5)Ba₂O_4−δ (x=0.0, 0.15, 0.25, 0.35) charge reservoir layers. The presence of Pb in the charge reservoir layer and its increased concentration, somehow, stops the flow of mobile carriers to the conducting CuO₂ planes. The decreased density of mobile carriers diminishes the critical temperature and magnitude of diamagnetism in the final compound. The increased oxygen diffusion in the unit cell achieved by post-annealing in oxygen replenishes the concentration of carriers in conducting CuO₂ planes, which increases the T _c (R=0) and the magnitude of diamagnetism. These experiments have shown that the density of mobile carriers plays a vital role in the mechanism of superconductivity and their depressed density suppresses the superconductivity parameters.