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.     

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.     

Photocurrent in superconducting YBa2Cu3O7−x films induced by an infrared free electron laser

Since the discovery of high-temperature cuprate superconductors, there has been much intensive study about the mechanism of them. However, identifying the dynamical mechanism behind them remains one of the great challenges in condensed matter physics. We investigated the high-temperature YBa₂Cu₃O_7−x superconducting films by using a free electron laser (FEL). The method is a type of photoelectron spectroscopy called a free electron laser internal photoemission. The spectrum of the photocurrent induced by FEL was measured in the case of 15 K and 100 K. We estimated the superconductive gap energy of YBa₂Cu₃O_7−x by comparing the photocurrent spectrum of the superconductive state with that of non-superconductive state.     

Infrared optical response of YBa2Cu3O7 and PrBa2Cu3O7 An ellipsometric study

Ellipsometry was used to study (110) and (001) oriented films of YBa₂Cu₃O₇ and PrBa₂Cu₃O₇ in the mid-and near-infrared spectral regions. Below a photon energy of 0.1 eV, the in-plane component of the dielectric tensor of YBa₂Cu₃O₇ is dominated by a Drude term with a squared plasma energy of (3.0 ± 0.3) eV². This “oscillator strength”, and the Lorentzian broadening energy of (0.104 ± 0.005) eV at room temperature, are confirmed by the changes induced in Pr-substituted material, and by low-temperature measurements in the near-infrared. The deviation from the Drude behavior observed above 0.1 eV is accounted for by a broad absorption band with an oscillator strength of (3.6 ± 0.1) eV² in YBa₂Cu₃O₇ which shifts to higher energies and takes over almost all of the oscillator strength of the Drude term when Y is substituted by Pr. The response to electric fields perpendicular to the planes is much weaker, with an upper bound of 0.63 eV² for the squared plasma energy. The in-plane loss function computed from the measured dielectric function follows the Drude-like lineshape, modified by the bound-state absorption band, down to the lowest energy reached in our measurements (0.058 eV).     

Intercalation thermodynamics and chemical diffusion of oxygen in the solid solution YBa2Cu3−xCoxO6+δ

The equilibrium oxygen content as a function of the temperature and oxygen pressure was measured for the solid solution YBa₂Cu_3−xCo_xO_6+δ, where x=0, 0.2, 0.4, 0.6, 0.8, by using coulometric titration in the temperature range 600–850°C and oxygen pressures between 10⁻⁵ and 1.0 atm. The change in the partial molar enthalpy and entropy of the intercalated oxygen was determined at different oxygen and cobalt contents. The oxygen chemical diffusion was studied by thermogravimetric relaxation in the oxygen-controlled atmosphere. The thermodynamic data were employed to determine how the chemical diffusion coefficient, the thermodynamic factor and the random-diffusion coefficient depend on oxygen content in specimens with different cobalt concentration. The oxygen intercalation thermodynamics and diffusivity results provide evidence of ordering phenomena on a microscopic scale in the basal plane of the tetragonal solid solution YBa₂Cu_3−xCo_xO_6+δ. A model for the oxygen diffusion is suggested to explain the large difference between the random and tracer diffusion coefficients in YBa₂Cu₃O_6+δ     

Crystal structure of YBa2Cu3O7−x thin films prepared by pulsed laser deposition with substrate bias voltage

The crystal structure of YBa₂Cu₃O_7−x thin films has been investigated by cross-section transmission electron microscopy. The samples were deposited on MgO (100) substrates at 670°C with substrate bias voltages of ±300 V. For the unbiased case, c-axis, a-axis and (103) oriented domains normal to the substrate surface were observed. In this film, the c-axis oriented domains are dominant, but the crystal often exhibits a longer c-lattice constant than that of the YBa₂Cu₃O_7−x system, so extra cationic layers are inserted in the YBa₂Cu₃O_7−x intrinsic stacking sequence. For the case of −300 V, rotated domains were dominant in the entire film; however, c-axis oriented domains also grow from the substrate surface. Small-angle semicoherent grain boundaries between them were observed. In the case of +300 V, all the grains show c-axis oriented YBa₂Cu₃O_7−x. The degree of preferential orientation of the grains is reduced at negative bias voltage of −300 V and the structure defects are reduced by applying a positive bias of +300 V.     

Phase diagrams of YBa2Cu4O8 and YBa2Cu3.5O7.5 in the pressure range 1 bar≤PO2≤3000 bar

The P-T-x phase diagram of the pseudobinary system (Y-Ba-Cu-O)-O₂ has been further investigated in the oxygen pressure range between 1 and 3000 bar. The stability ranges of the phases YBa₂Cu₄O₈ (124), YBa₂Cu_3.5O_7.5−x (123.5) and YBa₂Cu₃O_7−x (123) have been determined. Long duration experiments showed that the 123 phase is not stable at least down to 7 bar≤P≤20 bar oxygen and 900°C. It is not clear whether at lower pressures and temperatures the 123 phase is thermodynamically stable or metastable due to low reaction rates. In the presence of excess CuO, the 124 is the stable phase. The melting of 124 pellets at P_O2=2800 bar shows that even at this pressure the 124 compound melts incongruently. Using the phase diagram data we could change the T_c of 123.5 from 16 to 70 K by varying systematically the nonstoichiometry. Due to a narrow homogeneity range the T_c of 124 remained constant but is different for powder pellets (81 K) and for crystals (70 K), probably due to the influence of the flux. Single crystals of both 124 and 123.5 with dimensions up to 4 mm were grown from the flux under high oxygen pressure.     

Determination of different oxygen transport mechanisms and measurement of the oxygen ion conductivity of Y1Ba2Cu3O7−x

By undertaking AC electrochemical impedance experiments on yttria stabilised zirconia electrolytes with polished Y₁Ba₂Cu₃O_7−x electrodes, the activation energy for oxygen ion transport within the bulk of Y₁Ba₂Cu₃O_7−x, in air, over the temperature range 823 K–1043 K, was determined to be 1.50 ± 0.05 eV. At 1000 K the oxygen ionic conductivity was calculated to be around one order of magnitude lower than that in yttria stabilised zirconia. Typical calculated values were σ=5×10⁻⁵ (ω cm)⁻¹ and 6×10⁻³ (ω cm)⁻¹ at the respective temperatures 823 K and 1043 K. By employing a similar cell but with Y₁Ba₂Cu₃O_7−x paste electrodes, oxygen transfer between the Y₁Ba₂Cu₃O_7−x and the electrolyte was found to occur via a surface diffusional processes. Over the temperature range 873 K–1098 K, in air, the activation energy for in-diffusion at the surface was found to be 1.4±0.1 eV and that for out-diffusion at the surface to be 1.76±0.05 eV.     

Theoretical and experimental investigation of the linear optical response of YBa2Cu4O8 The relevance of LDA calculations

We report results of ellipsometric measurements of the dielectric tensor of YBa₂Cu₄O₈ as well as calculations employing density functional theory in the local density approximation (LDA). For the computation of the one-electron eigenvalues and states the linear-muffin-tin-orbital method (LMTO) was used. Measured and calculated results show good agreement. In particular, the calculation predicts different band structures for YBa₂Cu₃O₇ and YBa₂Cu₄O₈ in the vicinity of the Fermi energy which lead to significant differences in the optical spectra. One such difference is a region of small ε₂ in the near infrared which is a fingerprint of the high (relative to the top of the highest fully occupied band) Fermi energy as compared to the situation in YBa₂Cu₃O₇. Our experimental results confirm the theoretical findings.     

Preparation and superconducting properties of YBa2Cu4O8

Samples of YBa₂Cu₄O₈ are prepared by means of a new high oxygen pressure technique employing oxygen-HIP. Both magnetization and resistivity measurements show the superconductivity transition at 82.5 K. The lower and upper critical fields of YBa₂Cu₄O₈ are obtained from the magnetization measurements. The Ginzburg-Landau parameters, ζ(0)=17 Å, λ(0)=2400 Å, are estimated from these results.     

Critical current density of polycrystalline YBa2Cu3O7−δ consisting of tin-coated grains

Tin and its oxides have been introduced into the intergrain areas of polycrystalline YBa₂Cu₃O_7−δ by coating the crystalline grains with a thin layer of tin and sintering the ceramics in flowing oxygen and argon. The transport critical current density J_c at 77 K in a magnetic field of 0−1.5 T is enhanced as a result of the coating. A probable improvement of the intergrain weak links is suggested.     

Study of the magnetic properties of single-crystal Ba0.6K0.4BiO3

The magnetic properties of single-crystal Ba_0.6K_0.4BiO₃ were studied. The results show that this isotropic superconductor (cubic structure with T_c ≈ 32 K) exhibits irreversibility and relaxation properties similar to those observed in the layered, high temperature superconductors. For fields above 0.1 T, an irreversibility line B_irr = B_irr (0) (1 − t)ⁿ with n = 3/2 and B_irr (0) = 20 T is observed. The comparison among several superconducting systems with different anisotropies suggests that the irreversibility line is unlikely to be the melting line for the YBa₂Cu₃O_7−δ.     

Phase equilibria at low oxygen partial pressure in the Y---Ba---Cu---O system

The phase equilibria around YBa₂Cu₃O_7−x (123) and YBa₂Cu₄O₈ (124) phases at low oxygen partial pressure (1 atm) were investigated by X-ray diffraction and thermal analysis. The coexistence of 123 and 124 phase was confirmed under 1 atm oxygen pressure. By using the high temperature X-ray diffraction method, the univariant reaction YBa₂Cu₃O_7−x+Cu₂OY₂BaCu₂O₂+O₂ was identified. The oxygen partial pressure dependence of several univariant reactions has been investigated and the existence of two invariant reactions of L+O₂YBa₂Cu₃O_7−x+ BaCuO₂+CuO+Cu₂O and L+Y₂BaCuO₅+O₂YBa₂Cu₃O_7−x+CuO+Cu₂O was deduced to occur at 1103 K under 0.0032 atm O₂ and at 1143 K under 0.0085 atm O₂, respectively.     

Formation of Ca-doped YBa2Cu4O8 phase in thin films

Ca-doped YBa₂Cu₄O₈ (124) thin films are prepared on (100) SrTiO₃ substrates by annealing the amorphous films deposited using a pulsed laser deposition technique. The X-ray diffraction measurements show that the Ca-doped YBa₂Cu₄O₈ phase is formed by annealing below 800°C at a oxygen pressure of 1 atm. The 124 films have c-axis orientation normal to the substrates. As the Ca content increases, the proportion of the 123 impurity phase in the samples increases. The onset temperature of superconductivity of the Y(Ca)Ba₂Cu₄O₈ films increases from 79 K to 88 K with an increase Ca-substitution for 5 to 10% of Y.     

Temperature dependence of the exafs spectrum in YBa2Cu3O7−δ compounds

The temperature dependence of the extended X-ray absorption fine structure (EXAFS) is studied in the high T_c superconductors, YBa₂Cu₃O_7−δ. The measurements were done at the Cu K-edge for samples of two orthorhombic phases (T_c≈90 K and ≈58 K, respectively) and a nonsuperconducting tetragonal phase. Interatomic distances and mean square relative displacements σ² for Cu-O bonds are determined by the least squares refinement. The results indicate that values of σ² increase near T_c for both the orthorhombic samples. It is concluded that this anomalous behavior related to T_c is caused by an anomalous vibration of oxygen atoms in the Ba-O layer. Changes in the Cu-O distances from 300 to 20 K are not found.     

The influence of a zirconia environment on the melt processing of YBa2Cu3O7−x

In the self-flux growth of YBa₂Cu₃O_7−x single crystals in zirconia crucibles a large proportion of the boule consists of secondary phases, from which the YBa₂Cu₃O_7−x crystals are then mechanically separated. The same secondary phases also occur in thick films melt processed on zirconia substrates. The nature and relative proportions of the phases depend on the starting composition, the use of crucible or substrate and growth conditions. However, there are a number of common features, which are the subject of this paper. Scanning electron microscopy EDX analysis of crystal growth boules and thick films are reported. Considerable amounts of Zr are found in the flux phases, even at relatively large distances from the crucible or substrate interface. However, large Zr-doping of the 123 phases does not occur and the superconducting properties are not adversely affected by the presence of these small amounts of Zr.     

Transient creep of YBa2Cu3O7−x superconductor

Rapid changes of oxygen partial pressure (P_O2) between 10³ and 2.1×10⁴ Pa have been carried out during steady-state plastic deformation of polycrystalline YBa₂Cu₃O_7−x (YBCO) at temperatures between 825 and 900°C. Transient creep was observed after such P_O2 changes. The analysis of these creep transients allowed the determination of the chemical diffusion coefficient for reequilibration, which is identical to that found from thermogravimetry and electrical conductivity experiments for oxygen vacancies.     

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.     

Electrical transport and superconductivity in the Al2O3-Bi2Sr1.8Ca1.2Cu2Oy and MgO-Bi2Sr1.8Ca1.2Cu2Oy composites

We have measured the resistivities of Al₂O₃-Bi₂Sr_1.8Ca_1.2Cu₂O_y and MgO-Bi₂Sr_1.8Ca_1.2Cu₂O_y composites with the nominal Bi₂Sr_1.8Ca_1.2Cu₂O_y volume fraction, ₂₂₁₂, ranging from 0.15 to 1.00. For the Al₂O₃-Bi₂Sr_1.8Ca_1.2Cu ₂O_y composites, we find for the samples with ₂₂₁₂≥0.6 that the superconducting transition temperature, T_c, is not disturbed by the addition of Al₂O₃. For ₂₂₁₂<0.3, no zero-resistivity state is observed. For the MgO-Bi₂Sr_1.8Ca_1.2Cu₂O_y composites, T_c is barely disturbed for the samples with ρ₂₂₁₂≥0.7. No superconducting state is observed for the samples with ρ₂₂₁₂<0.35. The variation of (300 K) with ρ₂₂₁₂ indicates a three-dimensional percolating Bi-Sr-Ca-Cu-O matrix occurring at ρ₂₂₁₂≈0.19 and ≈0.15 in Al₂O₃-Bi₂Sr_1.8Ca_1.2 Cu₂O_y and MgO-Bi₂Sr_1.8Ca_1.2Cu₂O_y, respectively. Both resistivity and magnetization measurements suggest that the reactions of Bi₂Sr_1.8Ca_1.2Cu₂O_y with MgO are weaker than with Al₂O₃.     

Yb (Ba, Sr)2Cu4O8: a “124” phase superconductor with a reduced unit cell volume

Yb(Ba_1−xSr_x)₂Cu₄O₈ (0.1x0.3) superconductors of the YBa₂Cu₄O₈(“124”) structure were successfully synthesized using an O₂-hot-isostaticc-pressing (HIP) technique. The samples were characterized with respect to the crystal structure and superconducting properties. The lattice parameters of the samples decreased as the substitution of Sr for Ba proceeded. The superconducting transition temperatures of all the Yb-“124” samples were more or less the same, being around 80 K.