Crystallographic and microstructural aspects of the superconductor YBa2Cu3O7-y —an overview

Crystal structures and structural inhomogeneities observed in YBa₂Cu₃O_7-y are reviewed. It is brought out that a proper understanding of the nature of the structural inhomogeneities is essential for exploiting the technological potential of this material. The need for an adequate characterization of specimens used for experiments is emphasized. Practical implications of the ferroelastic nature of the material are discussed.     

Orthorhombic to tetragonal phase transition in high TC superconductor YBa2Cu3O7-y and NdBa2Cu3O7-z under high pressure

Abstract

X-ray powder diffraction measurements for YBa₂Cu₃O_7-y and NdBa₂Cu₃O_7-y were made at the intense synchrotron radiation source under high pressure up to 5 GPa. These samples were wrapped tightly in platinum foil to avoid deoxidizing atmosphere. The orthorhombic to tetragonal transition temperature increases with pressure in both samples. These results are discussed on the basis of the disordering of the oxygen atoms on the chain sites.     

An “EPR” study of YBa2Cu3O7 and related high-temperature superconductors

Besides ag ≈ 2 signal which disappears on cooling to the superconductingT _c , YBa₂Cu₃O₇ and related oxides show a near-zero-field signal in the superconducting state with certain unusual features attributable to a “superconducting glassy state”. Contribution No. 443 from Solid State and Structural Chemistry Unit.     

Identification of the high-temperature superconducting phase in the Y-Ba-Cu-O system as the perovskite YBa2Cu3O7±δ

The oxide responsible for high-temperature superconductivity (onset ∼100 K, zero resistance above liquid N₂ temperature) is found to be YBa₂Cu₃O₇±δ. Contribution No. 432 from the Solid State and Structural Chemistry Unit     

Anomalous behaviour of sound velocity in the highT c superconductor YBa2Cu3O7

The longitudinal acoustic wave velocity in YBa₂Cu₃O₇ has been measured in the range 300 to 85 K using the ultrasonic pulse superposition technique. The sound velocity shows a steep drop in its value at 260 K and decreases continuously till the superconducting transition temperature. BelowT _c the sound velocity increases steeply. A hysteresis is seen when the experiments are performed during a cooling-warming cycle. The results are compared with recent measurements by Ewertet al on the samples with the same chemical composition.     

Structure of grain boundaries in YBa2Cu3O7 thin-film step-edge junctions

The atomic structure of 90° [100] (or [010]) tilt grain boundaries in YBa₂Cu₃O₇ thin-film step-edge junctions and, for comparison, in the interface between a-axis and c-axis oriented YBa₂Cu₃O₇ grains is investigated by means of high-resolution transmission electron microscopy. For (100)(001)-type boundaries two different structures are found. In the first a (001) CuO₂ plane of one grain faces a (100) Y–Ba–O plane of the other grain, in the second a (001) BaO plane faces a (100) Cu–O plane. In the former structure an incomplete unit cell of YBa₂Cu₃O₇ terminates at the boundary and a smaller strain in the adjacent CuO₂ planes is detected in comparison with the latter. It is found that a combination of a partial dislocation with a 124 stacking fault is a way to accommodate the lattice mismatch between c and 3a of YBa₂Cu₃O₇ in the boundary. For a symmetric (103)(103)-type boundary a displacement of the Cu-atoms of the CuO₂ planes is found near the boundary plane. From this a redistribution of the oxygen atoms around the Y-atoms located right in the boundary plane is inferred. The possible effect of the boundary structure on the superconducting properties of YBa₂Cu₃O₇ films is discussed.     

Effect of nominal copper concentration in YBa2Cu3±x O7−δ on the superconducting transition

Variation of the copper concentration in the nominal composition YBa₂Cu_3±x O_7−δ markedly influences the superconducting transition. The transition occurs at the highest temperature with lower width, whenx = +0·25. Communication No. 82 from Materials Research Laboratory.     

Effect of Zr,Ti substitutions onT c in superconducting YBa2Cu3O7−δ system

Zr and Ti have been substituted in the system Y_1−x M _x Ba₂Cu₃O_7−δ(M=Zr, Ti,x=0.05,0.1). We find that theT _c value is unchanged, ∼90K for Zr substitutions up to 10% and in the case of Ti substitutions theT _c drops significantly. These changes may arise from their site preference.     

Relation between highT c superconductivity and structure: A study of Ba3+x Cu6O14+δ and YBa2Cu3O7−δ systems

Superconductivity is found in tetragonal La_3−x Ba_3+x Cu₆O_14+δ and La, Ba)_6−x Sr _x Cu₆O_14+δ even though they do not possess Cu-O chains or the K₂NiF₄ structure. Resistivity measurements confirm the occurrence of a transformation from chain-superconductivity to sheet-superconductivity in YBa₂Cu₃O_7−δ as δ is varied in the range 0.0–0.5. Contribution No. 481 from the Solid State and Structural Chemistry Unit     

Mössbauer study of Fe-substituted orthorhombic and tetragonal YBa2(Cu1-xFex)3O7-σ system

Mössbauer study of orthorhombic and tetragonal YBa₂(Cu_1-xFe_x)₃O_7-σ;x=0.02, 0.04, 0.08 has been done to investigate the two inequivalent Cu-sites. Fe substituting Cu having pyramidal oxygen co-ordination is in Fe³⁺ state while Fe substituting Cu having square planar co-ordination is in Fe³⁺ and Fe⁴⁺ states in dynamic equilibrium.     

Hysteresis behavior in Raman intensities in YBa2Cu3O7-y -family superconductors between T c and T o = 234 K

The intensity of the 646 cm^-1 Raman line in YBa₂Cu_3-x V _x O_7-y has been measured for cooling and heating from 77 K to 234 K. The intensity exhibits intensity hysteresis of order 20% in the cooling versus heating values between T _c = 89 K and T _o = 234 K. This effect is unexplained but is extremely similar to that reported by Ledbetter et al. for the bulk modulus and C ₁₁ elastic coefficient. In each case the hysteresis vanishes below T _c , independent of the value of T _c , which may be adjusted from 60 K to 94 K by changing oxygen concentration y. Qualitative interpretation requires that the structural phase transition near 234 K be intimately related to the superconducting transition at T _c presumably through partial ordering of oxygens.     

Specific contact resistivity of silver contacts on highT cYBa2Cu3O7 superconductors

Specific contact resistances of vacuum-evaporated silver contacts on new oxide superconductors, YBa₂Cu₃O₇ are measured using a modified Kelvin test structure. Contact resistivity increases continuously as the temperature decreases down to zero resistance point. AtT _c, its value is ∼0.15 ohm cm² which is high for technological applications. The nature of contacts appears different from that of semiconductor metal structures.     

Cu chemistry of YBa2Cu3O6+x investigated by nuclear quadrupole resonance

The nuclear quadrupole resonance (NQR) technique has been utilized to characterize the local oxygen coordination of inequivalent Cu sites in YBa₂Cu₃O_6+x(0 ≤ x ≤ 0.91). Essentially, four distinct NQR lines which correspond to 2, 3,4 oxygen coordinated Cu sites in the Cu-O chains and 5 oxygen coordinated Cu sites in the Cu-O planes have been observed. The zero-field NQR frequencies of these are centered at about 30.1, 24.0, 22.0 and 31.5 MHz for ⁶³Cu, respectively. For the antiferromagnetic ordered state (x ≤ 0.3), antiferromagnetic nuclear resonance (AFNR) has been observed at 90 MHz with quadrupole splittings associated with the moment-bearing Cu sites in the Cu-O planes. The relative intensities of these resonance lines depend on the oxygen content, and this gives us a microscopic understanding of the Cu chemistry of this system.     

Normal co-ordinate analysis of the zero wave-vector vibrations of DyBa2Cu3O7

Using Wilson’s F-G matrix method a normal co-ordinate analysis of the spectral frequencies and form of the zero-wave vector vibrations of the high temperature superconductor, orthorhombic DyBa₂Cu₃O₇ has been performed. The vibrational frequencies and the potential energy distribution of the 21 infrared-active and 15 Raman-active modes are presented. The potential constants employed here are presented and evaluated vibrational frequencies are compared with the available experimental values.     

An experimental approach to the improvement of critical current density in high-TC YBa2Cu3O x ceramics

A “grain coating” technique was developed to improve the intergranular links in YBa₂Cu₃O _x ceramics. Thin layers of additives such as Ag, SnO₂, Bi₂O₃ were introduced into the grain boundaries by vacuum evaporation. Notable J_c increments due to grain coating were observed. TEM investigation revealed that dislocations accompanied by stacking faults existed in these samples.     

Studies of synthesizing behaviors and superconductivity of sol-gel YBa2Cu3O7-x samples in flowing oxygen atmosphere

Systematic studies of synthesizing behaviors of sol-gel YBa₂Cu₃O_7−x samples in flowing oxygen atmosphere and their superconductivity have been performed. A set of high temperature ρ-T curves has been obtained for the whole synthesizing process. After four rounds of synthesizing, the resistivity of the sample was around ρ=1.00×10⁻³Ω · cm at room temperature. The ρ-T curve of the fourth round shows that the orthorhombic to tetragonal phase transformation of the sample occurs around 600 °C, which is lower than that of the YBa₂Cu₃O_7−x sample prepared by conventional solid-state reaction method. Other measurements, such as X-ray diffraction, SEM measurement and low temperature R-T and M-T measurement, were also performed. And the R-T and M-T measurement results suggest that during the synthesizing process, there exist some state at which the sample has better superconductivity than the other states. Moreover, we found screw dislocations presenting on the sample broken surface from the SEM images. This will change the concept that the screw dislocations can only grow on the surface of the YBCO thin films and single crystals.      

Spectral features of laser induced plasma from YBa2Cu3O7 and GdBa2Cu3O7 highT c superconductors

Laser induced plasma emission spectra from highT _c superconducting samples of YBa₂Cu₃O₇ and GdBa₂Cu₃O₇ obtained with 1.06μm radiation from a Q switched Nd:YAG laser beam has been analysed. The results clearly show the presence of diatomic oxides in addition to ionized species of the constituent metals in the plasma thus produced.     

Interface and grain boundary structures in YBa2Cu3O7-x and YBa2Cu4O8 materials

Y₂BaCuO₅YBa₂Cu₃O_7-x (Y211/Y123) interfaces in melt-processed YBa₂Cu₃O_7-x were studied by high-resolution transmission electron microscopy and energy dispersive X-ray spectroscopy. Yttrium enrichment and barium depletion were observed locally at the Y211/Y123 interfaces where Y123 (001) facets were present. This effect may be interpreted as the result of lattice substitution of Ba by Y near these interfaces. Cation nonstoichiometry was found near Y211/Y123 interfaces where liquid phases (Cu-Ba-O) were present. This chemical disorder introduces numerous point defects in the Y123, and these defects may act as additional pinning sites alongwith stacking faults. A comparison of grain boundary (GB) chemical composition in polycrystalline YBa₂Cu₃O_7-x and YBa₂Cu₄O₈(Y124), studied using nanoprobe parallel-detection electron energy-loss spectroscopy (EELS), is presented. The studies of Y124 show that stoichiometric grain boundaries can also form weak links between superconducting grains. It is suggested that weak-link behavior is determined largely by misorientation at grain boundaries.     

EPR study of some rare-earth ions (Dy3+, Tb3+, and Nd3+) in YBa2Cu3O6-compound

We investigate the low temperature X-band electron paramagnetic resonance (EPR) of YBa(2)Cu(3)O(x) compounds with x congruent with 6.0 doped with Dy(3+), Tb(3+), and Nd(3). The EPR spectra of Dy(3+) and Tb(3+) have been identified. The EPR of Tb(3+) is used also to study the effect of suppression of high T(c) superconductivity by doping with Tb(3+). The EPR of Nd(3+) is probably masked by the intense resonance of Cu(2+). All experimental EPR results compare well with theoretical estimations.     

Kinetics of oxygen desorption in Y Ba2Cu3O7-δ

In this paper the kinetics of oxygen desorption from Y Ba₂Cu₃O_7-δ has been investigated and measurements carried out in the temperature range 350–750 C. It is shown that the oxygen desorption is diffusion-controlled (and not surface-controlled), and characteristic of diffusion from small grains in a loosely coupled porous matrix. At every temperature a number of time constants with well-defined ratios appear and have been identified and measured. These time constants can be related to the average bulk diffusion constant which shows an Arrhenius behaviour with deviations around 750°C which are ascribed to the well-known orthorhombic to tetragonal transition. In this paper we establish the basic underlying physical mechanism of oxygen desorption in Y Ba₂Cu₃O_7-δ.