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Superconducting thin films of high Tc cuprates have been prepared using wet chemical precursors, which are spun on a substrate, pyrolyzed and heat-treated. This new method is simple and inexpensive, and is easily amenable to scale-up to cover large areas. No vacuum equipment is required. The technique allows easy manipulation of film stoichiometry and gives films having excellent compositional uniformity. A 1600 A film of Ba2YCu3O7 prepared by this method had a room temperature resistivity of 500/xfzcm, Tc/(onset) of 90K, and R=0 at 58K. The preparation and electrical and microstructural characterization of thin films of Ba2YCu3O7 and other high TC cuprates will be discussed.
Orientation ordered high-Tc oxide films of Y1Ba2Cu3O7 were prepared by molecular beam epitaxy on SrTiO3 substrates. A combination of effusion cells and e-beam evaporators was used with the addition of an oxygen jet. The superconducting phase is formed by further O2 anneal at temperatures ≥800° C. For SrTiO3 (100), the Y1Ba2Cu3O7 films grow in the orientation of either the c-axis or the a-axis perpendicular to the film plane. Films with predominant “c⊥” orientation exhibit a high degree of crystalline order with a rocking curve 0.3° wide. The Jc is about two times higher than those with the “a⊥” orientation of a comparable Tc (R=0). For a typical film of 9000Å thickness, a Tc (R=O) of 87K, and a Jc of 7 × 104 A/cm2 at 77K were reproducibly achieved. For SrTiO3 (110), X-ray showed twinning of (110) and (103) orientations in Y1Ba2Cu3O7, thus precluding the observation of anisotropy expected for the in-plane axes of  and .
Transmission and scanning electron microscopy were used to study some features of twins in the orthorhombic phase of Y1Ba2Cu3O7-Y compounds. A model that explains the formation and proliferation of thene defectr, is proposed. Some conclusions about the kinetics of formation of these defects are stated, which agree with observed changes in twin densities produced by different cooling rates. Electron energy loss spectrometry (EELS) was ucod to measure relative changes in oxygen, which give some information about the relative value and the stability of oxygen content in twinned regions. A Braggs-Williams model of the order-disorder transition, for oxygen occupancies in the Cu-O2 planes, predicts an enrichment of vacancies at the boundaries in these oxygen deficient perovskites. This could explain the observed deficiency in oxygen content with respect to the perfect Y1Ba2Cu3O7 stoichio-metry.
The interactions of YBa2Cu3O7-δ type high Tc superconductors with other metals and oxides are of significant technical importance because of the need for i) proper stabilizing normal metal for composite superconductor wire, ii) nonreactive crucible materials for melt processing or crystal growth, and iii) suitable nonpoisonous substrate materials for thin film/thick film superconducting devices. For these reasons, and also for the purpose of exploring possible improvements in Tc, Jc and mechanical properties, the effects of various metal and oxide additions (1–40% by weight) have been investigated. It is shown that many of the elements in the periodic table deteriorate the superconducting properties to a various degree ranging from a broadened transition or reduced Tc to a complete elimination of the superconducting behavior. However, silver, gold and cadmium were relatively benign or slightly improved the properties. These benign materials have potential for practical application in superconducting composites.
The effect of changes of oxygen stoichiometry on the properties of Ba2YC3O7-σ is discussed. Crystallographic, susceptability, resistivity, and specific heat data from 1 set of samples prepared by Zr gettered annealing are described and discussed.
Grain boundaries in YBa2Cu3O7−x. thin films deposited on yttria-stabilized cubic zirconia have been characterized using selected-area diffraction. In addition to twin boundaries, several types of low-angle and high-angle grain boundaries are frequently found in these films. The high-angle boundaries include 23.5°, 29°, and 45° rotations about  and 90° rotations about  or . These boundaries are compared to special high-angle grain boundaries in cubic materials.
We have explored the effects of ion beam irradiation on the electrical and structural properties of superconducting thin films of YBa2Cu3O7-δ. Damage created by nuclear energy loss processes degrades the superconducting transitions. In general, the onset temperatures do not vary significantly with ion fluence, but the transition widths broaden until the resistance no longer reaches zero. This behavior is strikingly similar to that observed in granular superconducting films where islands of superconductor are progressively decoupled from each other, destroying the phase coherence. Data from resistance measurements as well as from Rutherford Backscattering and channeling measurements suggest that ion bombardment is not changing the volume fraction of superconducting material substantially.
We have fabricated tunnel junctions between chemically etched single crystals of YBa2Cu3O7-δ and evaporated metal counterelectrodes which exhibit reproducible characteristics. Above the bulk critical temperature of YBa2Cu3O7-δ, Tc, the conductance, G(V), has a linear dependence with voltage and has some asymmetry. Below Tc, additional structure associated with the superconductivity appears in G(V). At T>>Tc there is a reproducible finite zero bias conductance.
Based on very recent experimental evidence about magnetic transitions in high-Tc superconductors the role of superconductivity and magnetism is analyzed. A model of interacting electrons in a one-dimensional system is constructed, taking into account that antiferromagnetic interactions in the underlying lattice are present. The origin of this antiferromagnetism could be due to local Y d-electrons or rare earth f-electrons, related to the structure. Self-consistent calculations in this model show the possibility of a new state, with a gap, in which there are electron pairs. The characteristics of this new state are discussed in relation to superconductivity. The results of this model suggest that an extension of it could be applied to the new superconducting ceramics.
Optical data over a broad energy range (∼ 0.01 eV to ∼ 6 eV) for a series of La2−xSrxCuO4-δ compounds are obtained in parallel with the Meissner effect and the superconductivity transition temperature, Tc. Two noteworthy trends in the optical spectra are observed as the Sr concentration is increased in small steps from x = 0 to x = 0.3. First is the appearance of a low frequency band in the reflectivity, R, whose strength follows closely the Meissner effect and Tc measured on the same set of samples. The position of the onset of this band is pinned at ∼0.9 eV for all values of x. The origin of this band in R is identified as an absorption process due to an electronic transition with a large oscillator strength. Second is the appearance and disappearance of an intense vibrational mode whose strength also tracks “superconductivity”. This sharp structure in the far infrared is a characteristic vibrational mode associated with the dopant induced electronic state.
We have prepared low leakage tunnel junctions on epitaxial YBa2Cu3O7 (YBCO) films grown on SrTiO3(001) by evaporating Pb counterelectrodes onto chemically etched YBCO surfaces. Structure in the voltage dependence of the tunneling conductance is reproducible and strongly resembles what has been obtained in similarly etched junctions on YBCO single crystals.
This study presents two methods for preparing the High Tc superconducting YBa2Cu3O7−x compound. Aqueous nitrate solutions consisting of Yttrium, Barium and Copper were mixed, dried, blended and the resulting homogeneous mixture calcined at 700–900°C for 2–4h to develop the superconducting (1,2,3) phase. As an alternative, oxalates of Yttrium, Copper and Barium were coprecipitated from the mixed metal nitrate solution using (Et3NH)2C2O4. The resulting pale blue coprecipitate was dried and calcined in air at 700–900°C/2–4h. Both methods provided high homogeneity precursors for the High Tc YBa2Cu3O7−x superconductor. Resistance measurements, SEM, x-ray and VSM were used to characterize the microstructures and properties.
Quench-condensed films of simple superconductors can be deposited with a morphology which is either granular (grain sizes on the scale of tens of angstroms) or homogeneous. Transport and tunneling studies of the normal and superconducting states of these films as a function of sheet resistance have revealed profound differences between them. In uniform films Tc. and the energy gap decrease continuously with decreasing film thickness. Superconductivity is destroyed by the reduction of the amplitude of the order parameter. In granular films, the grains are sufficiently large to support superconductivity in each grain. Long range phase coherence is destroyed by intergrain phase coherence breaking.
Zn substitution for Cu in YBa2Cu3O7 rapidly reduces the superconducting transition temperature, Tc. Superconductivity is quenched between x=0.08 (T =30 K) and x=0.10. The normal state paramagnetism grows with Zn substu-tition, presumably due to increased localization on the Cu sublattice. Susceptibility studies of oxygen depleted (nonsuperconducting) Zn-substituted samples support this. Strong non-linear isothermal magnetization suggesting an internal magnetic field is found at T=4.2 K in samples with Zn concentration near to the critical value for suppression of superconductivity. The results are discussed in terms of increased localization of d-electrons on the Cu sites with increasing Zn concentration, which is consistent with recent EPR data.
Single phase orthorhombic YBa2(Cuy1−xZnx)3O7 samples were formed for 0<x<0.16. The high T superconductivityXfor x=6 (T =90 K) is rapidly depressed with increasing x, and is quenched for x>0.08. Low field (<100 G) cooled magnetization studies show that the superconducting component decreases as x approaches the critical value for suppression of superconductivity, and this is supported by high resolution specific heat measurements in the vicinity of T. Temperature dependent electrical resistivity studies for x<0.08 show metallic behavior; for x>0.10 semiconducting behavior. The electrical resistance was studied at high quasihydrostatic pressures also, and for x=0.08 showed that T is depressed with increasing pressure: T → 0 K for P >10 GPa. This is in°contrast to YBa2(Cuy1−xZnx)3O7 where dT /dP>0. The data support evidence for the high sensitivity to chemical and ice perturbations of the physical properties of samples near the superconducting-normal transition region.