Synthesis and ionic conductivity of new layered perovskite compound, Ag2La2Ti3O10

A new layered perovskite compound, Ag₂La₂Ti₃O₁₀, was synthesized by an ion-exchange reaction of M₂La₂Ti₃O₁₀ (M = Na,K) with a AgNO₃ molten salt. The crystal structure and the ionic conductivity of the ion-exchanged compound were investigated. The ionic conductivities attributed to the interlayer silver ions were observed at high temperatures. The ionic conductivity of Ag₂La₂Ti₃O₁₀ was much higher than that of Na₂La₂Ti₃O₁₀, while the interlayer sodium ions in Na₂La₂Ti₃O₁₀ and silver ions in Ag₂La₂Ti₃O₁₀ have almost the same rock-salt type coordination. The higher conductivity of Ag₂La₂Ti₃O₁₀ is probably due to the higher polarizability of silver ions.     

Chemical diffusion of water in the high-temperature proton conductor Ba3Ca1.18Nb1.82O9-δ

Ba₃Ca_1.18Nb_1.82O_9-δ (also referred to as BCN18) is a promising high-temperature proton conductor. In the dry state it contains an abundant amount of vacancies in the oxygen sublattice. Water may enter the compound occupying the vacancies and supplying protons to the lattice. The conductivity of these protons may be used in future applications of high-temperature proton conductors as electrolytes for SOFCs and in sensors. Chemical diffusion of water in this compound is described by the coupled outward flux of Ovacancies and the inward flux of protons (OH^•). The chemical diffusivity is in general a complicated function of the concentrations and the individual diffusivities. In this work, the chemical diffusivity of water is determined by studying the kinetics of a) the weight increase in TG experiments, and b) of dilatometric length changes upon subjecting the samples to humid atmospheres. The chemical diffusivities determined using techniques a) and b) are in good agreement. Likewise, the present data are compatible with those determined in a previous thermal desorption study. The present data, however, only apply to situations where the initial proton concentration is rather low and where the proton content is not changed dramatically in the experiment. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997     

Electrical and mechanical properties of proton conducting SrCe0.95Yb0.05O3 − α

Yb³⁺-doped ceramic strontium cerate of exactly the composition SrCe_0.95Yb_0.05O_{3 − α} was prepared, having a relative density of 99.0 (± 0.3%). Great care was taken to obtain homogeneous, carbonate free material. Analysis are made of the X-ray powder diffraction pattern of the as-prepared dense ceramic, resulting in the orthorhombic unit cell parameters a = 6.997(2) Å, b = 12.296(3) Å, c = 8.588(2) Å, Z = 8 and d_x = 5.806(2) g cm⁻³. Bending strength values of the ceramic in non-proton and proton conducting state are found to be 177 and 194 MPa respectively. The ceramic kept under proton conducting conditions for 500 h at 300 °C to 800 °C in a N₂ flow containing 155 mbar water vapour and 245 mbar H₂, have shown to remain chemically and structurally stable. Impedance spectroscopy measurements of the bulk conductivity of the proton conducting ceramic revealed an activation energy of 53.2 kJ mol⁻¹ and a preexponential factor of 359.1 (Ω cm)⁻¹ K. In the non-proton conducting state the ceramic is mainly oxygen ion vacancy conducting, which indicates that charge compensation on substituting Yb⁺³ in SrCeO₃ takes place by oxygen ion vacancies.     

Field-induced pinning effect of Nd(Ba1−xNdx)2Cu3O7−δ single crystals grown by the traveling-solvent floating-zone method

We have studied the superconducting properties of Nd(Ba_1−xNd_x)₂Cu₃O_7−δ (Nd123, x ≈ 0.1) single crystals grown by the traveling-solvent floating-zone method under 0.1% O₂ in Ar atmosphere. The enhancement of the magnetization with increasing field is observed in the hysteresis (M-H) loop in fields both parallel and perpendicular to the c-axis of the Nd123 single crystals as well as in the bulk crystals prepared by the oxygen-controlled-melt-growth (OCMG) method. The composition variation of Ba/Nd is observed in the matrix of Nd123 crystals by an analytical TEM equipped with a cold field-emission gun. It turns out that the enhancement is due to the field-induced pinning effect ascribed to the weak superconducting Nd---Ba substitution regions in the Nd123 matrix.     

Mixed conductivity in SrCe0.95Yb0.05O3 protonic conductors

The results of electrical conductivity measurements on SrCe_0.95Yb_0.05O₃ under controlled oxygen partial pressure and temperature are presented. A defect model consistent with experimental results is proposed which provides for P_O2^−1/4 dependent n-type, P_o2-independent oxygen ion and P_O2^+1/4 dependent p-type conductivity components. The band gap, reduction, oxidation and ion-migration energies are determined from an analysis of the data in terms of the proposed defect model. These results suggest that some earlier data interpreted in terms of protonic conduction may require re-evaluation.     

Thermally activated flux dissipation in c-axis-oriented YBa2Cu3O7−δ ultrathin films

The resistive transitions of ultrathin YBa₂Cu₃O_7−δ (YBCO) films with thicknesses 75 and 200 Å were studied under magnetic fields. For the 75 Å film under a 5 T parallel magnetic field (Hbab-plane), no broadening of the resistive transition occurred. In the perpendicular magnetic field (H ab-plane), the broadening of the resistive transition of the 75 Å film is larger than that of the 200 Å thick film. The flux activation energy U was found to be linearly dependent on the temperature and logarithmically dependent on the magnetic field for both 75 and 200 Å films, which means the two samples have a two-dimensional vortex lattice. Furthermore, the activation energy U also increased with the film thickness, indicating that the magnetic correlation length in the c-axis direction l_c is larger than the 200 Å for bulk YBCO.     

Influence of fluctuations on thermal conductivity of high-Tc YBa2Cu3O7−δ superconductor

To study a behavior of the thermal conductivity near T_c specific heat and thermal diffusivity of the YBa₂Cu₃O_7−δ high-T_c ceramics were simultaneously measured. Close to T_c = 92.30 K the thermal diffusivity and the thermal conductivity discovered minima and the specific heat – maximum. Quantitative analysis of the influence of thermodynamical fluctuations showed the same power laws with Gaussian exponent equal to 0.5 and existing of crossover from the 3D Gaussian to 3D XY critical behavior in the specific heat and thermal conductivity at the approach to T_c. To explain the minimum in thermal conductivity at T_c we propose a mechanism of scattering of phonons on the superconducting fluctuations.     

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.     

Interlayer tunnelling in Bi2Sr2CaCu2O8+δ single crystals

We present measurements of the intrinsic quasi-particle conductivity along the c-axis of 2212-BSCCO single-crystal mesa structures in the superconducting and normal states. Direct measurement of the mesa temperature enables corrections to be made for self-heating and permits the acquisition of reliable I–V characteristics over a wide range of temperatures and voltages. Unlike a conventional superconductor, there is no evidence for any change in the quasi-particle conductivity at T_c, consistent with precursor pairing of electrons in the normal state. At low temperatures the initial low-voltage linear conductivity exhibits a T² dependence, approaching a limiting value at zero temperature.     

Effect of cobalt substitution on cationic distribution in LiNi1 − y CoyO2 electrode materials

A crystal chemistry study of LiNi_{1 − y}Co_yO₂ phases, used as positive electrode in lithium batteries, is presented. These materials crystallize in the rhombohedral system (space group: R m) with a layered structure. Rietveld profile refinement of the X-ray data shows that for low substitution amounts ( ≤ 0.20) extra-nickel ions are always present leading to the Li_{1 − z}Ni_{1 + z − t}CotO₂ (t = y(1 + z)) formula (z * > 0), while for y ≥ 0.30, a pure 2D structure is obtained (z = 0). The stabilization of the 2D character of the structure by cobalt substitution in lithium nickelate leads to the improvement of the electrochemical properties.     

Asymmetric phase diagram and phase separation in Pr0.5−δCa0.2+δSr0.3MnO3 (−0.04δ0.04)

We present electric and magnetic properties of polycrystalline Pr_0.5−δCa_0.2+δSr_0.3MnO₃, for δ between −0.04 and 0.04, where the hole concentration is n=0.5+δ. In this series, we study the effects of moving n away from 0.5 on both, the phase diagram and phase separated state. We found that the low temperature ferromagnetic fraction X_FM continuously decreases when n increases. As a result, the samples with n<0.5 (large X_FM) exhibit metallic resistivity at low T while for n>0.5 the insulating state predominates. We construct a detailed T–n phase diagram showing the asymmetries around half-doping.     

Low temperature magnetocaloric effects in Dy1Ba2Cu3O7−δ and Y1Ba2Cu3O7−δ high-Tc single crystals

The heat release has been measured in high temperature superconductors during and after a change of the external magnetic field μ₀H_a ≤ 0.5 T applied parallel to the c-axis at 0.1 K ≤ T ≤ 0.45 K. Two Y123 and one Dy123 twinned single crystals were investigated. An analysis of the heat release based on the Bean model and on a model for thin superconductors in perpendicular geometry recently proposed by Brandt et al. has been carried out. During field sweep we measured ∝ H_a²dH_a/dt. This dependence can be understood within the Bean model for longitudinal geometry. The critical current densities obtained with this method are in good agreement with those from magnetization measurements. We also present measurements, and a first quantitative analysis, of dissipation due to the time relaxation of the flux line lattice after a field sweep. For the heat release a t⁻¹ dependence has been found which corresponds to a logarithmic time dependence of the magnetization. The normalized relaxation rate we obtained is in agreement with literature values.     

Ba2YCu3O7−δ crystal surface layers: Orthorhombic splitting, dislocations, and chemical etching

We find by transmission electron diffraction that the orthorhombic splitting of the upper surface layers ( <1 μm) of single crystal Ba₂YCu₃O_7−δ is reduced, differing by 10 to 30 percent from the bulk value. We also find by transmission electron microscopy that in general the surfaces are of inferior quality and, thus, not representative of the bulk. These results have important consequences for those experiments that probe only the upper surface layers. By etching with Br/ethanol and HClO₄/NaClO₄ the poor quality surfaces are removed.     

Fabrication and growth rate estimation of PrBa2Cu3O7−δ single crystal by the modified top seeded crystal pulling method

Recently, we succeeded in fabricating single crystals of PrBa₂Cu₃O_7−δ by a modified top seeded crystal pulling method called the SRL-CP (Solute Rich Liquid-Crystal Pulling) method. Y₂O₃ and MgO polycrystalline crucibles and a MgO single crystal crucible were used to grow the single crystals. The crystal growth temperature was set in the range of 968°C to 972°C. The grown crystals were identified as PrBa₂Cu₃O_7−δ by X-ray diffraction. In the case of using Y₂O₃ crucibles the composition of the grown crystals was Y_xPr_1−xBa₂Cu₃O_7−δ (0.48 < x < 0.57) and in the case of using MgO crucibles a relatively small amount of Mg contamination to the grown crystals occurred at a typical concentration of approximately 1 at.% of the sum of cations. According to the crystal growth model of the SRL-CP method [1–5], a maximum growth rate of 1.7 × 10⁻⁵ cm/s was calculated with the aid of the phase diagram studies we reported earlier [6]. This value is reasonably in agreement with the experimental results.     

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.     

Magnetostrictive behaviour of Fe73.5Si13.5B9Nb3−xMoxCu1 alloys

Magnetostriction, dilatation and calorimetric measurements were performed on FINEMET type as-quenched and heat treated ribbons. Nb was gradually replaced by Mo in order to study the influence of the refractory elements exchange on several magnetostriction parameters. The results could be correlated with magnetic and structural transformations throughout thermal treatments and assured that the whole series is suitable for technical applications.     

Self-assembly of β-Ga2O3 nanobelts

Self-assembly of β-Ga₂O₃ (beta-gallium oxide) nanobelts with diameters of 50–100 nm and lengths of tens to hundreds of microns have been studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). Under appropriate conditions such as nanobelts concentration, controlled solvent evaporation, β-Ga₂O₃ nanobelts assemble into a fan-like structure on the substrate. A tendency of these nanobelts to align parallel to each other was also observed. The mechanism behind the formation of self-assembly of β-Ga₂O₃ nanobelts has been proposed on the basis of lateral capillary forces.     

On ionic conduction in the α-phase of PbSnF4

The structure re-refinement of tetragonal PbSnF₄ was executed using data reported earlier. The rms amplitude in M2(Sn) site is larger in (001) plane than along the c-axis and the thermal vibrations of F3 fluorine ions are very large, i.e. B_eq = 12.415(20) A². M2F₈ polyhedra form a distorted cube. The fluorine ions on the F3 site are present between the M2 ion layers. The fluorine ions on the F3 site are located between the M2 ion layers and their weak bonds to Sn ions play an important role in the conduction. The ionic conductivity in the (001) plane is higher than that in the 001 direction.     

Structural study and magnetoresistance effect of epitaxial La0.67Sr0.33MnO3–δ and Pr0.7Ca0.3MnO3−δ multilayer films

La_0.67Sr_0.33MnO_3−δ (LSMO) and Pr_0.7Ca_0.3MnO_3−δ (PCMO) multilayer epitaxial films, which were fabricated with different LSMO and PCMO layer thickness on LaAlO₃ single crystal substrates of (0 0 1) orientation by a direct current magnetron sputtering technique, were studied further, after the structure, magnetoresistance effect and magnetic properties of LSMO/PCMO/LSMO (LPL) trilayer epitaxial films were systemically studied. The superlattice structures of multilayer films were observed according to the diffraction peaks of X-ray diffraction patterns at small angles. The metal–insulator transition temperature (T_P) and peak resistivity (ρ_max) obviously changed when we altered the thickness of PCMO middle layer and the intra-field related with the thickness of those layers and their interaction. Considering the effect of the distribution of electrical field and current, and the interaction among the layers of LSMO and PCMO, an effective fact n* was introduced to replace n (the number of layer). All the calculated values of ρ (the resistivity of multilayer films) accorded with the experimental values.     

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.