Phonon Raman scattering in Nd1+xBa2−xCu3O7−δ and Pr1+xBa2−xCu3O7−δ single crystals

The polarized Raman spectra of Nd_1+xBa_2−xCu₃O_7−δ (−0.023≤x≤0.107) and Pr_1+xBa_2−xCu₃O_7−δ (0.01≤x≤0.15) single crystals have been investigated. It was found that the Cu(2) A_g mode softens by 6 cm⁻¹ in Nd 1:2:3 and 4 cm⁻¹ in Pr 1:2:3 as x increases. These frequency shifts cannot be explained by the change in the relevant bond lengths due to Nd(Pr)-substitution for Ba. The variations with x of the two low frequency modes may be affected by change of their hybridization and/or change of their force constants. The linewidths of Ba mode in Pr 1:2:3 are broader than those in Y 1:2:3. This result suggests that the Pr substitution on Ba sites occurred even in a very small value of x. In x(yy) geometry the relative intensity of the Ba and O(4) modes in Nd 1:2:3 is greater than those in Pr 1:2:3. The difference between Nd 1:2:3 and Pr 1:2:3 in the relative intensity of the Ba and O(4) modes may be produced by the chains.     

Electrochemical behaviour of (La1 − xSrx)sCo1 − yNiyO3 − δ as porous SOFC cathodes

This paper shows that storage at room temperature and ambient atmosphere appears to affect the polarisation resistance significantly and R_P decreased initially with storage time. This improvement was more pronounced when stored in moisturised air. The performance was, however, also found to decrease when stored for sufficiently long periods. The absolute values of the electrode response of these materials are very difficult to reproduce and the performance appears to be largely dependent on the manufacturing process of the powder or the electrode itself. In spite of this, the electrode behaviours exhibited similar patterns with respect to the dependence on T and P_O2. An increase in polarisation resistance with time at SOFC operating conditions was observed, which was related exclusively to the electrode reaction kinetics and not to oxygen concentration polarisation. It was also found to be higher when measured in moisturised air.     

Ramans study of Y1−xPrxBa2Cu3O7−δ and YB2Cu3−xZnxO7−δ single crystals

Single crystals with known T_c values of Y_1−xPr_xBa₂Cu₃O_7−δ (Y---Pr1:2:3) and YBa₂Cu_3−xZn_3−xZn_xO_7−δ (Y---Zn1:2:3) systems are studied by Raman measurements. The Raman spectra for (Y---Pr1:2:3) single crystals show that the frequencies of Ba and O_z modes increase as the Pr content increases. The results are consistent with the hole-localization scheme proposed for the suppression of superconductivity in the polycrystalline Y---Pr1:2:3 systems. On the other hand, in the Y---Zn1:2:3 system, all the Raman modes do not change in frequencies. However, the FWHM of the Cu(2) mode increases with the decrease of T_c, indicating strong scattering of charge carriers by the substituted Zn ions in the CuO₂ planes. The induced disorder in the CuO₂ planes may be related with suppression of T_c in the Y---Zn1:2:3 system. Thus, the suppression mechanism in the Y---Zn1:2:3 systems seems to be different from that in the Y---Pr1:2:3 systems.     

Oxygen diffusion and surface exchange in La1−xSrxFe0.8Cr0.2O3−δ (x=0.2, 0.4 and 0.6)

Oxygen tracer diffusion (D*) and surface exchange rate constant (k*) have been measured, using isotopic exchange and depth profiling by secondary ion mass spectrometry (SIMS), in La_1−xSr_xFe_0.8Cr_0.2O_3−δ (x=0.2, 0.4 and 0.6). Measurements were made as a function of temperature (700–1000 °C) and oxygen partial pressure (0.21–10⁻²¹ atm) in dry oxygen, water vapour and water vapour/hydrogen/nitrogen mixtures. At high oxygen activity, D* was found to increase with increasing temperature and Sr content. The activation energies for D* in air are 2.13 eV (x=0.2), 1.53 eV (x=0.4) and 1.21 eV (x=0.6). As the oxygen activity decreases, D* increases as expected qualitatively from the increase in oxygen vacancy concentration. Under strongly reducing conditions, the measured values of D* at 1000 °C range from 10⁻⁸ cm² s⁻¹ for x=0.2 to 10⁻⁷ cm² s⁻¹ for x=0.4 and 0.6. The activation energies determined at constant H₂O/H₂ ratio are 1.21 eV (x=0.2), 1.59 eV (x=0.4) and 0.82 eV (x=0.6).

The surface exchange rate constant of oxygen for the H₂O molecule is similar in magnitude to that for the O₂ molecule and both increase with increasing Sr concentration.     

Effect of the RE ionic size on the REBa2Cu3O7−δ ceramics oxygenated at 250 bar

REBa₂Cu₃O_7−δ (RE=Ho, Y, Dy, Gd, Sm, Nd) ceramics have been oxygenated at 1 bar pressure (LP) and, subsequently, at 250 bar (HP). Despite the noticed slight uptake of oxygen (up to the value of 0.07), after the HP processing, the electrical resistivity (ρ) of all samples increased, what was attributed to the deterioration of the grain boundaries. The increase of ρ was much more pronounced and also accompanied by a change of ρ(T) characteristics into a semiconducting-like one in the case of 123 compounds based on REs which ionic size is large enough to form solid solutions of RE_1+xBa_2−xCu₃O_y type (i.e., RE=Gd, Sm, Nd). As shown in the literature, such 123s usually contain more structural defects. Thus, the observed effect may be attributed to the migration of the defects induced by the elevated pressure oxygenation. The defects could be trapped near the grain boundaries resulting in the deterioration of their electrical properties. The possible role of the oxygen-pressure-induced modifications of the impurity phases has been also discussed. The materials obtained in the HP process may be regarded as 3D arrays of superconducting grains coupled by the Josephson junction or weak links only, as was shown in a tunneling experiment.     

Field induced flux pinning in Nd1+xBa2−xCu3O7−δ single crystal

The flux pinning behavior of a Nd_1+xBa_2−xCu₃O_7−δ (Nd123) single crystal, which exhibited a peak effect, has been studied by monitoring the time decay of the magnetic moment. The apparent pinning energy (U₀^*) was deduced from flux creep data on the basis of the Anderson-Kim model. The magnetic field dependence of U₀^* showed maxima at peak fields which depended on the temperatures, in a similar manner to those of critical current densities. In addition, the temperature dependence of U₀^* showed several features. To explain the increase in U₀^* with the field as well as its temperature and field dependence, we made a numerical calculation by introducing an additional pinning energy which increased with increasing field. The results are in good agreement with the experimental data, especially at temperatures above 60 K, where the contribution of field induced pinning centers is believed to be dominant.     

Magnetic behavior of 3d dopants in superconducting REBa2Cu3−xFexO7+δ (RE=Dy, Er)

Mössbauer studies on ⁵⁷Fe-doped superconducting REBa₂Cu₃O_7+δ (RE=Er, Dy) were made as a function of temperature for x=0.15 and 0.30. The magnetic behavior of the 3d dopants, which mainly occupy Cu(1) sites, undergoes antiferromagnetic ordering which is coexistent with superconductivity at low temperature. The dimensionality of the magnetic interaction changes from 2D to 3D when the rare earth changes from Er to Dy. the line-widths of the Mössbauer subspectra are characteristic of magnetic fluctuation behavior in the vicinity of a phase transition. Combining these results with those of Fe-doped Y-123 (pseudo 1D) and Gd (3D), the magnitude of the rare earth moments appears to be strongly correlated with the dimensionality of the magnetic interaction of Fe dopants in these compounds. However, the Mössbauer spectrum for ¹⁵⁵Gd in GdBa₂Cu_2.85Fe_0.15O_7+δ (T_{N(Fe) 14 K}) shows no magnetic order at 4.9 K.     

Trapping mechanism of superconductivity suppression induced by Pr substitution in the Ho1−xPrxBa2Cu3O7−δ system

Pr concentration dependence of the superconducting transition temperature T_c in the Ho_1−xPr_xBa₂Cu₃O_7−δ system is determined from measurements of DC electrical resistance. This dependence coincides with that for the parallely studied Y_1−xPr_xBa₂Cu₃O_7−δ reference system. Both systems have the same value of the critical concentration x_c=0.58, in accordance with nearly equal ionic radii of Ho³⁺ and Y³⁺ ions. It has been shown that the T_c(x) curve can be described with a single mechanism based on a decreasing number of sheet holes trapped by Pr^IV-ions, if one takes also into account that the number of these ions changes with x.     

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.     

Properties of YBa2Cu3O7−δ/YBa2CoxCu3−xOy/YBa2Cu3O7−δ Josephson edge junctions with 0.1 x 0.3 and the effect of flux flow on their normal resistance

YBa₂Cu₃O_7−δ (YBCO) based SNS edge junctions with cobalt doped YBCO barriers were prepared and characterized. At 77 K, good junctions had RSJ-like I–V curves with excess current, magnetic suppression of I_c of about 50% or more, and clear microwave steps. The conductance values 1/R_N at 77 K of junctions with different barrier thickness and composition, were proportional to the junction areas A, but show little correlation with the thickness of the barriers t_B in the range of 15t_B100nm. The corresponding I_cR_N products were observed to scale as J^0.66±0.09_c, similar to what was found by others. At the same time, the measured values of R_N are much smaller than what is expected based on the dimensions of the junction and the resistivity of the barrier material. To explain all of this, we propose a model in which at high supercurrent densities, flux flow of Josephson vortices in the junction leads to R_N values which are lower than expected. This model predicts

Full-size image (1K)

, which fits the observed results very well.     

Unusual resistivity broadening in the mixed state of NdBa2Cu3O7−δ crystals grown by a crystal-pulling technique

In order to clarify the origin of a strong peak effect in the magnetization curve of NdBa₂Cu₃O_7−δ crystals, we investigated the superconductivity transition behavior of the in-plane resistivity in static magnetic fields up to 8 T. Comparing the results for the samples exhibiting and not exhibiting the peak effect, we found that the former (peak effect sample) shows lower resistivity above the vortex melting temperature. This implies that the pinning force is effective in the vortex liquid state. We also found that the normal state resistivity behaviors of some samples were unusual, indicating inhomogeneous current flow. These results suggest an existence of sheet-like pinning centers perpendicular to the conduction planes.     

Magnetic properties and specific heat of LaMn1−xTixO3+δ (0<x0.2)

We present a magnetic study of the insulating perovskite LaMn_1−xTi_xO_3+δ (0<x0.2) including measurements of magnetization, susceptibility, and magnetic relaxation. The Curie temperature was found to decrease with increasing content of Ti. Two distinct magnetic transitions, irreversibility, non-exponential relaxation and aging effects confirm a reentrant spin–glass state for x=0.2. The time decay of the magnetization has an algebraic functional form for times up to 2 h. The specific heat also displays characteristic features of a spin–glass system by a linear low-temperature dependence and a broadened peak near the temperature of the reentrant transition.     

Peak effect and oxygen ordering in YBa2Cu3O7−δ single crystals

We have investigated the second magnetization peak in pure YBa₂Cu₃O_7−δ single crystals with various oxygen contents (6.91<7−δ<6.97) and degrees of oxygen vacancy ordering, as achieved by low (1 bar) and high (100 bar) oxygen pressure annealing. Although the position of the peak changes drastically with oxygen stoichiometry, no dependence on the distribution of oxygen vacancies has been found for temperatures below 70 K. For T>70 K, however, ordering effects become important as demonstrated by the disappearance of the peak for the high pressure annealed samples. These results suggest that while at low temperatures, pinning of the vortex system by clusters or a more homogeneous distribution of oxygen vacancies is similar, at elevated T, the former are much stronger pinning sites leading to larger hysteresis and the presence of the peak.     

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.     

Characterization of nonstoichiometric nickel manganite spinels NixMn3−x□3δ/4O4+δ by temperature programmed reduction

Cation deficient spinels Ni_xMn_3−x□_3δ/4O_4+δ (0≤x≤1) have been prepared by thermal decomposition of mixed oxalates Ni_x/3Mn_(3−x)/3(C₂O₄)·nH₂O in air at 623 K. They have been characterised by temperature programmed reduction (TPR) under H₂, the reaction being followed by gravimetric and powder X-ray diffraction measurements. It has been shown that TPR proceeds in several steps. The first steps correspond to the loss of nonstoichiometric oxygen leading to the formation of a stoichiometric oxide. During the following stages the manganese cations are reduced, causing the spinel structure to be destroyed, and the formation of solid solution of NiO in a cubic MnO. Subsequently, Ni²⁺ cations undergo a reduction to metallic nickel, and, finally, a mixture of nonstoichiometric MnO_1−δ and metallic nickel is formed. These oxides contain a high level of vacancies which vary with the nickel content with a maximum of δ≈1 near x=0.6. This nonstoichiometry is ascribed both to the presence of Ni³⁺ and excess of Mn⁴⁺.     

Flux jump avalanches in torque studies of single crystal YBa2Cu3O7−δ

A series of avalanche-like jumps are observed in the mixed state of single crystal YBa₂Cu₃O_7−δ (YBCO) superconductors. Emerging as a saw-tooth pattern in torque vs. sample orientation in magnetic field, these jumps are discontinuous on our most resolute angular scale. While reminiscent of the classical flux jump instability, the present jumps are instead proposed to be associated with the layered nature of the material and twin boundary (TB) pinning, the combination of which promotes a crossover from a tilted to a kinked vortex structure.     

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     

Superconductivity magnetism and low temperature specific heat in YBa2(Cu1−xFex)3O7−δ with δ0 and δ1

Magnetic and low temperature specific heat measurements have been performed on iron doped YBa₂(Cu_1−xFe_x)₃O_7−δ samples with different oxygen contents (δ0 and δ1). Iron doping induces an orthorhombic to tetragonal transition and a decrease of both T_c and diamagnetic signal. Low temperature specific heat measurements reveal a Schottky type anomaly for δ0 samples with x=0.01 (1.8 K) and x=0.02 (3 K). This anomaly is attributed to magnetic interactions within iron limited chains. A numerical analysis of this effect is proposed.     

Defect chemistry and oxygen transport of (La0.6Sr0.4 − xMx)0.99Co0.2Fe0.8O3 − δ, M = Ca (x = 0.05, 0.1), Ba (x = 0.1, 0.2), Sr: Part I: Defect chemistry

This paper is the first part of a two part series, where the effects of varying the A-site dopant on the defect chemistry, the diffusion coefficient and the surface catalytic properties of the materials (La_0.6Sr_0.4 − xM_x)_0.99Co_0.2Fe_0.8O_3 − δ, M = Sr, Ca (x = 0.05, 0.1), Ba (x = 0.1, 0.2) (LSMFC) have been investigated. In part I, the findings on the defect chemistry are reported, while the transport properties are reported in part II. Substitution of Sr²⁺ ions with Ca²⁺ ions (smaller ionic radius) and Ba²⁺ ions (larger ionic radius) strains the crystal structure differently for each composition while keeping the average valence of the cations constant. The Ba²⁺ containing materials show the largest oxygen loss at elevated temperatures, while the purely Sr²⁺ doped material showed the smallest oxygen loss. This was reflected in the partial oxidation entropy of the materials. The measured oxygen loss was modelled with point defect chemistry models. Measurements at very low p_O2 showed several phase transitions.