The thermodynamic equilibrium of the formation process of High-Tc superconducting phase YBa2Cu3O7−x

Analysing the equilibrium state of the formation reaction of the high-T_c superconducting phase 1:2:3 (YBa₂Cu₃O_7−x) on the base of the pressure-temperature-oxygen content (P-T−x) correlation research and using the Van't-Hoff equation, the Gibbs free energy (ΔG_m) of the reaction has been calculated for the first time. It is seen that the absolute value of ΔG_m is not large and of the order of 2.5 kcal · mole⁻¹. This leads to an instability of the 1:2:3 phase. Also, from the calculated values of ΔG_m relative stability regions of the 1:2:3 phase are determined for different values of x. Combinatively analysing the relation lg P = A−B/T (where A – the x-dependent constant, and value of B was determined to be equal to 10518 atm. K) and the value of ΔG_m, we come to the conclusion that the synthesis of YBa₂Cu₃O_{7 − x} when x → 0 must be carried out under high oxygen pressure and low temperature for a lasting time, because the reaction rate is limited by slow diffusion in the solid phase.     

Magneto‐transport properties of polycrystalline YBa2(Cu1‐xMx)3O7‐δ (M = B and Mn)

The magnetic and transport properties of polycrystalline YBa₂ (Cu_1‐xM_x)₃ O_7‐δ (M = B and Mn) superconductor was investigated. Samples of YBa₂(Cu_1‐xB_x)₃O_7‐δ doped with several concentrations of boron B(x = 0.05 and 0.1) were investigated using magnetization measurements. A YBa₂(Cu_1‐xMn_x)₃O_7‐δ sample doped with Mn with concentration of x = 0.02 was investigated using current‐voltage (I‐V) measurements. Our results on the YBa₂(Cu_1‐xB_x)₃O_7‐δ samples reveal a considerable increase in the hysterisis width of the magnetization, M versus the applied magnetic field H with increasing boron concentration. The lower critical field was also found to be enhanced by boron doping. The critical current density, J_c was found to be significantly enhanced in the Mn‐doped sample. The enhancement of J_c was found to be more significant at the lower temperatures for all applied magnetic fields used (0 Oe, 300 Oe, and 500 Oe). Thus, chemical doping is suggested to enhance the vortex pinning forces in the YBCO samples. From the resistivity (R‐T) measurements, chemical doping of the samples was found to have no significant effect on the critical temperature, T_c. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Interactions between YBa2Cu3O7-x and K2Co3

The interactions between YBa₂Cu₃O_7-x and K₂CO₃ have been studied using thermochemical methods, isothermal annealing of diffusion pairs, optical microscopy, X-ray diffraction, and microprobe analyses. The experiments have shown existence of solubility of YBa₂Cu₃O_7-x or its constituents in both solid and liquid K₂CO₃. The barium ions are preferably dissolved in K₂CO₃, whereas potassium cations do not enter massively into the bulk of the YBa₂Cu₃O_7-x-phase. A eutectic-type phase diagram is supposed for the system K₂CO₃–YBa₂Cu₃O_7-x. The so called “green phase” Y₂BaCuO₅ and a K–Cu–O compound have been found in the contact zone at 813 °C while a “black phase” layer with nominal composition Y_1.6Cu_2.8O_5.4 has grown at 707 °C.     

The influence of small deviations from stoichiometry on the properties of Y?Ba?Cu?O superconductor ceramics

According to a central composite design samples with deviations from stoichiometry YBa₂Cu₃O_7−x of ±2.5 wt% in the ingredients were prepared. The influence of these deviations on phase content, superconducting properties and microstructure of the ceramics was studied.     

Temperature variation of the structural and thermal characteristics of YBa2Cu3O7−x in the range from 90 to 400 K

The X-ray studies of the tetragonal YBa₂Cu₃O_7−x compound are performed at different temperatures from 400 to 90 K and the temperature variation of the thermal expansion coefficients and the Debye characteristic temperature is determined. The anisotropy of thermal expansion is investigated. It is found that the two dynamical characteristics monotonously decrease with temperature lowering whereas for the superconducting orthorhombic modification their temperature dependences are anomalous. The mean thermal expansion coefficient as well as the overall Debye temperature for the tetragonal phase are smaller than those for the orthorhombic one.     

Influence of synthesis and postgrowth treatment conditions on the structural homogeneity of YBa2Cu3Ox single crystals

The effect of synthesis and postgrowth treatment (by annealing at various temperatures and partial oxygen pressures) conditions on structural homogeneity of YBa₂Cu₃O_x single crystals has been studied. The obtaining of single crystals with both high oxygen content and high critical temperatures T_c has been optimized. The wide range of postgrowth treatment conditions proposed allows to receive single crystals with given oxygen content from 6.2 to 7.0.     

Growth Kinetics of High-Tc and Low-Tc Phases in Bi2-xPbxCa2Sr2Cu3Oy Superconducting Compounds

Superconducting samples of the composition Bi_2-xPb_xCa₂Sr₂Cu₃O_y (x = 0.0, 0.1, 0.2, 0.3, 0.4, and 0.5) are prepared by co-decomposition of metal nitrates. DTA, TGA, density, and porosity studies have been performed on these samples. Characterisation techniques like XRD, SEM, EDXA, d.c. resistance, and a.c. magnetic susceptibility have been employed to study the growth of High-T_c (HTP) and Low-T_c (LTP) phases upon lead substitution for bismuth. Results have revealed the growth of HTP with increase in Pb conc. up to x = 0.3. Further increase in Pb appears to results in the deterioration of HTP resulting in the formation of LTP and Ca₂PbO₄ impurity phase. Transport critical current density (J_c) measurements performed on the samples indicate that Pb doping followed by densification remarkably improves the current carrying capacity of the materials.     

Resistance and inductance studies of Bi2−xPbxCa2Sr2Cu3Oy superconducting compounds

Bi_2−xPb_xCa₂Sr₂Cu₃O_y compounds with (x = 0, 0.1, 0.2, 0.25, 0.3 and 0.4) were prepared by solid state reaction. The resistance and inductance results showed that transition temperature increases with increase in lead concentration. The highest value of T_c(0) observed is 109 K for Bi_1.70Pb_0.30Ca₂Sr₂ · Cu₃O_y. The change of inductance per unit volume at liquid nitrogen temperature as a function of composition showed maximum change in x = 0.30 Pb-doped sample. The results showed that the inductance change is maximum in samples which also showed highest T_c.     

Effect of Boron Doping in Bi-based 2223 Superconductors

Samples with the stoichiometric composition Bi_2−xPb_xSr₂Ca₂Cu_3−yB_yO_z (x = 0.3, y = 0.2, 0.25, 0.3, 0.4) ceramics were prepared by a solid state reaction method. The samples were annealed at 850 °C for 100 hours (treatment A), and the other at 850 °C for 200 hours (treatment B). From the X-ray diffraction data of a ceramic sample it is revealed that all the samples were mixed phases of 2212 and 2223. The variation of the lattice parameters with the dopant level are represented. From the D.C. four-probe electrical resistivity data it was found that for the samples subjected to treatment B the T_c(0) values were higher than those with treatment A. The A.C. susceptibility data were collected by change in the inductance method. The effect of boron doping on the phase formation and T_c(0) is presented and the volume fraction of the phases estimated from the X-ray data. The presence of boron in the samples was confirmed by the inductive coupled plasma method. The microstructure of the samples was studied by scanning electron microscopy.     

Oxygen potentials,stoichiometry, superconducting,and magnetic properties in the Y?Ba?Cu?O system

The relationship between stoichiometry in YBa₂Cu₃O_x and oxygen potential was investigated by barometry and compared with in-situ X-ray diffraction experiments between 300 and 1000 °C (6 < x < 7). The physical properties are influenced even by small deviations in x. Y₂BaCuO₅ was included in the investigations and found to be antiferromagnetic with T_N ≈ 30 K.     

Influence of simultaneous doping of Tl and Bi on microstructure and critical current density of HgBa2Ca2Cu3O8+δ

It has been found that simultaneous doping of Tl and Bi at Hg site of HgBa₂Ca₂Cu₃O_8+δ HTSC phase induces interesting microstructural variants in the form of long period polytypoid (LPP) like structure embodying native defect substructures. It has been observed that the as synthesized (HgTl_0.2−xBi_x)Ba₂Ca₂Cu₃O_8+δ (with x = 0.05, 0.10, 0.15) phases have superconducting onset transition temperature (T_c) of about ∼133 K. However, the intragrain critical current density (J_c) for the various materials with different compositions varies significantly. It varies from 6.2 × 10⁶ A/cm² to 2.9 × 10⁶ A/cm² at 5 K and 1 T for (HgTl_0.10Bi₁₀)Ba₂Ca₂Cu₃O_8+δ and (HgTl_0.15Bi_0.05)Ba₂Ca₂Cu₃O_8+δ HTSC phase respectively. A correlation between the intragrain J_c and the defect substructures has been found to be present. This correlation has been described and disscussed. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermal Expansion and Superconductivity in Alkali Metal- and Silver-doped Bi?Sr?Ca?Cu?O System

Samples with the nominal composition Bi₂Sr₂CaCu₂O_y with na doped at the Ca site and K doped at the Sr site are prepared by solid state reaction method. From the X-ray diffraction data it is found that all the the samples have exhibited a single phase 2212. The D.C. electrical resistivity data show that for Na-doped samples the T_c (zero) varies from 80 K to 85 K and for K-doped samples it is from 79 K to 82 K. The loss of oxygen from these samples around 400°C was confirmed by high temperature dilatometry. The variation of the thermal expansion coefficient (“α”) with temperature for different alkali dopings are discussed. Also the samples with the nominal composition Bi₄Sr₃Ca₃Cu_4−xAg_xO_y (with x = 0, 0.1, 0.2, 0.3) were studied.     

Growth of ultrathin twin-free <Emphasis Type="Italic">b</Emphasis>-oriented YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7 – <Emphasis Type="Italic">x</Emphasis></Subscript> films

Twin-free b-oriented YBa₂Cu₃O_{7 – x} films with a thickness less than 40 nm have been epitaxially grown on (100)SrLaGaO₄ crystals. Based on the temperature dependence of resistance, the onset temperature of the transition to the superconducting state is found to be 90 K; the transition width is 4 K. The film growth has been performed in two stages. A (100)PrBa₂Cu₃O_{7 – x} buffer layer was previously grown on a (100)SrLaGaO₄ substrate by rf magnetron sputtering in an Ar–O₂ gas mixture at a continuous and monotonic increase in temperature from 660 to 830°C. The main YBa₂Cu₃O_{7 – x} film was grown on the buffer layer surface by pulsed laser deposition in an oxygen medium at a fixed temperature (800°C). The above processes were implemented in different chambers, which were connected by a vacuum channel for transporting samples. Both films were grown in situ, without contacting atmosphere in all growth stages. An X-ray diffraction study has shown that the YBa₂Cu₃O_{7 – x} films are single-crystal and free of precipitates of other phases and domains of other orientations.     

Effect of Lithium Doping in the Bi-2212 Superconducting System

Samples with the nominal composition Bi₂Sr₂Ca_1–xLi_xCu₂O_y (x = 0.2,0.4, and 0.6) and Bi₂Sr₂CaCu_2−x L1_xO_z (x = 0.4, 0.6, and 1.0) were prepared by the solid state reaction method. The role of L1 at both Ca and Cu sites in the Bi-2212 composition were studied. From the X-ray diffraction data it was found that the L1-doped at the Ca site increases the c-axis and that doped at the Cu site decreases the c-axis. From the D.C. four-probe resistivity data it was found that Li-doped at the Ca site reduces the T_c and the L1-doped at the Cu site gives T_c(0) above the liquid nitrogen temperature. It was observed that the L1 doping reduces the melting point of Bi-2212 composition. The presence of Lithium was confirmed by inductive the coupled plasma method.     

Mechanical Damping of YBa2Cu3O7 –x at Temperatures above 300 K

Damping of ultrasonic waves with frequencies in the 100 kHz region was measured in the temperature region 300 … 1000 K. Two peaks could be observed (near 400 K or near 700 K, respectively). Occurrence of these peaks depends on oxygen content of the sample. The higher temperature peak is attributed to phase transition Pmmm 〈– – –〉 P 4/mmm of YBa₂Cu₃O_{7 – x}.     

Use of a fluorine-containing solvent in the synthesis of YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7 − δ</Subscript> single crystals

A laboratory technological procedure has been developed for the synthesis of high-temperature superconducting YBa₂Cu₃O_{7 ? δ} single crystals (T _c ～ 90 K, ΔT _c ～ 1.0 K) up to 0.25 cm² in size from a nonstoichiometric fluorine-containing flux of (YO_1.5)(BaO)_{4 ? x}(BaF₂)_x(CuO)₁₀, where 2 ≥ x ≥ 0, using a combination of enhanced nucleation and directional crystallization by the Czochralski method. Studies using differential thermal analysis demonstrated that the addition of BaF₂ decreased the eutectic-crystallization temperature and increased the crystal-growth rate. The optimum concentration of BaF₂ in the starting melt composition was found (x = 0.2). The single-crystal surface was studied by atomic-force nanoscopy. The morphology of single crystals that have been synthesized from a melt of their own components differs substantially from that of crystals grown from a BaF₂-containing melt.     

Blocky and spheroidal growth in Y1.5Ba2Cu3Ox system

Solidification of Y_1.5Ba₂Cu₃O_x system was studied with the aim to find the temperature of self-nucleation. The microstructure after cooling from isothermal dwells in the temperature range 984–995 °C was analysed. It is shown that blocky YBa₂Cu₃O_7?δ crystals were self-nucleated and grown during isothermal dwells below 988 °C and spheroidal multicrystals were formed during cooling from isothermal dwells at higher temperatures. The symmetrical and radial YBa₂Cu₃O_7?δ crystal branches of spheroids grow in the 〈110〉 crystal direction.     

Direct observations of pseudo-binary NdBa2Cu3Ox–Ba3Cu10O13 phase diagram and NdBa2Cu3Ox crystallization under reduced oxygen atmosphere

The pseudo-binary NdBa₂Cu₃O_x–Ba₃Cu₁₀O₁₃ phase diagrams and the crystallization of NdBa₂Cu₃O_x have been in situ observed using high-temperature optical microscope under three different oxygen atmospheres namely 1%, 0.1% and 0.0097% oxygen in argon. It has been observed that the liquidus line becomes narrower both in composition and temperature with decreasing oxygen pressure. This result suggested that under reduced oxygen atmosphere, the NdBa₂Cu₃O_x crystals could only be grown from a peritectic melt consisting of Nd₄Ba₂Cu₂O₁₀ and liquid. The crystallization temperature of NdBa₂Cu₃O_x was found to decrease logarithmically with decreasing oxygen content in the atmosphere.     

Concentration Magnetic Phase Transitions in the (La1−xCaxMnO3 System

Comprehensive investigations into crystal structures, electrical and magnetic properties of the (La_1−xCa_x)MnO₃ (x = 0 ÷ 0.6) solid solutions are performed. Two concentration magnetic phase transitions are found: antiferromagnetic-ferromagnetic with x = 0.14 and ferromagnetic (T_c = 150 K) - ferromagnetic (T_c = 260 K) at f = 0.2. It is shown that the first of them is due to the crystal structure O′ O orthorhombic transition, the second - to the increase of ferromagnetic interaction at the expense of additional interaction through conduction electrons. A diagram of the magnetic states for (La_1−xCa_x)MnO₃ at x = 0 / 0.6 is given.     

Microstructural changes in epitaxial YBa2Cu3O7−δ thin films due to creation of O vacancies

Structural and transport properties of YBa₂Cu₃O_7−δ thin films subjected to different heat treatments and, consequently, having different O vacancy contents are investigated. It is observed that lattice parameters of the films follow the trend of the bulk material, indicating that either the additional stresses created in c-axis oriented films by O vacancies are negligibly small or they are relaxed at elevated temperatures. In addition, heat treatment under relatively low O₂ partial pressures, used to create O vacancies, leads to considerable reduction in local variations of lattice spacings in YBa₂Cu₃O_7−δ thin films.