Preparation, characterization and oxide ion conductivity in U-substituted Bi4V2O11

A Bi₂V_{1 − x − y}U_xBi_yO_{5.5 + 0.5x − y} solid solution derived from Bi₄V₂O₁₁ has been prepared and characterized with x up to 0.125 for y = 0. Partial substitution of U⁶⁺ for V⁵⁺ in Bi₄V₂O₁₁ leads to the stabilization at room temperature of the high-oxide ion conducting γ-phase, in contrast with other M⁶⁺ dopants which stabilize the β-phase. The lower conductivity in U substituted system compared with BICUVOX.10 is attributed to its higher activation energy. Conductivity values and activation energies of the U substituted phases compare well with Bi₂UO₆.     

Synthesis and investigation of the complex copper oxides Bi2Sr2R2−xCexCu2O10+δ (R=rare earth)

Bi-2222 phases were prepared by solid state reactions and were studied using X-ray diffraction, chemical and EDS-analysis. Compounds with composition Bi₂Sr₂R_1.33Ce_0.67Cu₂O_10+δ were obtained for R=Pr, Nd, Sm-Er. The phases Bi₂Sr₂Cu₂O_10+δ with similar structure but without Ce were prepared for R = Pr, Sm-Dy. For Bi₂Sr₂Eu_2−xCe_xCu₂O_10+δ the solubility limit was determined and the effect of treatment under different oxygen pressures was investigated. Weak diamagnetic signals (<3%) were detected for some of these samples.     

Nax/2Bi1−x/2MoxV1−xO4 and Bi1−x/3MoxV1−xO4 New Scheelite-related phases

New Scheelite-related solid solutions of the compositions Na_x/2Bi_1−x/2Mo_xV_1−xO₄ (0≤x≤1) and Bi_1−x/3 Mo_xV_1−xO₄(0≤x≤0.2) have been synthesised by the substitution of Na and Mo at the A and B sites respectively of the ABO₄ type ferroelastic BiVO₄. The phases were characterised using chemical analysis, powder X-ray diffraction, scanning electron microscopy, EDAX, and Raman spectroscopy. While almost a continuous solid solution is obtained for the series Na_x/2Bi_1−x/2Mo_xV_1−xO₄, the absence of Na at the A-site results only in a narrow stability region for the other series, Bi_1−x/3 Mo_xV_1−xO₄ where 0≤x≤0.2. Raman spectra of selected samples at room temperature also suggest that vanadium and molybdenum atoms are disordered at the tetrahedral sites.     

Low-temperature AC conductivity of Bi2Sr2CaCu2O8+δ

We report measurements of anamolously large dissipative conductivities, σ₁, in Bi₂Sr₂CaCu₂O_8+δ at low temperatures. We have measured the complex conductivity of Bi₂Sr₂CaCu₂O_8+δ thin films at 100–600 GHz as a function of doping from the underdoped to the overdoped state. At low temperatures there exists a residual σ₁ which scales with the T=0 superfluid density as the doping is varied. This residual σ₁ is larger than the possible contribution to σ₁ from a thermal population of quasiparticles (QP) at the d-wave gap nodes.     

O KVV Auger emission versus resonant photoemission at the O K edge of high-Tc superconductors

Photoelectron spectroscopy results on single crystals of the superconductors Bi₂Sr₂CaCu₂O₈,Bi₂Sr₂CuO₆, Ba_0.6K_0.4BiO₃ and the semiconductor Ba_0.9K_0.1BiO₃ are reported for the photon energy region around the O K absorption threshold. The development of the O-KVV Auger structure has been carefully monitored as a function of photon energy. A non-monotonic behavior displaying a feature at a constant binding energy of about 14 eV was found for Bi₂Sr₂CaCu₂O₈ and Bi₂Sr₂CuO₆ in a narrow photon energy region of 1 eV at the main edge of the O K absorption spectrum around 530 eV. The corresponding enhancement, connected with the autoionization of O 2p states, is absent in Ba_1−xK_xBiO ₃ in contrast to Bi₂Sr₂CaCu₂O₈ and Bi₂Sr₂CuO₆. The resonant enhancement is more pronounced for Bi₂Sr₂CuO₆ as compared to Bi₂Sr₂CaCu₂O₈, which can be explained by a lower charge carrier concentration in the former case, leading to a more localized nature of intermediate O 2p states. The model parameters Cu d–d and O p–p Coulomb interactions and the charge transfer energy Δ are estimated from the experiments.     

Evidence for pinning by (Sr,Ca)2CuOy particles in partial-melting processed bulk Bi2Sr2CaCu2O8+δ ceramics

Flux distributions of partial-melting processed Bi₂Sr₂CaCu₂O_8+δ ceramics are obtained using magneto-optic imaging. In remanent states (μ₀H_a=0 T), large amounts of trapped flux are observed along (Sr,Ca)₂CuO_y particles embedded in the Bi₂Sr₂CaCu₂O_8+δ matrix. Despite the relatively large size of these particles (up to 30 μm), the pinning effect is similar to that of Y₂BaCuO₅ particles in melt-processed YBa₂Cu₃O_7−δ. Furthermore, we discuss how the pinning capability of non-superconducting particles of different sizes and densities will show up in magneto-optic images.     

Study of the interfacial structure and chemistry of CVD κ-Al2O3/TiC multilayer coatings

This article describes the interfacial regions in CVD grown TiC/κ-Al₂O₃ multilayers. A number of microanalytical techniques were used including HREM, EDX and EELS. Occasionally, the first 50 nm of the alumina layers deposited on the intermediate TiC layers grew as a cubic alumina, heavily faulted, containing small amounts of sulphur (S), maybe as a stabiliser. The presence of slightly rounded TiC (111) facets may act as preferred nucleation sites for the cubic Al₂O₃ phase, with a ‘cube on cube’ orientation relationship. In this way the nucleation of κ-Al₂O₃ is less favourable. After some tens of nanometres the cubic phase cannot be stabilised any longer and the layer continues to grow as κ-Al₂O₃. A number of observations point towards the reaction zone (RZ) being η- and/or γ-Al₂O₃. The diffraction work and the FFT analysis of the HREM images show that the RZ is an fcc phase with a=7.9 Å, which matches with η- and γ-Al₂O₃. The EELS Al fine structure indicate more tetrahedral Al ions than in κ-Al₂O₃, as in η- and γ-Al₂O₃. The RZ contains small amounts of S, as has been reported for γ-Al₂O₃. Due to the structural similarities between η- and γ-Al₂O₃ it was not possible to determine which of these cubic phases is present in the RZ.     

Intergranular properties of YBCO and BSCCO ceramic superconductors at low fields

Isothermal low-field AC susceptibility measurements have been used to analyze the intergranular critical current density J_c(T) on sintered, non-oriented YBa₂Cu₃O_7−δ and Bi₂Sr₂CaCu₂O_8+δ ceramic samples at zero field. Below the critical temperature, potential variations, J_c(T) ≈ (1−t_j)^m with t_j = T/T_j, have been found, T_j being the onset of grain's coherence, but with different exponents, supporting that different mechanisms limit the intergranular J_c values. Moreover, the effect of texture has been also considered on Bi₂Sr₂CaCu₂O_8+δ ceramics grown by the laser floating zone method, which have stronger intergranular junctions. Their high-temperature behaviour is limited by intrinsic effects, while at low temperatures the quality of the junctions is the limiting factor. The temperature dependence of the χ′(h₀) extrapolation at zero filed has also been correlated with the evolution of the intergranular penetration depth, λ_J(T).     

Effect of lead addition to Bi-based 2222 superconducting cuprates Bi2-xPbxSr2(Y, Ce)2Cu2O10+δ

Bi_2-xPb_xSr₂(Y, Ce)₂Cu₂O_10+δ, a new family of lead containing Bi-2222 compounds has been synthesized and effects of annealing in high pressure of oxygen studied. Lead-free Bi₂Sr₂(Y, Ce)₂Cu₂O_10+δ synthesized under flowing oxygen is known to be non-superconducting, but annealing under high oxygen pressure (100 bar) at 500°C, induced superconductivity with T_c=25 K. On substitution of lead (x>0.4), the superconductivity appears even in samples synthesized under flowing oxygen (1 bar). T_c increases with oxygen annealing pressure for all compositions, and it also increases with Pb content at a given oxygen pressure. These findings are discussed.     

Direct observation of flux-creep in high-Tc superconductors using the high-resolution Faraday effect

Using the capability of the high-resolution Faraday effect (HRF) to allow dynamic observations of the Shubnikov phase, we directly observed effects of flux-creep in high -T_c superconductors. In this paper we show measurements on (RE) Ba₂Cu₃O_7-δ with RE=Y, Dy, Gd and on Bi₂Sr₂CaCu₂O_8−δ single crystals and also on YBaCuO thin films and sintered materials. Furthermore, this technique enables us also to measure the flux creep locally. From the obtained photographs we determine the time dependence of the total flux in the samples. Using these data and the model of Hagen et al. the effective activation energies have been determined for these materials.     

The role of Bi2O3 as a network modifier and a network former in xBi2O3 · (1 − x)LiBO2 glass system

The effect of Bi₂O₃ on the glass transition temperature, electrical conductivity and structure of LiBO₂ glass has been investigated. T_g vs. composition curve shows three different linear regions, while there is an overall decrease in T_g with the increase in Bi₂O₃ content. The slope of these three straight lines is in a decreasing order. These results are interpreted in terms of the increase in the number of non-bridging oxygen atoms, substitution of Bi-O bond in place of B-O bond and change in Li⁺ ion concentration. The conductivity vs. composition curve exhibits two maxima which are interpreted in terms of the structural modification effect of Bi₂O₃ on LiBO₂ network and mixed-former effect, respectively. Results obtained from the XPS studies of the samples of composition x 0.005, have shown that the number of non-bridging oxygen atoms from B-O bond increases with the increase in Bi₂O₃ content. It has a maximum value at x = 0.003 where the conductivity has also exhibited a maximum value. Further increase of Bi₂O₃ content causes decrease in it. For higher Bi₂O₃ content (x * > 0.005), O 1s spectra of Bi₂O₃ has been separated out from that of Bi₂O₃. Bismuth ions have been substituted for boron ions as network former ions.     

Observation of enhanced dielectric permittivity in Bi doped BaFe12O19 ferrite

The dielectric properties of a 2.5 mol% Bi₂O₃ doped Ba-ferrite (BaFe₁₂O₁₉) have been investigated. The specimen shows a drastically enhanced (≈ 10⁵ times) permittivity (ε) through local polarization of Fe³⁺ electronic charges activated with nearby Bi³⁺ sites. The ε value also depends reasonably on thermal annealing (causes grain growth) of the samples. The specimens comprising large particle sizes (1–20 μ m) usually exhibit smaller ε values and low dielectric losses.     

Oxygen nonstoichiometry effect on structural modulation in Bi-2212 cuprate superconductors

The X-ray diffraction patterns for Bi₂Sr₂Ca_1−xY_xCu₂O_8+y sintered in air or Ar indicated that the reduction in the number of excess oxygen ions induced a structural change from orthorhombic to pseudotetragonal. When the oxygen contents decreased with the reducing treatment, the period of modulation in Bi₂Sr₂Ca_1−xY_xCu₂O_8+y increased. This result supported the model of excess oxygen ions in the Bi---O sheet. However, it was difficult to understand the change of modulation period with increasing Y contents using the model of excess oxygen ions in the Bi---O layers. Also, it is included that the Y substitution for Ca and La substitution for Sr in the Bi₂Sr₂CaCu₂O_8+y system result in parallel effects for the modulation structure.     

Realization and properties of ramp-type YBa2Cu3O7−δ/Au/Nb junctions

All-thin-film ramp type Josephson junctions between YBa₂Cu₃O_7−δ and Nb have been fabricated. This procedure allows connections between high-T_c and low-T_c superconductors at different crystal sides of the high-T_c superconductor on one chip, which is of great interest for novel phase devices. A thin Au layer is incorporated as a chemical barrier to avoid oxygen transfer from the YBa₂Cu₃O_7−δ to the Nb. Critical current densities up to 600 A/cm² are obtained at T=4.2 K, with typical R_nA values of 0.8 μΩ cm². The variation of the magnetic field dependence of the critical current with the angle between the junction barrier and the YBa₂Cu₃O_7−δ crystal axes is explained by considering a predominant d_x²−y² order parameter symmetry of the YBa₂Cu₃O_7−δ. The successful fabrication of these junctions allows the implementation of novel superconducting electronics, such as complementary Josephson circuitry or proposed qubit concepts, using the unconventional order parameter symmetry of the high-T_c superconductor.     

The nuclear contribution to the specific heat of single crystals of YBa2Cu3O7 and Bi2Sr2CaCu2O8

Specific heat data below 1 K of Bi₂Sr₂CaCu₂O₈ and YBa₂Cu₃O₇ are analyzed. For YBa₂Cu₃O₇ the nuclear specific heat, C_N, amounts to 38T⁻² μJ/mol K. C_N for Bi₂Sr₂CaCu₂O₈ exceeds that of YBa₂Cu₃O₇ by a factor of 15. The nuclear quadrupolar specific heat contribution alone is insufficient to explain the data for YBa₂Cu₃O₇, while lack of NQR data does not allow such a comparison in Bi₂Sr₂CaCu₂O₈ to be made. The contribution to C_N from nuclear spins coupled via the contact hyperfine interaction with correlated magnetic spins (in the CuO₂ plane) is derived as a function of the correlation length. This contribution can be treated independently from the quadrupolar term. We show that the excess specific heat in YBa₂Cu₃O₇ likely originates in a few percentage of an impurity (oxygen deficient) phase with a strong hyperfine field on the Cu nuclei.     

Solid-state synthesis of potassium β- and β″-gallates

Direct synthesis of K-β- and β″-gallates by Ga₂O₃–K₂O solid-state reaction is described. The formation of K-β- or β″-gallates depends on the initial Ga₂O₃ phase. -Ga₂O₃ leads to K-β-gallate; β-Ga₂O₃ leads to K-β″-gallate. K-β″-Gallate is stable <1200°C. The high temperature stability of K-β″-gallate can be enhanced by doping with aliovalent ions.     

Temperature dependence of the critical current in YBa2Cu3O7−δ and Bi2Sr2Ca1Cu2O8 Josephson junctions

We have studied the stationary Josephson effect on YBa₂Cu₃O_7−δ (T_c=90 K) and Bi₂Sr₂Ca₁Cu₂ O₈ (T_c=80 K and 87 K for two samples of different origin) ceramic based junctions. The temperature dependence of the critical current near T_c has been found as I_c≈(T_c-T) for the Y-Ba-Cu-O samples indicating that they should be classified as S-N-I-N-S type junctions. The I-V curves of the Bi-Sr-Ca-Cu samples show the typical behaviour of S-I-S structures. Using Ambegaokar-Baratoff's theory for Bi₂Sr₂Ca₁Cu₂O₈, the temperature dependence of the superconducting state gap Δ(T) was calculated and it was evaluated that 1.452Δ(0)/k_BT_c3.5.     

Effect of Hg addition on synthesis of Bi-based superconductors

We have investigated the effect of Hg addition on the superconducting properties of BiSrCaCuO system. Polycrystalline samples with nominal composition Bi₂Sr_2−xHg_xCa₁Cu₂O_y and Bi₂Sr_2−xHg_xCa₂Cu₃O_y (x=0.3) were synthesized and used to investigate the phase evolution by XRD, superconducting behaviour by R–T measurement and the structural grain boundary effects by SEM. From these measurements, it has been noticed that the phases obtained with both types of compositions are the same as Bi2212 but the T_c values are different. With additional annealing, T_{c zero} values were raised from 60 to 72 K in Bi₂Sr_2−xHg_xCa₁Cu₂O_y and 64 to 92 K in Bi₂Sr_2−xHg_xCa₂Cu₃O_y. Also, an improved grain boundary linkage has been observed by SEM for the 92 K sample.     

The crystallographic symmetries of single BaPb1−xBixO3 crystals grown from BaCO3-PbO2-Bi2O3 solutions

Single crystals of Perovskite-type oxide BaPb_1−xBi_xO₃ are grown from BaCO₃-PbO₂-Bi₂O₃ solutions which are weighed in two kinds of mixing ratios: X/2 mol % BaCO₃ − (100−X) mol % PbO₂ − X/2 mol % Bi₂O₃ and (10+X/2) mol % BaCO₃ − (90−X) mol % PbO₂ − X/2 mol % Bi₂O₃ These room temperature crystal structures are examined by using an X-ray powder diffraction method. The crystals grown from X/2−(100−X)−X/2 mol % solutions are orthorhombic at room temperature, while the structures are tetragonal with crystals grown from relatively Ba rich and Pb poor ( (10+X/2)−(90−X)−X/2 mol % ) solutions. This result indicates that the difference in the mixing ratio of the initial materials brings about a drastic structural change. The orthorhombic and the tetragonal crystals of x0.25 exhibit superconducting transition at 10K and 12K, respectively. The transition temperature in the latter is 2K higher than the former. In the light of this result, some difference between orthorhombic and tetragonal crystals is considered to influence superconductivity in this system.     

Origin of the metal-insulator transition in the superconducting series Bi2Sr2Ca1−xYxCu2O8+δ

The metal-insulator transition in the solid solution Bi₂Sr₂Ca_1−xY_xCu₂O_8+δ (0≤x≤1) has been investigated by TGA (oxygen content) and by X-ray absorption spectroscopy (Bi and Cu valence states). Resistivity and AC magnetic susceptibility measurements have shown that the superconducting properties and the metallic behavior vanish for x>0.55. The oxygen content δ is larger than x/2 for x≤0.3 and smaller than x/2 for x≥0.6. For x=0, the Cu K edge shows a shift towards high energy with respect to the Cu(II) oxide La₂CuO₄; this shift decreases with increasing x in agreement with the decrease of the doping hole density and the variations of the physical properties. For 0≤x≤0.3, the Bi L₃ edge shows a shift of 1 eV towards low energy with respect to the Bi(III) oxide Bi₂O₃ in agreement with the charge transfer between [CuO₂]_∞ and [BiO]_∞ planes. This shift also decreases with increasing x, but is still present for the x=0.6 composition for which δ is smaller than x/2. A model of the metal-insulator transition in this series is proposed based on the fact that the intercalation of excess oxygen raises the bottom of the Bi-O band with respect to the Fermi level and decreases the contribution of the Bi-O electron pocket to the hole density.