Mechanisms of interaction of YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript> <Emphasis Type="Italic">y</Emphasis> </Subscript> with water vapor at low-temperature annealing

Abstract—The interaction of YBa₂Cu₃O_y (123) with water vapor at temperatures T ≤ 150° has been studied. It has been shown that, with an increase in temperature, the mechanism of its interaction with water changes. Near room temperature, the main process is hydrolytic decomposition. At T ~ 100°C, the absorption of water is significantly reduced, because the role of hydrolysis becomes less important and water penetrates the structure weakly and is incorporated into oxygen vacancies mainly in the form of OH–-groups, which leads to the transition of YBa₂Cu₃O_y from the tetragonal to orthorhombic phase. With an increase in temperature to 150°C, the absorption of water increases again. In this case, the main mechanism is the penetration of water to the 123 structure, which leads to splitting of Cu–O chains and a phase transition from the 123 to pseudo-124 structure. The role of different mechanisms of interaction with water essentially depends on the oxygen content in the 123 structure. At a low oxygen index (y = 6.3), the role of hydrolysis is more important, and, at y ≥ 6.5, the incorporation of water into the structure prevails. It has been revealed that, at T = 150°C, after absorption of water, YBa₂Cu₃O_6.96 becomes a proton conductor.     

Analysis of nonlinearity of magnetization of YBa2Cu3O7 − x by the magnetic field modulation method

Temperature dependences of the magnetization harmonics of YBa₂Cu₃O_{7 ? x} monodomain samples are studied experimentally at temperatures of 77–120 K. It is found that nonlinearity of magnetization of YBa₂Cu₃O_{7 ? x} (higher harmonics generation) is observed up to temperatures T = 103–112 K, which are much higher than the superconducting transition temperature of this compound. At the same temperatures, the temperature dependence of resistivity begins to deviate from linearity. The observed singularity of the magnetization of YBa₂Cu₃O_{7 ? x} is associated with the emergence of a pseudogap state in this compound.     

Setup for studying nonlinear magnetic properties of high-temperature superconductors with the aid of magnetization harmonics

A setup for measuring cophasal and quadrature components of higher harmonics of an electromotive-force signal of the response of a high-temperature superconductor makes it possible to study nonlinear magnetic properties of superconductors in variable magnetic fields of up to 1 kOe and constant magnetic fields of up to 10 T in the temperature range of 5?C300 K. This setup was used to measure the temperature dependences of the absolute values of the real and imaginary parts of the first and third harmonics of the magnetization of textured Yba₂Cu₃O_{7 ? x} polycrystalline samples in the temperature range of 77?C220 K at various values of variable and constant magnetic fields. An analysis of resulting data made it possible to reveal the presence of different dynamical modes of the magnetic flux in YBa₂Cu₃O_{7 ? x} that were dominant in different temperature ranges. The nonlinearity of the magnetization of YBa₂Cu₃O_{7 ? x} (the appearance of higher harmonics) was observed up to temperatures in the range of T = 103?C112 K, which were substantially higher than the temperature of the transition of this compound to a superconducting state. The observed feature in the magnetization of YBa₂Cu₃O_{7 ? x} was associated with the emergence of a pseudogap state in this compound.     

Detection of YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7−x</Subscript> magnetization nonlinearity in a pseudogap region

The temperature dependences of magnetization higher harmonics were studied experimentally in single-domain YBa₂Cu₃O_7?x samples above T _c . YBa₂Cu₃O_7?x magnetization nonlinearity was found in different samples up to temperatures T = 103–112 K, which is much higher than the temperature of transition into the superconducting state of the given compound. The observed specific feature of YBa₂Cu₃O_7?x magnetization is associated with the occurrence of pseudogap state in this compound.     

Magnetization harmonics for YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7 − <Emphasis Type="Italic">x</Emphasis></Subscript> textured polycrystals above the superconducting transition temperature

The temperature dependences of the third and other higher magnetization harmonics for YBa₂Cu₃O_{7 ? x} textured polycrystals are experimentally investigated in the temperature range 77–120 K. It is revealed that the magnetization of the YBa₂Cu₃O_{7 ? x} textured polycrystals exhibits a nonlinear behavior up to temperatures considerably higher than the superconducting transition temperature. The observed nonlinearity of the magnetization of the YBa₂Cu₃O_{7 ? x} textured polycrystals is attributed to the pseudogap state that appears for this compound at a temperature T ～ 102 K.     

Novel configuration of processing bulk textured YB2Cu3O7−x superconductor by seeded infiltration growth method

Mono-domain YBa₂Cu₃O_7?x (Y123) bulk superconductors have been processed using seeded infiltration growth technique (SIG). The combination of melt infiltrated liquid source (Ba₃Cu₅O₈) into the Y₂BaCuO₅ (Y211) pre-form and the nucleation of Y123 domain from SmBa₂Cu₃O₇ crystal seed has been investigated. The different configurations of SIG process were compared in this study. In addition, the effect of the starting Y211 particles size has been studied. The results reveal that, the Y211 particle size and different configurations strongly influence the properties of the final bulk superconductor sample.     

Effect of vapors of the simplest alcohols on the structure and properties of YBa2Cu3Oy compounds

With low-temperature treatments (200–300°C), the effect of alcohol vapors on the structural and electrophysical properties of YBa₂Cu₃O_y (123) having different oxygen content has been studied. It has been established that CuO and YBa₂Cu₃O_y are catalysts for the dehydration of alcohols to form water and aldehydes. Similar to the action of water vapors, the treatment in vapors of the simplest alcohols leads to hydration of 123 and its transformation into the pseudo-124 phase. In this case, planar stacking faults are formed to be centres of pinning and can improve the critical characteristics of high-temperature superconductors (HTSС) in magnetic fields. The influence of the alcohol vapors is more ‘mild’ as compared to the treatment in water vapors. At t?=?300°C, the alcohols are reducing agents of copper, followed by the decomposition of 123 into simple compounds.     

Growth and formation of the microstructure of YBCO films deposited by magnetron sputtering on fianite substrates

The dependence of the electrophysical and structural properties of the high-T _c YBa₂Cu₃O_{7 ? δ} superconductor films deposited by magnetron sputtering on fianite on the growth temperature is studied. Scanning electron microscopy and X-ray diffraction demonstrate that the layer-by-layer island growth of an YBa₂Cu₃O_{7 ? δ} film occurs on fianite substrates without an additional buffer layer. An increase in the deposition temperature leads to the division of the growing film into regions with strongly different microstructures. The regions of the first type are represented by a high-quality YBa₂Cu₃O_{7 ? δ} layer, and the regions of the second type consists of an YBa₂Cu₃O_{7 ? δ} layer with well-pronounced granule boundaries, which hinder the passage of an electric current.     

Systematic Mössbauer study of YBa2Cu3−x Fe x Oδ and PrBa2Cu3−x Fe x Oδ as a function of temperature

We study the similitudes and differences between YBa₂Cu_3?x Fe _x O_δ and PrBa₂Cu_3?x Fe _x O_δ systems, using Mössbauer spectroscopy. Both systems, withz=0.04, were studied at several temperatures. The spectra of PrBa₂Cu_3?x Fe _x O_δ showed four asymmetric quadrupole doublets with apparently different line widths, which were fitted with four symmetric superimposed quadrupole doublets with the same line width, but assuming a small (～4–6 kOe) residual magnetic field in the Fe sites, which are mainly the Cu(1) sites of the 1–2–3 structure. On the other hand, the PrBa₂Cu_3?x Fe _x O_δ spectra showed only three asymmetric quadrupole doublets which can be fitted with three superimposed symmetric doublets and a residual magnetic field. In this case, the Fe atoms also occupy the Cu(1) sites of the 1–2–3 structure. The temperature variations of the Mössbauer spectra and their parameters seem to indicate that, in the Pr-system, a structural change takes place between 12 K and 40 K.     

Superconductivity and magnetic order in RBa2Cu3Oz

Mössbauer studies of⁵⁷Fe in RBa_2?y K _y (Cu_1?x Fe _x )₃O_z, with R=Y and Pr;y=0 and 0.5;x=0.01, 0.05 and 0.1 andz between 5.9 and 7.1, have been performed. A minority of the iron ions enter the Cu(2) site and reveal its magnetic order. In nonsuperconducting YBa_1.5K_0.5(Cu_0.95Fe_0.05)₃O_6.1 two distinctly inequivalent magnetic iron sites are observed, probably corresponding to iron in the Cu(2) site with different Ba?K neighbours. In superconducting (T _c =60 K) YBa_1.5K_0.5(Cu_0.95Fe_0.05)₃O_6.5 one Cu(2) subsite remains magnetic (T _N=440 K). The implications of these findings on the valencies of the Cu ions are discussed.     

Influence of chemical composition on the stability of YBa2Cu3O y in a humid atmosphere

The influence of replacements of yttrium and barium in YBa₂Cu₃O _y and doping of this compound with CeO₂, ZrO₂, and Pr₂O₃ on the capability of absorbing water from the annealing atmosphere at T = 200°C has been studied. The complication of the chemical composition of the 123-type compounds leads to an enhancement of their stability to aggressive components of the gaseous phase (H₂O, CO₂). These compounds have a variable chemical composition both in oxygen and water and can exist in three modifications: the oxygen-ordered ortho-phase, the oxygen-disordered tetra-phase, and the pseudocubic phase with a variable water content, which at T = 200°C separates into an oxygen-deficient water-enriched phase and an oxygen-rich anhydrous phase.     

Anomalous proximity effect in superconducting oxide structures with an antiferromagnetic layer

The electrophysical parameters of superconductor/antiferromagnetic insulator structures based on the Nb/Au/Ca_1?x Sr _x CuO₂/YBa₂Cu₃O_7?δ hybrid heterostructure have been examined. YBa₂Cu₃O_7?δ and Ca_1?x Sr _x SuO₂ epitaxial films are grown by the laser ablation method on NdGaO₃ single crystal substrates, the thickness of the Ca_1?x Sr _x CuO₂ layer varies from 20 to 50 nm, and x = 0.15 and 0.5. The superconducting pair potential in the interface between the YBa₂Cu₃O_7?δ superconductor and Ca_1?x Sr _x CuO₂ antiferromagnet is found to penetrate into the antiferromagnet at distances much larger than the coherence length calculated for the ferromagnetic layer. The critical current of the superconducting transition manufactured at such an interface is highly sensitive to the magnetic field.     

Effect of low-temperature treatment and subsequent high-temperature annealing on the critical current density of YBa2Cu3O y

The field dependences of the critical current density of the HTSC compound YBa₂Cu₃O _y recovered at T = 920?C950°C after the low-temperature treatment have been investigated. At T = 200°C, structural defects are formed in a wet environment, which are capable of initiating pinning of magnetic vortices. A short-term (1?C3 h) recovery annealing performed at T = 930?C950°C leaves in the samples a fairly large amount of structural defects formed during the low-temperature treatment, which results in a substantial increase in the critical current density in magnetic fields of ??2 T as compared to the ceramics not subjected to double annealing. A longer high-temperature treatment removes the structural defects formed and brings the electrophysical properties of YBa₂Cu₃O _y to the level characteristic of the ceramics produced by standard technology.     

Effect of the microstructure of epitaxial YBa2Cu3O7 − x films on their electrophysical and nonlinear microwave properties

The local nonlinear microwave response of YBa₂Cu₃O_{7 ? x} films was measured by near-zone field microscopy with a spatial resolution of 50 μm, and YBa₂Cu₃O_{7 ? x} film microbridges were locally studied by low-temperature scanning microscopy with a spatial resolution of 4 μm. The microstructure of epitaxial YBa₂Cu₃O_{7 ? x} films was examined using x-ray diffraction and electron microscopy. A correlation is detected between the average crystallite size and the half-widths of the temperature dependences of the third-harmonic power (W _TH) and the electron-beam-induced voltage (W _EBIV). The experimental results are described in terms of a model of a two-phase medium taking into account the nonlinear I-V characteristic of the superconductor. For large crystallites, the nonlinear microwave response is shown to be caused by intracrystallite vortex pinning. As the average crystallite size decreases, an additional contribution to the nonlinear response appears due to the pinning of a magnetic flux by the Josephson network of crystallite boundaries. Calculations show that a three-fold increase in the crystallite size decreases the nonlinearity coefficient of YBa₂Cu₃O_{7 ? x} films by two orders of magnitude.     

Phase diagram for stripes in YBa2Cu3O6+x superconductors

Neutron scattering has been used to measure the charge and spin structure in the YBa₂Cu₃O_6+x superconductors. Incommensurate static charge ordering is found at low doping levels while only charge fluctuations are found at higher doping. The spin structure is complex with both a commensurate resonance and incommensurate structure observed at low temperatures. The scattering results are used to construct a phase diagram for stripes in the YBa₂Cu₃O_6+x system.     

Cation nonstoichiometry and its contribution to the nanostructured inhomogeneity of tetra and ortho modifications of YBa2Cu3O7 − δ oxide

The cation composition and structure of YBa₂Cu₃O_{7 ? δ} (YBCO, the 123 phase) oxide samples synthesized at 990°C in air and annealed in oxygen at 450°C are studied via elemental analysis in a transmission electron microscope and high-resolution electron microscopy. The occurrence of cation nonstoichiometry and nanostructured inhomogeneity of the 123 phase in tetragonal and orthorhombic (superconducting) structures is confirmed. The nanostructured inhomogeneity of the 123 phase is attributed to the presence of nanocrystallites (2–5 nm) of oxides with different cation compositions belonging to the Y _n Ba _m Cu _{m + n} O _y series.     

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.     

Spectroscopic studies of the high-Tc superconducting cuprate perovskites

We present XRD, ESR, IR, DR(UV, VIS) as well as resistivity and magnetic susceptibility data of single phase superconducting perovskites YBa₂Cu₃O_x and EuBa₂Cu₃O_x. A rich phonon structure for both oxide compounds has been observed with a peak at: 72, 108, 135, 148, 172, 570 and 620 cm^-1. The edge of the low energy side was observed at 55 cm^-1. The estimated carrier density for YBa₂Cu₃O_x is (1–2) × 10²¹ cm^-3. A weak ESR signal has also been observed for superconducting phases which is associated with the lattice defects.We also report ESR and optical measurements of constitutent materials as well as not superconducting phases Y₂Cu₂O₅ and BaCuO₂.     

Two-magnon Raman scattering in dielectric and superconducting YBa2Cu3O6+x crystals

Two-magnon Raman scattering in dielectric, as well as superconducting, YBa₂Cu₃O_{6 + x} single crystals with mobile oxygen content x = 0.2–0.7 and superconducting transition temperature T _c = 0–74 K is studied in detail. Doping with oxygen in the range of x = 0.2–0.5 leads to two-magnon scattering peak broadening and a shift in the spectral position of the peak towards lower energies. The most significant qualitative changes in two-magnon scattering in YBa₂Cu₃O_{6 + x} crystals are observed in a narrow oxygen concentration range near x = 0.7. This is explained by a considerable decrease in the correlation length ξ_AF of antiferromagnetic (AF) correlations upon an increase in the concentration of free carriers. For instance, doping is accompanied with a reduction of ξ_AF to values of several lattice constants a for x ≈ 0.7, a transition to the regime of short-range AF order, and local scattering of light from a small AF cluster with a size of 3 × 4 lattice constants. An increase in the free charge carrier concentration destroys the short-range AF order in a narrow range of the stoichiometry index near x = 0.7. Experimental data also indicate heterogeneity of cuprate planes at microscopic level, which leads to coexistence of superconducting and AF regions in YBa₂Cu₃O_{6 + x} super-conducting crystals.     

Leggett mode in cuprate superconductors and the electromagnetic properties of Josephson junctions

The effect of multiple Andreev reflections in YBa₂Cu₃O_{7 ? x} and Tl₂Ba₂Ca₂Cu₃O_{10 ? ??} has been studied. Several independent subharmonic gap structures associated with the multigap character of these superconductors have been revealed on the I(V) and dI/dV characteristics of Andreev contacts. An additional fine structure has been observed, which can be attributed to the emission of Leggett plasmons. The electromagnetic properties of Josephson junctions at a microcrack in Tl₂Ba₂Ca₂Cu₃O_{10 ? ??} have been examined. The magnetic-field dependences of the critical current, as well as Fiske geometric resonances, have been studied in the Josephson regime (SIS type). The fundamental frequency of resonances and the Swihart velocity have been determined.