Electronic structures of superconductors YBa2Cu3−x M x O y (M=Sn,Ni)

Based on the EHMO approach, the energy band structures for superconductors YBa₂Cu_3–x Sn _x O _y (y>7) and YBa₂Cu_3–x Ni _x O_y (y<7) were calulated in the present paper. The influence of the cation doping at the Cu site in the unit cell and the oxygen content on their electronic structures was studied. The results showed that the cation doping at the Cu site resulted in the great decreases in the bandwidths of the broad anisotropic Cu-O bands and the densities of states. In YBa₂Cu_3–x Sn _x O _y , however, these decreases are compensated by the increase in the oxygen content caused by the Sn-doping, which results in a small change in the total densities of states. For YBa₂Cu_3–x Ni _x O _y , the effect of the doping on its electronic structures in dominant. The Ni-doping, therefore, results in a great change in the electronic structures. In addition, the study on the projected densities of states of the Ni-doped system revealed that the 2D Cu-O planes in the Y-Ba-Cu-O system played a dominant role in superconductivity.     

Influence of partial substitution of zinc for copper on electronic structures of YBa2Cu3O y

Summary By use of an approximate band-structure treatment based on the EHMO approach, the energy band structures for the Zn-doped superconductor YBa₂Cu_3–x Zn _x O _y were calculated in the present paper and the influence of partial substitution of zinc for copper on the electronic structures for orthorhombic YBa₂Cu₃O_y was studied. From analysis of the band structures and the densities of states for YBa₂Cu_3–x Zn _x O _y , it was demonstrated that the 2D Cu-O planes in the Y-Ba-Cu-O superconducting system have a direct and dominant influence on superconductivity, whereas the role of the 1D Cu-O ribbons and the O(4) atoms is also of some importance.     

Positron annihilation studies in YBa2Cu3O x (6<x≤7)

Positron lifetime and Doppler broadening of the annihilation line measurements, as a function of temperature between 14 and 300 K, have been performed on four YBa₂Cu₃O _x (6<x7) samples with different oxygen deficiency. It was found that the positron lifetime and theS parameter values increase as the oxygen deficiency increases in the YBa₂Cu₃O _x (6<x7) samples. It was also observed that the positron annihilation parameers show different temperature dependence in the YBa₂Cu₃O _x (6<x7) samples associated with their different oxygen deficiency.     

The effect of Fe-doping on superconductivity of YBa2Cu30 y

In the present paper, an approximate band-structure treatment based on the EHMO approach is suggested and used to calculate the electronic structures of the Fe-doped superconductors YBa₂Cu_3–x Fe _x O _y . The present treatment gives, indeed, average band structures and average densities of states as the doping fraction increases. From investigations of the influence of the Fe-doping at the Cu-site on their properties, it is shown that as the Fe-doping fractionx in YBa₂Cu_3–x Fe _x O _y is raised from 0.0 to 0.5, (i) the broad anisotropic bands arising from the 1D Cu-O chains and the 2D Cu-O planes are displaced and depart from the Fermi levelE _f toward the high-energy zone by degrees, while the total electronic densities of states nearE _f are drastically decreased; (ii) the band arising from the Cu-O chains doped by Fe is gradually separated from the broad anisotropic bands arising from the 2D Cu-O planes; (iii) at the doping fractionx = 0.5, the Fe-doping results in an energy gap (about 0.2 eV) near E_f; (iv) the oxygen content is not a predominant factor for the superconducting properties of the Fe-doped Y-Ba-Cu-O system; (v) the total densities of states atE _f,N(E _f), and their decrease caused by the Fe-doping arise mainly from the 2D Cu-O planes, which implies the important role of the 2D Cu-O planes in the Y-Ba-Cu-O superconducting system.     

Synthesis and ac susceptibility of YCa2Cu3O7−δ

The bulk superconducting YCa₂Cu₃O_7−δ compounds are prepared at an ordinary pressure of oxygen by conventional solid-state reaction method. The formation of sample is tested by means of XRD and is studied for their ac susceptibility below room temperature up to 77.5 K. The samples are found single-phase orthorhombic structure and found superconducting at 83.5 K. It is shown that the analysis is consistent with published data on YBa₂Cu₃O_7−δ oxide superconductor.     

Study on the effects of fluorine and oxygen deficiency on YBa_2Cu_3O_7 by ab initio method

The calculations of clusters modeling the fluorine-doping and oxygen deficiency of YBa2Cu3O2,have been performed by the method of all-electron ab initio Hartree-Fock with self-consistent crystal field Results show that in CuO planes electric charge significantly increases,the chemical valence of Cu decreases and the covalent bonding of Cu-O greatly weakens owing to oxygen deficiency,while the effect of F restores the local electronic structure of YBa2Cu3O7 The reported opinion that F occupied the oxygen vacancy in Cu-O chains seems disputable according to the calculated bonding characteristics.     

Mechanism of formation of YBa2Cu4O8 superconductor in the sol-gel synthesis

It was shown that a single phase YBa₂Cu₄O₈ (124-phase) could be formed from gels at 1 atm oxygen pressure, and the mechanism of its formation was elucidated. It was found that there are two key routes for the sol-gel formation of the 124-phase, one involving the tetragonal YBa₂Cu₃O _y with a low concentration of oxygen defects (tetra-I phase) and the other involving the Ba₂Cu₃O_5.9 as important intermediates of the 124-phase. The rapid formation of these intermediate compounds from the gel was attributed to the small particle size of the oxides and carbonates precipitating at the initial stage of heating. It was thought that the small particles characteristic of sol-gel processing lead to the rapid formation of the intermediate compounds and subsequent precipitation of the 124-phase.     

Thermal analysis and thermal expansion studies on high density YBa2−xLaxCu3O7−δ, 0x0.2

The compositions in the YBa_2−xLa_xCu₃O_7−δ (0x0.2) system were prepared by the solid state reaction, employing a novel high-temperature oxygen sintering route. The modified sintering route yields dense slab like microstructures with large grains. The decomposition (incongruent melting) temperature of the YBa₂Cu₃O_7−δ (Y-123) phase was found to shift to higher temperatures with increasing oxygen partial pressure and lanthanum content. Structure remained orthorhombic up to x=0.2 with a decrease in the orthorhombic strain ((b−a)/b). Iodometric titration indicated a systematic increase in the oxygen content with increasing lanthanum content. Thermo-gravimetric studies in various oxygen partial pressures revealed that the oxygen diffusion in to the YBa₂Cu₃O_7−δ (δ>0.5) lattice is an exothermic event and takes place at temperatures not less than 573 K. High-temperature thermal-expansion measurements in air indicated that the nonlinearity in thermal expansion behaviour was reduced by the substitution of lanthanum.     

Interface structure and misfit relaxation in YBa2Cu3O7‐δ/PrBa2Cu3O7‐δ heterostructures on SrTiO3(001) substrates

Structural properties of YBa₂Cu₃O_7‐δ/PrBa₂Cu₃O_7‐δ heterointerfaces have been investigated by aberration‐corrected electron microscopy. Experimental evidence shows that c‐axis‐oriented YBa₂Cu₃O_7‐δ/PrBa₂Cu₃O_7‐δ heterostructures with atomically sharp interface epitaxially grow on SrTiO₃(001) substrates. In terms of the contrast analysis, no apparent interdiffusion between YBa₂Cu₃O_7‐δ and PrBa₂Cu₃O_7‐δ occurs at the interface. In addition, stand‐off misfit dislocations and planar faults appear within PrBa₂Cu₃O_7‐δ layer near the interface. Both misfit dislocations and interfacial dislocations resulting from the termination of planar faults contribute to misfit relaxation at the YBa₂Cu₃O_7‐δ/PrBa₂Cu₃O_7‐δ interface. The defect configuration of planar faults and stand‐off misfit dislocations is explored. Copyright © 2013 John Wiley & Sons, Ltd.     

Metal-organic deposition of YBa2Cu3Ox and Bi2Sr2Ca1Cu2Ox films on various substrates starting from different fluorine-free metallorganic compounds

YBa₂Cu₃O_x (Y-123) and Bi₂Sr₂Ca₁Cu₂O_x (Bi-2212) films on various substrates have been prepared by Metal-Organic Deposition starting from different metallorganic fluorine-free compounds and using a very simple instrumentation. The processing conditions include a rapid pyrolysis step in air and an annealing step in oxygen for Y-123 and in air for Bi-2212. The films obtained have been characterized by X-ray diffraction (XRD) and the formation of a superconducting phase of Y-123 or Bi-2212 was confirmed measuring the critical temperature (T _c) with Ac-susceptibility and resistive measurements. Microstructure and final cationic ratios have been studied by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS).     

Reactions between YBa2Cu3O7−δ and La2O3 and SrCO3

Solid state reactions at 925°C between the high-T _c ceramic superconductor YBa₂Cu₃O_7?δ and La₂O₃ and SrCO₃, respectively, mixed in various molar ratiosr=MeO_n/YBa₂Cu₃O_7?δ, were studied using X-ray powder diffraction and scanning electron microscopy. The reaction between YBa₂Cu₃O_7?δ and La₂O₃ yielded (La_1?xBa_x)₂CuO_4?δ, withx≈0.075?0.10. La_2?xBa_1+xCu₂O_6?δ, withx≈0.2?0.25 and La-doped (Y_1?xLa_x)₂BaCuO₅, withx≈0.10?0.15. Forr=3.0, Y-doped La₂BaCuO₅ resulted also. The reaction between YBa₂Cu₃O_7?δ and SrCO₃ yielded (Sr_1?zBa_z)₂CuO₃, withz≈0.1, Y₂(Ba_1?zSr_z)CuO₅, withz=0.1?0.15, and a nonsuperconducting compound with an approximate composition of Y(Ba_0.5Sr_0.5)₅Cu_3.5O_10±δ. At values ofr≤2.0, unsubstituted YBa₂Cu₃O_7?delta was found in the reaction products.     

Electronic structure and chemical bonding in Ba-Cu-O layer systems

The cluster method of discrete variation was used to study compounds containing chains of plane-coordinated copper ions separating oxygen-copper planes. We also examined real YBa₂Cu₃O₇ and hypothetical MBa₃Cu₄O₉ systems (M is a tetravalent metal ion). A study was carried out on the transformation of the valence band and structure of the molecular orbitals in the Fermi level in going from YBa₂Cu₃O₇ to MBa₃Cu₄O₉. The chemical bonding was analyzed and the role of the interchain interaction in the bonding of the copper and oxygen atoms in different crystallographic positions was determined.Institute of Chemistry, Urals Branch, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 5, pp. 17–20, September–October, 1989.     

Application of model of ideal solution of interaction products (ISIP) and thermodynamic modeling (TM) for description of superconducting phases in the system YBaCuO

The thermochemical properties of Cu₂O₃ were calculated. The stability of Cu₂O₃ was studied with the help of TM methods. It was shown that this oxide can exist in oxygen atmosphere (P=10⁵ Pa) at temperatures below 380 K. A variant of the ISIP model was used with TM to determine the Cu⁺, Cu²⁺ and Cu³⁺ contents and oxygen indexes in YBa₂Cu₃O_x (123-O_x), YBa₂Cu_3.5O_y (123.5-O_y), YBa₂Cu₄O_z (124-O_z), YBa₂Cu₅O_q (125-O_q) and YBa₂Cu₆O_m (126-O_m) solutions at 100–1200 K in oxygen medium (P=10⁵ Pa). Methods for determination of some thermodynamic properties and oxygen indices are suggested for a superconductor family in the system YBaCuO.     

Ba2Cu3O5+δ as an intermediate phase during the synthesis of YBa2Cu4O8

We propose a reaction model for the synthesis of YBa₂Cu₄O₈ under normal pressure conditions, which contains 4 partial reaction steps. In a first step bariumnitrate and copperoxide react to Ba₂Cu₃O_5+δ. This substance will be formed for each mixtures Ba:Cu=2∶3...3∶2. The following two partial reaction steps are connected to Ba₂Cu₃O_5+δ, which reacts with Y₂O₃ and CuO to YBa₂Cu₄O₈ or decomposes to BaCuO₂ and CuO. In a last step parts of BaCuO₂ reacts with Y₂O₃ and CuO to YBa₂Cu₄O₈.     

A study of YBa2(Cu1?xMex)3O6 + δ (Me = Al, Co, Fe) electrophysical and electrochemical properties

The structure, thermal expansion coefficient, and electroconductivity of YBa₂(Cu_1−x Al _x )₃O_6+δ (x = 0.0–0.9) were studied at 20 to 900°C in air. The most conducting compositions of YBa₂(Cu_1−x Me _x )₃O_6+δ (Me = Al, Co, Fe) were determined. The electrochemical activity of electrodes with the most conducting compositions of YBa₂(Cu_1−x Me _x )₃O_6+δ (Me = Al, Co, Fe) was studied in a wide polarization range in the contact with 0.9ZrO₂ + 0.1Y₂O₃ solid electrolyte in air at the temperatures of 700 to 900°C. Original Russian Text ? V.K. Gil’derman, I.D. Remez, 2009, published in Elektrokhimiya, 2009, Vol. 45, No. 5, pp. 612–615. Published by report at IX Conference “Fundamental Problems of Solid State Ionics”, Chernogolovka, 2008.     

Positron annihilation studies in highT c superconductor YBa2Cu3Cd x O y (x=0, 0.05)

Positron lifetime and Doppler broadening of the annihilation line measurements were performed in highT _c superconducting samples YBa₂Cu₃Cd _x O _y ,x=0, 0.05 and 6.9<y<7, as a function of temperature in the region of 14–300 K. It was found that the positron lifetime and theS parameter values are lower in the Cd doped sample than those in the undoped one. It was also observed that the positron annihilation parameters show similar temperature dependence for the undoped and Cd doped samples. We conclude that the Cd doping in highT _c superconductor YBa₂Cu₃Cd _x O _y , 6.9<y<7 fills defects associated with oxygen vacancies probably in oxygen deficient regions which can trap positrons.     

Electronic structure and properties of isolectronically substituted compounds Y1Ba2−m M m Cu3O7 and Y1Ba2−m M m Cu4O8 (M=Be,Mg, Ca,Sr, Ba,Ra)

According to cluster calculations, the electronic structures of compounds based on Y₁Ba₂Cu₃O₇ and Y₁Ba₂Cu₄O₈ with isoelectronically substituted barium have some qualitative distinctions. These compounds behave differently upon barium substitution by other elements due to differences in the character of their highest occupied and lowest unoccupied molecular orbitals. Substitution of barium by radium is expected to lead to an increase in oxygen stability without a significant decrease in the critical temperature of superconduction transition T_s. In order to raise T_s, it is of interest to study the systems YBa_2−m(Be or Mg)_mCu₃O_x and YBa_2−m(Ca, Sr)_mCu₃O_x. On partial substitution of barium by calcium in YBa₂Cu₄O₈, the mechanism of T_s elevation may involve contraction of the forbidden band due to oxygen sublattice distortions in the vicinity of Ba centers. D. I. Mendeleev Russian Chemical Engineering University, Novomoskovsk Branch. Translated fromZhurnal Strukturnoi Khimii, Vol. 35, No. 2, pp. 24–31, March–April, 1994. Translated by O. Kharlamova     

Ein alternativer Weg zur Darstellung von Bi2Sr2CaCu2Ox,YBa2Cu3O7−δ, und YBa2Cu3−xMxO7−δ (M  Ni,Ag und x ≤ 33 Mol%)

An Alternative Method for Preparation of Bi₂Sr₂CaCu₃O_x, YBa₂Cu₃O_7?δ, and YBa₂Cu_3?xM_xO_7?δ (M ? Ni, Ag and x ≤ 33 Mol%) Oxidation of quenched melts of metals in a well defined argon/oxygen atmosphere has been found as an alternative method to prepare hight purity samples of Bi₂Sr₂CaCu₂O_x without Pb-stabilization. A special equipment for the oxidation of powder samples will be described. By our new method it is also possible to prepare YBa₂Cu₃O_7?δ and derivatives of this compound, where Cu is substituted by high amounts of Ni or Ag.     

Thermogravimetric study of the nonstoichiometric regions in the Y-Ba-Cu-O system

The paper presents the results of studies on thermal reduction and oxidation of the nonstoichiometric phases from the Y-Ba-Cu-O in air.The thermogravimetric (TG, DTA) experiments were performed in air in order to establish the ranges of stoichiometry and temperature of oxidation and reduction of YBa₂Cu₃O_x, YBa₄Cu₃O_x, YBa₅Cu₂O_x and Y₃Ba₈CusO_x.It has been found, that at 950°C in air there are four oxygen deficient ternary cuprates: YBa₂Cu₃O_6.02, YBa₄Cu₃O_8.01, YBa₅Cu₂O_8.35, Y₃Ba₈Cu₅O_16.45 and stoichiometric Y₂BaCuO₅. When these nonstoichiometric cuprates are cooled slowly to room temperature in air they oxidize to the following compositions: YBa₂Cu₃O_6.98, YBa₄Cu₃O_8.97, Y₃Ba₈Cu₅O₁₈ and YBa₅Cu₂O_8.97.This work has been supported by the CPBR 6.6.64 research programme.