Assessment of role of iron ions on the physical and spectroscopic properties of multi-component Na2O−PbO−Bi2O3−SiO2 glass ceramics

Multi-component glass ceramics composition Na₂O?PbO?Bi₂O₃?SiO₂ doped with different concentrations of Fe₂O₃ as nucleating agent were characterised by XRD, SEM (scanning electron microscope) and DTA (differential thermal analysis) techniques. Optical absorption, EPR, FTIR and Raman studies are also carried out on these glass ceramics. Absorption bands observed at about 457, 489, 678 and 820 nm are the characteristics of Fe³⁺ ions whereas the band observed at about 964 nm is due to Fe²⁺ ions. EPR studies suggested that Fe³⁺ ions entered in the lattice as tetragonally distorted octahedral symmetry or rhombic sites at low concentration of Fe₂O₃, whereas at higher concentration of Fe₂O₃ (beyond 1 mol%), the super exchange type of interactions between multivalency iron ions begin to dominate. FTIR and Raman spectra have revealed the behaviour of various structural units in the glass ceramic matrix. The analysis of these spectroscopic studies indicates that iron ions do exist in Fe³⁺ and Fe²⁺ state.     

Fluorination of superconducting Ba2YCu3O9−δ

Using a series of samples ranging in composition from δ = 2 to δ = 3 we have successfully introduced substantial amounts of fluorine into samples of superconducting Ba₂YCu₃O_9-δ by annealing under F₂ gas flows at low temperatures. These syntheses yielded single phase materials containing up to 1.05 F per formula unit. ¹⁹F NMR experiments have confirmed that fluorine is incorporated into the lattice and susceptibility and transport measurements indicate that the samples are superconducting with critical temperatures in the range 80 to 89 K.     

Tunneling conductance of a Bi2−xPbxSr2Ca2Cu3O10−y-SnO2 junction

Fine structures were observed in the tunneling conductance of a sintered Bi 2223-SnO₂ junction. The structures are weaker than those of a single crystalline Bi2212. They correspond to the Raman spectrum of Bi2223 and approximately to the phonon density of states of Bi2212. The structures must therefore be phonon structures, and phonons may contribute substantially to highT _c superconductivity. Multiphonon structures are scarcely discernible. Hence we propose a new model, in place of the prior multiphonon model, to explain the rapid increase inT _c with the CuO₂ layer number. 2 (21 K)=68±4 meV inT _c=98±5 K. 2 (0)/k _B T _c is 8.1±0.9. The temperature dependence of the gap was also observed and discussed.     

Magnetic properties of superconducting EuBa2Cu3O7−x

The magnetic properties of superconducting EuBa₂Cu₃O_7–x with resistiveT _c 96.5 K are measured. The normal state magnetic susceptibility is analyzed within the framework of the Van Vleck-Frank theory, leading to the conclusion that the strong moments of the Eu³⁺ ions are uncorrelated, and do not affect the superconducting state.     

Normal state resistivity of YBa2Cu3O7−x

A systematic study has been carried out on the normal state resistivity of YBa₂Cu₃O_7–x . Samples were cut from the same well-annealed material and were quenched from different temperatures (T _Q ). The resistivity is metallic whenT _Q 500 °C and becomes semiconductor-like whenT _Q 600 °C. The data on the latter was interpreted in terms of the three-dimensional localization model proposed by Mott.The work at USCD was supported by the California MICRO program     

Infrared spectra of superconducting La2−xSrxCuO4 and YBa2Cu3O7−δ

Abstract

Abstract Infrared spectra of La_2?xSr_xCuO₄ and YBa₂Cu₃O_7?δ are discussed, specially with respect to the disappearance of the high-frequency (～650 cm) band of the superconducting compositions at 300K. Some of the bands persist at 300K eventhough the materials are fairly conducting. YBa₂Cu₃O_7?δ does not show evidence in the far IR spectrum for the presence of an optical gap.     

Oxygen ion conduction in 12CaO·7Al2O3: O2− conduction mechanism and possibility of O− fast conduction

12CaO·7Al₂O₃ (C12A7) with a unique nano-porous structure and free O^2? ions entrapped in sub-nanometer-sized cages is a fast oxygen-ion-conducting material. These free O^2– may be replaced by various oxygen-related species, OH^?, O^2? and O^?, by tuning the atmosphere during the heat treatment. We examined the conduction mechanism for stoichiometric C12A7 (C12A7:O^2?), in which O^2? ions exist as counter anions in sub-nanometer-sized cages, by Raman measurement of C12A7:O^2? annealed in a dry ¹⁸O₂ atmosphere. It was revealed that the primary ion conducting species is an O^2? ion which diffuses via exchange with O^2? in the cage wall. An experimental result on the sample containing O^? ions implied that O^? is more mobile than O^2? in C12A7. Ab initio calculations on the diffusion paths of O^2? and O^? ions in C12A7 supported the above experimental results.     

Synthesis and characterization of (Bi2O3)1−x−y−z(Gd2O3)x (Sm2O3)y(Eu2O3)z quaternary solid solutions for solid oxide fuel cell

Sm₂O₃, Gd₂O₃, Eu₂O₃ triple-doped Bi₂O₃ based quaternary solid solutions were synthesized as a candidate electrolyte material using the solid-state reaction technique. The structural, thermal and electrical conductivity features of the ceramic samples were examined and compared by using X-ray powder diffraction (XRD), thermal gravimetry/differantial thermal analysis (TG/DTA) and the four-point probe technique (4PPT). The result of XRD measurements indicated that the (Bi₂O₃)_{(1−x−y−z)}(Gd₂O₃)_x(Sm₂O₃)_y(Eu₂O₃)_z (x = 10/y = 10/z = 5, 15, 20 mol % and x = 10/y = 5, 10, 15, 20/z = 10 mol %) samples have a stable face-centered cubic δ-phase and mixed phase crystallographic structure. The phase stability was also checked by the DTA evaluations results. The temperature dependent electrical conductivity measurements showed that the highest electrical conductivity was observed for the sample of the (Bi₂O₃)_0.75(Gd₂O₃)_0.10(Sm₂O₃)_0.05(Eu₂O₃)_0.10 system which has a stable and δ-phase was found as 6.67 × 10⁻³ (Ω cm)⁻¹ at 650 °C. This sample can be used as an electrolyte material in the solid oxide fuel cells (SOFCs) which is possible to operate at intermediate temperature ranges. The activation energy was also calculated at a low temperature range (350–650 °C) and high temperature range (above 650 °C). The values for the samples vary from 0.63 eV to 1.08 eV at low temperature and at high temperature they vary from 0.43 eV to 0.75 eV.     

Anisotropic optical properties of single-crystal GdBa2Cu3O7−δ

The optical spectrum of reduced-T _c GdBa₂Cu₃O_7– has been measured for polarizations parallel and perpendicular to theab plane. The sample was an oxygen-deficient single crystal with a large face containing thec axis. The polarized reflectance from this face was measured from 20–300 K in the spectral region from 30–3000 cm^–1, with 300 K data to 30000 cm^–1. Kramers-Kronig analysis was used to determine the spectral dependence of theab and thec components of the dielectric tensor. The optical properties are strongly anisotropic. Theab-plane response resembles that of other reduced-T _c materials whereas thec axis, in contrast, shows only the presence of several phonons. There is a complete absence of charge carrier response alongc aboveand belowT _c. This observation allows us to set an upper limit to the free-carrier spectral weight for transport perpendicular to the CuO₂ planes.Permanent address: Institute of Physics, CSAV, Prague, Czechoslovakia     

Local electronic structure of Cu2O,CuO and YBa2Cu3O7−δ

Cu 3d and O 2p electronic states of Cu₂O, CuO, and the highT _c compound YBa₂Cu₃O_7– have been probed by means of high resolution x-ray emission spectroscopy (XES). The CuL and OK XES bands are compared in detail with recently reported x-ray photoelectron and ultraviolet photoelectron spectroscopy (XPS and UPS) measurements and densities of states obtained by local density functional (LDF) theory. The XES data show that the hybridization between Cu 3d and O 2p states is completely modified in CuO and YBa₂Cu₃O_7–, whered-d correlation energy is large, as compared to LDF predictions. Such is not the case for Cu₂O where agreement between theory and experiment is good.The Cu 3d states are found to be highly localized in YBa₂Cu₃O_7– (though less so than in CuO). The O 2p states lie at lower binding energies than in the simpler oxides and are mainly situated above the Cu 3d states. The respective positions of the centre of gravity of the OK emission bands on an x-ray energy scale indicate that the oxygen sites are less well screened by the O 2p states in the highT _c compound. This provides indirect evidence for the presence ofd-like states at the oxygen sites.     

Europium-doped nanocrystalline Y2O3−La2O3 solid solutions with bixbyite structure

Nanocrystals of Y₂O₃ and La₂O₃ solid solutions were synthesized with a cubic bixbyite structure containing La₂O₃ content of up to 50 mol%. This is comparatively higher than that in bulk materials of the same structure, where La₂O₃ content of only 20 mol% can be obtained. A set of europium-doped (Y_1−xLa_x)₂O₃ (x=0.1, 0.2, 0.3, 0.4) cubic bixbyite solid solutions with crystallites of approximately 10 nm in size was prepared using the polymer complex solution method. Structural analysis was performed using X-ray diffraction measurements, Rietveld full profile refinement, and from Eu³⁺ luminescence emission. The energy levels of the Eu³⁺ ion, second order crystal field parameters, and crystal field strength were obtained for all compositions of solid solutions. We show that the crystal field parameters linearly depend on unit cell parameter and that these dependencies may be considered as part of an overall dependence for the entire sesquioxide family.     

Influence of Zn concentration on electrical resistance of SmBa2(ZnxCu1−x 3O9−δ

It is known that perovskite type structures (ReBa₂Cu₃O_9–) exhibit superconductivity at temperatures below 90 K /1–3/. The substitution of other ions for Cu is interesting because the Cu-O interactions are probably responsible for the supercoductivity in those systems /4/. In the system Y-Ba-(Ag,Cu)-O Saito found that the gradual decrease of T_c with the increase of Ag concentration is due to the presence of the different phases /5/.In this letter we are reporting the experimental measurements of the electrical resistance of SmBa₂Cu₃O_9– oxygen defect perovskites with Zn substituted for Cu.     

Relaxation phenomena in Cr3+ doped Al2O3−Fe 2 57 O3 systems

Mössbauer absorption spectra have been measured for Cr³⁺ doped Al₂O₃?Fe ₂ ⁵⁷ O₃ systems for different values of the Cr³⁺ concentration at room temperature. The cross relaxation between Fe³⁺ and Cr³⁺ ions, which destroys the paramagnetic hyperfine structure of Fe⁵⁷ observed in undoped Al₂O₃?Fe ₂ ⁵⁷ O₃, is thoroughly studied. The experimental results suggest a new kind of cross-relaxation process involving three spins, i.e. two Fe³⁺.ions and one Cr³⁺. The process, though it is a higher-order one, is highly effective because it is energy-conserving.     

Effects of heating on the Raman spectra of YBa2Cu3O7−δ

We report effects of heating to the intensities of Raman modes in the spectra of single-crystals embedded in ceramic YBa₂Cu₃O_7– pellets, and compare the results with those from YBa₂Cu₃O_7– thin-films. Heating was done by either increasing the laser-beam power or resistively heating in a heating cell. From the measurements on a single-crystal in z(xx) polarization, we find that the relative intensity of the B_1g mode of the plane oxygens to that of the A_1g mode of apical oxygens decreases strongly as the samples are heated. For a crystal in near x(zz) polarization, the relative intensity of the two modes increases up to certain value. In thin-films, however, no such change was observed even when heated to higher temperatures than the crystals were. Therefore, we interpret that the change in the relative intensity of the two modes of single-crystals is not due to electronic or structural changes nor thermal decomposition in the heated samples. We propose that a single-crystal, when heated, is fractured into many micro-crystals and these micro-crystals thermally fluctuate in orientations. For thin-films, such fluctuation in orientations might be hindered because there are only a few layers of micro-crystals on top of the substrate. Scanning electron micrographs (SEM) of the heated part of the samples seem to provide the evidence of the micro-crystals.     

Study of YBa2Cu3O7−δ ceramics/Al interface

Properties of oxide layers at the interface between Al metal and YBa₂Cu₃O_7−δ ceramics were investigated using X-ray diffraction (XRD), X-ray photoelectron spectra (XPS) and impedance measurements. There have been found the oriented grains having their c-plane parallel to the surface of YBa₂Cu₃O_7−δ. When Al metal was evaporated onto the ceramics sample, the aluminum oxide layer was produced at the interface between Al and YBa₂Cu₃O_7−δ because Al metal oxidizes more easily. The oxygen-deficiency was observed at the ceramics side of the interface as examined by X-ray photoelectron spectra. This oxygen-deficiency can be partly replenished by post annealing whereas it can be fully replenished for the sample to which the mechanical polishing is applied beforehand in order to remove the oriented grains. The thickness of aluminum oxide layer was evaluated by means of the impedance measurements using the alternating current three-terminal method.     

Twins of YBa2Cu3O7−x and origin of four orientation variants

Abstract

Twins are often visible in YBa₂Cu₃O_7?x samples by X-ray diffraction and electron imaging or diffraction. The origin of four different orientation variants are related here to the 4/mmm to mmm transformation.     

Features of the twin structure of YBa2Cu3O7−x epitaxial films

X-ray diffraction is used to investigate YBa₂Cu₃O_7?x (YBCO) films on NdGaO₃(110) and a ${{(100)CeO_2 } \mathord{\left/ {\vphantom {{(100)CeO_2 } {(1\bar 102)}}} \right. \kern-0em} {(1\bar 102)}}Al_2 O_3 $ heterostructure. Symmetric, asymmetric, and axial geometries for θ and θ/2θ scans are used to obtain diffraction spectra from different crystallographic planes. The orientational and quantitative twinning characteristics of the films are determined. While the crystallographic parameters of these two types of film (the films are c-axis oriented with c=11.67 Å) are similar, there are differences in the twin structure. In particular, the features of the NdGaO₃ structure lead to the appearance of an angle differing from 90° (90.20°) between the possible (110) and θ/2θ twin planes in a YBCO film and a different number of twin components in each system of twins. It is concluded from an analysis of the broadening of reflections, which are sensitive to twinning, that there is not twinning in a 60% film of YBCO on Al₂O₃ with a CeO₂ buffer layer.     

NMR study of Na3−xRu4O9

Low-dimensional conductor Na_3−xRu₄O₉ has been studied by means of ²³Na nuclear magnetic resonance measurement in order to clarify the electronic state of this compound. The magnetic susceptibility χ is almost constant from 100 to 300 K, then increases with temperature, and shows a kink at 584 K. The temperature dependence of the Knight shift K is almost in proportion to χ. From the result of the temperature dependence of spin–lattice relaxation time, it has been found that this compound has an energy gap, Δ, which is closely correlated with the gap-like behavior of χ. Consequently, we consider that there exists a spin-singlet state in all or a part of RuO₆ chains in Na_3−xRu₄O₉.     

EPR study of the high-TC superconductor YBa2Cu3O7−δ

EPR spectra of superconducting YBa₂Cu₃O_7-δ and insulating Y₂BaCuO₅ have been examined. The intensity of Cu²⁺ ions in YBa₂Cu₃O_7-δ is about 1/3000 of that in Y₂BaCuO₅ at room temperature. Owing to the Meissner effect in the superconducting state, the EPR signal of Cu²⁺ ions in YBa₂Cu₃O_7-δ disappears; moreover the EPR signal of DPPH deposited on the YBa₂Cu₃O_7-δ specimen is shifted. An additional EPR line is found for YBa₂(Cu_2.94Cr_0.06)O_7-δ at temperatures below 113K; this can be related to the phenomenon of superconductivity.     

Specific heat studies of high-Tc superconductor YBa2Cu3O7−x

Specific heat studies of the high-T_c superconducting compound YBa₂Cu₃O_7−x with bulk transition temperature at 92K are reported. A distinct anomaly of electronic origin in the specific heat is observed with granular-like behavior corresponding to a Sommerfeld constant γ = 7±2mJ(moleCuK²)^±1 Debye temperature (φo ≈ 400K) is obtained by fitting the experimental data with the theoretical Debye specific heat.