Polycrystalline samples of tetragonal YBa2Cu3O6.25 were transformed into the superconducting orthorhombic phase by annealing in an oxygen atmosphere at temperatures ranging from 400–850°C and then slowly cooled to room temperature (15°C/h). Transmission electron microscopy (TEM) images of these samples and samples prepared in the usual way show layers of amorphous or highly disordered material, several 100 nm thick, at a large fraction of the grain boundaries. Also all samples contain 10–100 nm thick sheets of disordered material which lie in the a-b planes and tend to run through the entire crystal grain. In the a-b planes we also observe dislocation loops, particularly in the as-quenched tetragonal samples and stacking faults in the heat-treated samples. We also frequently observe set of twins with orthogonal habit planes within a crystal grain. We attribute the low critical current density in YBa2Cu3O7 to these planar faults and the disordered grain boundary regions, and discuss the TEM observations with reference to resistivity and inductive measurements.

The oxygen ordering and exchange properties of Ba2−xLa1+xCu3O7±δ and BaLa4Cu5O13±δ are detailed. The crucial role of oxygen ordering for superconductivity is described.

The limiting substitution of Co or Fe for Cu in the orthorhombic superconducting phase YBa2Cu3O7−x yields the tetragonal, semiconducting compositions YBa2Cu2CoO7.25 and YBa2Cu2.5Fe0.5O7.19 after annealing at 400°C and slow-cooling in O2. Single-crystal x-ray structural analyses, conductivity and magnetic-susceptibility measurements, and TGA data provide evidence for Co or Fe substitution at the Cu(1) position and intercalation of peroxide ions (O2)2-. The two compositions decompose for disintercala-tion of oxygen beyond O6.7 for M=Co and O6.4 for M=Fe when heated in N2. The Cu(2) atoms of tetragonal YBa2Cu3O6 appear to be antiferromagnetic below a TN = 240 K, which is similar to comparable Cu-O planar nets in stoichiometric La2LnO4.

The structural, magnetic and superconducting properties of the mixed compounds YBa2Cu3−xMxO7-y (M = Ni,Zn,Fe and Co) are reported. Values of y, determined by titration, are found to be dependent on the nature and amount of the doping. The range of solubility is greater for the Fe and Co compounds (x = 1) than for those with Ni or Zn (x = 0.3). The undoped material is orthorhombic and remains orthorhombic after substitution for Cu by Ni or Zn, whereas a tetragonal phase is observed when Fe, Co are substituted for Cu. DC resistance and AC susceptibility measurements show that Tc is depressed from 90K (x = 0) to 45K (x = 0.2) for both the Ni and Zn doped compounds and Tc is destroyed in the Fe and Co doped compounds when x reaches 0.4. We suggest that a valence of 2 be assigned to the Ni and Zn and 3 to the Fe and Co ions.

We describe the properties of a model for the absorption of oxygen in the basal planes of YBa2 Cu3 O7-y. The model consists of a layered oxygen lattice gas in equilibrium with an external source of O2 wherethe Cu-mediated oxygen-oxygen interactions are coupled to the elastic energy of the crystal. Our predictions for the dependence of oxygen-ordering, and unit cell dimensions with temperature and oxygen partial pressure are in quantitative agreement with experiment.

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.

The ordering in the Cu-O basal plane of the high Tc superconductor YBa2Cu3Oz is investigated. Asymmetric pairwise interactions between nearest and next nearest neighbors are assumed. Ordering instabilities in two-dimensional k-space are mapped out as a function of the interactions and the ordered ground state superstructures consisting of occupied and empty oxygen sites are determined. A temperature-composition phase diagram is calculated by means of the Cluster Variation Method. The thermodynamic behavior of the superconducting compound is discussed in the light of these results.

Simple ionic models are applied to YBa2 Cu3 O7. It is found that additional forces are needed to constrain the barium and the planar coordinated copper atoms to be stable in their observed positions. These additional forces are compared to forces calculated from first principles. It is observed that the restoring forces are small for motion of the “in chain” oxygen atoms perpendicular to the chains.

The superconductivity of pseudo-quternary system Y1−xMx Ba2 Cu3 O7-δ, YBa2 Cu3−xM x O7-δ, where M stands Co,Cr,&Zn and with x=0,0.001,0.005,0.01 & 0.02, has been investigated.

The XRD analysis shows that the perovskite structure is preserved and a stabilization effect on orthorhombic structure by 3d elements addition was proposed. On the contrary, the microstructure has been modified prominently and it is determined by the sintering mechanism involved and/or diffusion process in each doped sample. Second phase precipitate can be found at grain surface. The superconductivity, however, has not been greatly affected.

Fluorine substitution for oxygen in the high Tc superconducting ceramic oxides is not only fundamentally but also technologically interesting. We have previously reported the observation of superconducting zero resistance transition at 155–168K, subsequently confirmed by several other groups. We have also observed diamagnetic signals and flux trapping at temperatures as high as 305K. The samples were made from solid-state reaction in a pressed pellet form. Because of the BaF2 formation and the small volume fraction, we have not yet been able to identify the specific high Tc phases.

In the course of elucidating and optimizing the fluorination effect, we have carried out other means of low-temperature fluorination experiments. The zero resistance at 154K was repeated.

In addition to the observation of these high 1c results, we found that a dopant amount of fluorine promotes the oriented crystal growth. We also found that the replacement of weakly bonded oxygen by fluorine can greatly enhance the material's stability by eliminating the serious problem of oxygen diffusion.

The superconducting performance, in particular the critical current, of polycrystalline YBa2Cu3O7 will depend strongly on the structure of grain boundaries and the nature and number of defects in the microstructure. To characterize the atomic structure of defects and grain boundaries in these materials, a high resolution electron microscopy study has been initiated. Emphasis has been placed on the technique of phase contrast imaging with corresponding computer simulation and processing for optimum interpretation of results.

Electron microscopical analysis of brown powders of composition YBa2Cu3O6.5 produced by oil quenching and conventionally produced orthorhombic GdBa2Cu3O7-δ show in both cases clear evidence for site exchange both between the different heavy metals and the heavy metals and the copper sites. For instance, the brown powder is a mixture of phases which are based upon two trigonal phases, both with a=0.536 and c=0.666 nm, one with the Y atoms stacked on the (111) planes of the parent perovskite structure and the second where the Y atoms of this structure have interchanged with one of the copper sites. The GdBa2Cu3O7-δ, material shows numerous planar defects on (001) planes which can be understood as copper rich regions with additional copper planes in the Ba or Gd sites. These results, together with earlier reports of order-disorder in YBa2Cu3O7-δ, strongly indicate that there exist ordering energies in these materials which may be important with respect to the current indications of the important of grain boundary phases in degrading the performance of some superconductors.

Since the discovery of the new high Tc cuprate superconductors [1,2] the oxygen stoichiometry of the compounds was of principal importance for the occurrence of the superconductivity.

Rapid solidification of YBa2Cu3O7−x, EuBa2Cu3O7−x and GdBa2Cu3O7−x has resulted in the formation of amorphous materials with crystallization temperatures in the range of 730–750°C. Higher temperature anneals in oxygen result in the evolution of the orthorhombic phase. The peritectic decomposition temperature for MBa2Cu3O7−x→M2BaCuO7 + liquid (M=Y, Eu, Gd) is in the range of 1035–1085°C with the Eu and Gd compositions having the highest values.

Enthalpies of formation of the perovskite-related oxides, La1.85 Sr0.15CuO4, YBa2Cu3Oy, with y = 6.93, 6.69, and 6.47 have been determined at 298.15 K by perchloric acid solution calorimetry. Enthalpies of formation and free energies of reactions with H2 O(g) and CO2 (g) have been evaluated. The partial molar enthalpy of solution of oxygen in YBa2 Cu3Oy has been determined and compared with values derived from measurements or the equilibrium partial vapor pressures of oxygen. The significance of the defect state thermochemistry in conductivity is identified.

Correlations between observed defect structures and the orientation of planes involved in grain boundary (GB) formation in single phase, near ideal density orthorhombic Ba2YCu3O7−x are presented. Coherent boundaries involving only a low energy network of dislocations at the interface are associated with boundaries not involving the (001) basal plane, while basal-plane-faced GBs are highly defective. These results are interpreted using a model for local stress based on the known anisotropie thermal contraction of the material during cooling from sintering temperatures. Scanning Auger microscopy of in situ fractured surfaces demonstrates that there is preferential segregation of carbon at the GBs as well.

Ordering of oxygen atoms in YBa2Cu3O6+x has been analysed by employing statistical thermodynamics ana the results are compared with the experimental data. The axial lengths a and b at room temperature were determined experimentally as a function of oxygen content and were found to show good agreement with the calculated lengths a and b. Special care was taken in the above experiment to dope oxygen atoms into the sample at low temperatures, typically 400° C. The superconducting transition temperature of the sample doped with oxygen at 400°C(starting material:YBa2Cu3O6.1.(decreases linearly with decreasing the oxygen content from 6+x=6.9(92 K) to 6.38(30 K) and decreased sharply around 6+x=6.35(5 K). No distinct superconducting phase corresponding to further ordered orthorhombic phase has been observed in this case.

The temperature and concentration dependence of the electron paramagnetic resonance spectra of YBa2(Cu1−xZnx)3O7 has been measured for 0≤x≤0.16. Zn substituted on the Cu-site cause a rapid nearly linear depression of the superconducting transition temperature Tc with Tc going to zero in the vicinity of x=0.10. Only weak EPR spectra due to ≤1% of the Cu-ions are seen in the superconducting phase of YBa2Cu3O7. These spectra are most likely attributed to Cu-ions in the vicinity of grain boundaries and do not represent a bulk response. However, a strong asymmetric resonance is observed in the Zn-substituted samples with x>0.1. The EPR results obtained for YBa2(Cu1−xZnx)3O7 are discussed in terms of a possible localization of d-electrons.

The dependence of the superconducting properties of RBa2Cu3−xMxOz (R = Y, Gd, M = Cr, Mn, Fe, Co, Ni, and x = 0.0, 0.025, 0.05, 0.1, 1.0, 3.0) on the oxidizing environment used during the processing (sintering/annealing) of these materials has been investigated. Samples of nominal composition, YBa2Cu3Oz, were prepared from the same starting materials and subjected to two different controlled heat treatments, under both controlled oxygen and ozone atmospheres. Measurements of ac electrical resistance versus temperature indicate that the critical temperatures are increased, and the widths of the superconducting transitions are narrowed for identically heat-treated samples when processed under ozone atmosphere rather than under an oxygen environment. Thermogravimetric analysis data indicate this trend to be correlated with increased oxygen content and thermal stability. This effect is also observable for materials with metal substitution for Cu, although the measured Tc's are generally lower for increased values of x. X-ray powder diffraction analysis showed the materials to be mostly single phase.

The effects of varying oxygen content on the superconducting transition temperature Tc, resistivity, and crystal structure of HoBa2Cu3O7−x (0 < x < 1) have been investigated. The variation of Tc wltn 8 is very similar to that previously reported by several authors for YBa2Cu3O7−x [1,2]. In particular a plateau in the Tc vs x curve is observed for values of x between 0.3 and 0.4 witfi the value of Tc,(10 % onset measured magnetically) remaining relatively constant at about 55 K. The width of the superconducting transition, as measured both resistively and magnetically, is substantially narrower for x= 0.35 + 0.05 than for slightly larger or smaller values of x. High resolution powder x-ray diffraction analysis was used to measure the lattice constants of both the orthorhombic and tetragonal phases as x was varied. With increasing x the temperature coefficient of the resistivity changed from positive (metallic) for x ≤0.2 to negative (semiconducting) for x ≥, 0.3. Since the general shape of the Tc vs x curve was unaffected by the complete substitution of magnetic Ho for Y, these results suggest an ordering of the oxygen vacancies in the a-b plane and the existence of an ordered compound with a Tc of 55 K.