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.     

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.     

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     

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.     

双层反铁磁体K3Cu2F7 中轨道序驱动的自旋二聚化

基于自旋-轨道-晶格Hamilton量,应用团簇自洽场方法,研究了双层钙钛矿结构材料K₃Cu₂F₇基态的晶格、磁及轨道结构,发现近孤立的双层的对称破缺和Jahn-Teller晶格畸变使得Cu²⁺离子在每层内交替占据 z²-x²〉/ z²-y²〉轨道,进而导致双层的层间表现为强的反铁磁耦合,层内为弱的铁磁耦合.强反铁磁耦合导致层间     

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.     

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.     

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     

Effect of heavy atom disorder on the intensities of powder XRD lines of YBa2Cu3O7-y

Abstract

It is shown that heavy atom disorder resulting from Y ? Ba, Ba ? Cu and Y ? Cu interchanges due to local stoichiometric constraints can cause significant changes in the intensities of X-ray powder diffraction lines of YBa₂Cu₃O_7-y . A comparison of the theoretically predicted intensities with published patterns for specimens prepared by the conventional dry route reveals that Ba ? Cu interchanges involving copper atoms in the CuO₂ planes can occur quite frequently and may be mistaken for (00l) texture.     

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.     

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.     

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.     

Raman Spectra of YBa2Cu3O7-y with Different Types of Fluorine Additions

Raman spectra have been measured and structurally interpreted for YBa₂Cu₃O_7-y treated by different types of fluorine additions, including both initially doping appropriate fluorides into the starting materials to be fired, and NF₃ treating of the pure superconductor oxide. Both x-ray diffraction and low-temperature inductance measurements have also been conducted. All presented data indicated that phase impurities were generated during the former processes. However, related data indicated that NF₃ treatment of the pure oxide samples generated no new crystalline phases, but caused substitution or addition of F at O sites in the oxide phase.     

Specific heat anomaly in the 90 K superconductor HoBa2Cu3O7−y

We report here the results of our heat capacityC _p measurements on a monophasic material HoBa₂Cu₃O_7−y . ΔC _p/T_c, the jump inC _p at the superconducting transition temperature (=91 K) of the material is measured to be 31 mJ/mol-K².     

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.     

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.     

固相线下Pr1-xBa2-yCax+yCu3O7±δ体系的相关系和晶体结构

 利用X射线衍射分析和Rietveld结构精修的方法研究了固相线下Pr_1-xBa_2-yCa_x+yCu₃O_7±δ体系的相关系和晶体结构。研究表明：950 ℃、空气条件下，Pr_1-xBa_2-yCa_x+yCu₃O_7±δ（y=0）体系系列样品总是含有两相：Pr123（PrBa₂Cu₃O_7±δ）和BaCuO₂；而且，随Ca含量的增加，杂相BaCuO₂的含量也随之增加。Pr_1-xBa_2-yCa_x+yCu₃O_7±δ（x=0）体系y=0.1、0.2、0.3、0.4的样品都只含有Pr123单相；y=0.5的样品含有3相：Pr123、Ca₂CuO₃和Pr₄Ca₁₀Cu₂₄O₄₁。另外，Pr_1-xBa_2-yCa_x+yCu₃O_7±δ（x=0）系列样品（y=0.1、0.2、0.3、0.4）中Pr123相还发生了正交-四方晶系的结构转化。y=0.1和0.2的样品为正交晶系，晶胞参数分别为a=0.390 33(4)和0.389 36(1) nm，b=0.389 53(4)和0.387 73(1) nm，c=1.173 38(4) 和1.168 20(2) nm；y=0.3和0.4的样品为四方晶系，晶胞参数分别为a=b=0.387 80(0) 和0.387 67(0) nm，c=1.166 00(2) 和1.165 20(2) nm。在Pr123结构中，Ba离子可以被Pr离子代替，但不能被Ca离子所代替。Ca离子占据部分Pr离子的位置。在Pr_1-xBa_2-yCa_x+yCu₃O_7±δ（x=0）体系中Pr、Ba和Ca离子间的相互替代中，离子半径比化学性质起到了更大的作用。在950 ℃、空气条件下，Ca离子在Pr_1-xBa_2-yCa_x+yCu₃O_7±δ体系中的最大溶解量是当x=0时，y≤0.4。     

Effects of divalent impurities on the fluctuation conductivity of YBa2Cu3O7 single crystals

We have studied experimentally the in-plane fluctuation conductivity near the superconducting transition in single crystal samples of YBa₂Cu₃O₇, Y_0.98Ca_0.02Ba₂Cu₃O₇, YBa_1.9Sr_0.1Cu₃O₇ and YBa₂Cu_2.97Zn_0.03O₇. In order to test the stability of the observed fluctuation regimes, low magnetic fields were applied perpendicular to the Cu-O₂ atomic planes. When the transition is approached from above we first observe a three-dimensional (3D) Gaussian regime then a crossover to a genuine critical region where the exponent is consistent with the predictions of the 3D-XY-E universality class. Decreasing further the temperature towards T_c, our results systematically reveal the occurrence of a regime beyond 3D-XY characterized by a very small critical exponent. We propose that this regime is precursory to a weak first-order superconducting transition driven by antiferromagnetic excitations related to the pseudogap phenomenon. The dilution of divalent impurities in YBa₂Cu₃O₇ does not affect the stability of the fluctuation regime beyond 3D-XY and in the case of Ca doping a further approach towards the first-order behaviour is observed.     

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.     

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.