Engineered flux pinning centres in Pb-doped high temperature superconducting “Bi2Sr2CaCu2O8” ceramics

The Pb solubility of Bi₂Sr₂CaCu₂O₈ is determined within the concentration range Bi_2.18-x Pb _x Sr₂CaCu_8+d with 0 x 0.6 and the temperature range from 800 to 900°C. From a consideration of the Pb solubility in Bi₂Sr₂CaCu₂O₈ a simple annealing procedure was developed to precipitate (Pb,Bi)₄(Sr,Ca)₅Cu0_10+d (451 phase) in high-temperature superconducting Pb-rich Bi₂Sr₂CaCu₂O₈ ceramics. The precipitation results in a two-fold increase of the critical current density which is believed to express improved pinning properties of the superconducting ceramics. The microstructures of the samples with increased critical current density were studied with respect to the grain size and volume content of the 451 phase.     

Superconductivity of barium-doped Bi2Sr2CaCu2Oy

Sintered ceramic samples of Bi₂Sr_2–x Ba _x CaCu₂O_y with nominal barium fraction 0x0.3 have been prepared by the solid-state reaction method. WDS studies verified that barium enters the superconducting phase. For slowly cooled samples, the midpointT _c of the superconducting transition is significantly increased by barium doping, whereas for quenched samplesT _c is little affected. The increase ofT _c with increasing barium fraction is consistent with a decrease in the hole concentration in the superconducting layers.     

Structure and Diamagnetic Properties of (Pb0.6SnyCu0.4 ? y)Sr2(Y1 ? xCax)Cu2Oz

The effect of Sn doping in (Pb_0.6Sn _y Cu_{0.4 – y} )Sr₂(Y_{1 – x} Ca _x )Cu₂O _z with 0 y 0.3 and 0 x 0.7 was investigated. It was established that a nearly pure 1212 phase can be obtained at 0 y 0.1 and 0 x 0.3. The obtained XRD patterns as well as the results of the EDX and ICP-AES analyses showed that Sn substitution is possible in the (Pb,Cu)-1212 phase. Superconductivity was observed at 0.4 x 0.7. The onset of the diamagnetic transitions varied from 10 to 30 K. The influence of the strong Pb deficiency on the superconducting properties of the samples was discussed.     

Fabrication of Bi2Sr2CaCu2Ox films on metal substrates by the chemical process using metal alkoxides

The formation behaviour of Bi₂Sr₂CaCu₂O_x from compounds prepared by hydrolysis of metal alkoxides was studied and Bi₂Sr₂CaCu₂O_x films on metal substrates were fabricated using a metal alkoxide solution. Bi₂Sr₂CaCu₂O_x was formed through intermediate phases such as Bi₂Sr₂Cu₁O_x, Bi₂CuO₄, SrCO₃, CaCO₃ and CuO. Bi₂CuO₄ was initially formed with SrCO₃, CaCO₃ and CuO, and then reacted with SrCO₃ to form Bi₂Sr₂Cu₁O_x. Bi₂Sr₂Cu₁O_x reacted with CaCO₃ and CuO to give Bi₂Sr₂CaCu₂O_x. Bi₂Sr₂CaCu₂O_x films were successfully fabricated on nickel substrates using the metal alkoxide solution at the nominal composition of BiSrCaCu=2223. Bi₂Sr₂CaCu₂O_x was precipitated on Ni substrates at firing temperature of 770 °C or above, and a sharp T _c was obtained at the firing temperature of 800 °C.     

Codeposition of Metallic Components in the Growth of Thin PbTe?Ga? Films on Si Substrates

In depositing thin PbTeGa films onto Si and SiO₂/Si substrates by the hot-wall method, Pb_{1 – x} Ga _x melts were used as Ga vapor sources in combination with separate Pb and Te vapor sources. The vaporization of Pb_{1 – x} Ga _x (0.15 x 0.95) melts was studied between 1000 and 1300 K in the reaction chamber of the deposition unit. Using electron probe x-ray microanalysis, all the deposited films were shown to contain Ga. Pb_{1 – x} Ga _x melts were also used as separate Pb and Ga vapor sources.     

Synthesis and Superconductivity of New Cuprates (Pb0.8W0.2)Sr2(Nd1 ? xCax)Cu2O7 ? δ

New cuprates with nominal composition (Pb_0.8W_0.2)Sr₂(Nd_{1 – x} Ca _x )Cu₂O_{7 –} (0x1) were synthesized by solid-state reaction in N₂. The crystal structure was characterized by X-ray powder diffraction (XRD) as tetragonal. Direct current electrical resistance measurements were applied to check the existence of superconductivity in these cuprates. Superconductivity with T _c (onset) up to 82 K is observed when x = 0.6. Synthesis in N₂ is necessary in obtaining superconductivity in these cuprates. Preparation in air or post-treatment in flowing oxygen destroys superconductivity. A comparison is made with previous Pb-based 1212 superconducting oxides. The valence of Pb and the possible position of W in the lattice are discussed.     

Effect of the Oxidation State of Pb on the Superconducting Transition Temperature of Bi2 – x Pb x Sr2CaCu2O8 + δ

A procedure is developed for determining the Pb⁴⁺ concentration in Pb-substituted Bi-based 2212 superconductors. The effect of the Pb⁴⁺ : Pb²⁺ ratio on the superconducting transition temperature of 2212 is studied. The results indicate that the highest T _c is offered by Bi_1.8Pb_0.2Sr₂CaCu₂O_{8 +} containing the smallest amounts of Pb and Cu in their higher oxidation states.     

A new model for the formation of high-T c phase in superconductive (Bi, Pb)2Sr2Ca2Cu3O x glass-ceramics

The formation mechanism of the high-T _c phase through the glass-ceramic route and the role of Pb on the formation of this phase have been investigated. It was found that a new compound with the chemical composition Pb₂Sr_{3 – x} Ca _x CuO _y (x = 1.8) precipitates at around 550C. This phase is stable up to 800C, where it begins to decompose, and at 850 C it completely disappears. It was found that some part of the released Pb diffuses into the 2212 phase leading to the formation of Pb-containing 2212 phase, (Bi, Pb)₂Sr₂CaCu₂O _x . On the other hand, an endothermic peak, probably arising from the melting of (Bi, Pb)₂Sr₂CaCu₂O _x phase or melting at grain boundaries containing Pb²⁺, was observed at 856C only in Pb-containing samples that were heat treated. The liquid phase attributed to the endothermic peak may enhance the formation of high-T _c phase (2223 phase). The growth kinetics for the high-T _c phase were analysed using the Johnson-Mehl-Avrami equation; the results indicate that the growth of the high-T _c phase is controlled by a diffusion process and the activation energy for its formation in the initial stage (shorter than 96 h) is 576 ± 45 kJ mol^–1.     

Microscopic State of Low Doped Manganites La1 ? xSrxMnO3 Probed by ESR

The electron spin resonance (ESR) measurements were performed in single crystals of La_{1 – x} Sr _x MnO₃ (0.05 x 0.125) in order to study the interplay of crystal field, Dzyaloshinsky–Moriya interaction, Jahn–Teller (JT) effect, and orbital order. The angular dependence of the ESR linewidth of an untwinned La_0.95Sr_0.05MnO₃ single crystal has been analyzed in the high-temperature approximation, which takes into account the microscopic geometry of the four nonequivalent Mn positions in the orthorhombic unit cell. A strong mixing of the |3z ² – r ²> and |x ² – y ²> states for the real orbital configuration was found. Magnetic inhomogeneities observed in the ESR spectra across the composition range 0.075 x 0.125 can be attributed to the presence of ferromagnetic clusters (magnetic spin polarons) in the paramagnetic state. New polaronic models are proposed.     

Significant Improvement in Superconductivity by Substituting Pb at Bi-site in Bi2?xPbxSr2CaCu2O8 with x=0.0 to 0.40

Here we report the synthesis and superconducting properties of bulk Bi_2−x Pb _x Sr₂CaCu₂O₈ (x=0.0 to 0.4) compound. Though the superconducting transition temperature (T _c) decreases marginally, the critical current density under magnetic field J _c(H) increases with Pb content. An optimization is observed for x=0.16 with J _c(H) (7.894×10³ A/cm²) that is nearly doubled in comparison to the pristine compound. It seems that controlled substitution of Pb at Bi-site in bulk Bi-2212 (Bi₂Sr₂CaCu₂O₈) system can enhance the superconducting critical parameters. These results are explained on the basis of possible improved inter- and intra-granular properties with Pb substitution in Bi_2−x Pb _x Sr₂CaCu₂O₈ system.     

Valence Charge Fluctuations and Tc Retention in Tl1?xPbxSr1+xLa1?xCuO5?y (0.0 ≤ x ≤0.5) System

Structural and x-ray photoelectron spectroscopy (XPS) studies of the Tl_1–xPb_xSr_1+xLa_1–xCuO_5–y (0.0x0.5) system have been carried out. The unit cell parameters increase with x. Irrespective of x the T_c is retained in this series and the optimum hole concentration (n_h) is maintained for x 0.5. An increase in Tl 4f and O ls binding energy with x suggests a reduction in their oxidation state. Origin of holes is discussed in terms of charge transfer between Tl, Pb and CuO₂ layers.     

Pb and In Codeposition in the Vacuum Growth of PbTe<In> Films on Si Substrates

Pb_{1 – x} In _x melts were proposed to be used as In vapor sources, in combination with separate Pb and Te sources, in depositing PbTe films onto Si substrates by a modified hot-wall method. Under the assumption that the presence of Pb in Pb_{1 – x} In _x melts may raise the In partial pressure, the vaporization behavior of Pb_{1 – x} In _x (0.05 x 0.70) was studied between 900 and 1200 K in the reaction chamber of the deposition unit. Using electron probe x-ray microanalysis and x-ray diffraction, all the deposited films were shown to contain In. The In content of the Pb_{1 – y} In _y deposits varied in the range 0.002 <y < 0.07 and increased with increasing In concentration in the Pb_{1 – x} In _x melt and with increasing vapor source temperature. The vapor over molten Pb_{1 – x} In _x was shown to exhibit a positive deviation from ideality.     

Anomalous High-Temperature Properties of BaPbO3-Based Solid Solutions

The thermal expansion, thermal stability, and electrical resistivity of the Ba_{1 – x} M _x Pb_{1 + y} O_{3 +} (M = Sr, Ca; 0 x 1.0, 0 y 0.2) and Ba_{1 – x} M" _x Pb_{1 – y} M" _y O_{3 +} (M" = K, La; M" = Sc, Sb; x, y= 0.01) ceramic materials were studied between 293 and 1073 K in air. The linear thermal expansion coefficient of the ceramics was found to increase abruptly at 700 K, from (10–14) × 10^–6K^–1in the range 300–600 K to (13–18) × 10^–6K^–1in the range 800–1000 K. The electrical resistivity of the ceramics passes through a sharp maximum near 750 K, with the largest jump in resistivity at the compositions Ba_0.6Sr_0.4PbO₃and Ba_0.9Ca_0.1PbO₃. The anomaly in thermal expansion is likely associated with the rearrangement of the lead–oxygen polyhedra in the structure of the solid solutions, and the jump in resistivity is attributable to changes in the average oxidation state of Pb ions in the surface layer of the ceramics.     

Transport and Magnetic Properties of Bi1.7Pb0.4Sr1.5Ca2.5Cu3.6Ox/(LiCl)y Superconductors

We investigated the superconducting critical temperature, the intra- and intergranular critical current density, and the thermopower properties of Bi_1.7Pb_0.4Sr_1.5Ca_2.5Cu_3.6O _x /(LiCl) _y samples. All these properties have been compared with those of Bi_1.7Pb_0.4Sr_1.5Ca_2.5Cu_3.6O _x /(LiF) _y specimens. It was found that the critical temperature determined from resistive and AC complex susceptibility measurements show a maximum and the transition width shows a minimum for the intermediate values of y. Powder X-ray diffraction studies and the AC complex susceptibility measurements reveal that in our samples the amount of Bi₂Sr₂Ca₂Cu₃O_{10 +} high-temperature superconducting phase is maximum for y 0.02. The amount of LiCl in Bi_1.7Pb_0.4Sr_1.5Ca_2.5Cu_3.6O _x /(LiCl) _y changes the superconducting properties of the grains as well as of the intergrain matrix. The splitting of the peak in the temperature dependence of the imaginary part of the complex susceptibility, corresponding to the dissipation inside the grains, was also observed.     

Growth of In-Doped PbTe Films on Si Substrates

Data on the evaporation behavior of Pb_{1 – x} In _x (0.10 x 0.70) melts were used to devise a procedure for the growth of vapor-phase In doped PbTe thin films on Si substrates. This approach offers the possibility of growing single-phase, homogeneous Pb_{1 – y} In _y Te films of controlled composition by adjusting the composition and temperature of Pb_{1 – x} In _x (0.10 x 0.50) melts. X-ray diffraction characterization demonstrates that the films grown on Si with no oxide layer consist of slightly misoriented crystallites, with their (100) axes normal to the film surface, whereas the films grown on substrates covered with a SiO₂ layer are polycrystalline, with a strong (100) texture.     

Electrical characteristics of SrxBi2.4Ta2O9 thin film and Pt/Sr0.85Bi2.4Ta2O9/Al2O3/Si structure

Sr _x Bi_2.4Ta₂O₉ (0.7 x 1.3) thin films were processed by metalorganic decomposition and their ferroelectric characteristics were investigated. The Sr-deficient Sr _x Bi_2.4Ta₂O₉ films exhibited well-developed ferroelectric hysteresis curves compared to those of the Sr-excess films, and Sr_0.85Bi_2.4Ta₂O₉ film had the optimum electrical characteristics among Sr _x Bi_2.4Ta₂O₉ films. Electrical characteristics of the Pt/SBT/Al₂O₃/Si structure using Sr_0.85Bi_2.4Ta₂O₉(SBT) film were investigated for metalferroelectric-insulator-semiconductor field-effect-transistor (MFIS-FET) applications. Memory window of C-V hysteresis characteristics of the Pt/SBT/Al₂O₃/Si structure became large with decreasing the Al₂O₃ thickness, and the Pt/SBT(400 nm)/Al₂O₃ (10 nm)/Si structure gave memory window of 2.2 V at sweeping voltages of ±5 V. The Pt/SBT/Al₂O₃/Si structure can be proposed for MFIS-FET applications.     

Resistivity Anisotropy and Hall Coefficient of Pb-Doped Bi2212 Single Crystals

In-plane and out-of-plane resistivity and Hall coefficient measurements were carried out on Bi _2.1-x Pb _x Sr ₂ CaCu ₂ O _y (x = 0 0.6) single crystals with various oxygen concentration. The resistivity anisotropy was decreased with an increase of oxygen concentration and Pb content. Hall coefficient, R _H , measurement revealed that the Pb-doping increases carrier concentration in the present system, however, its essential effect on reducing anisotropy was confirmed by comparing R _H and ² of the Pb-free and Pb-doped crystals.     

Effect of Co substitution for Mn on Y1−x Sr x MnO3 properties for SOFC cathode material

Y_0.6Sr_0.4Mn_1–y Co _y O₃ (0 y 0.4) perovskite oxides were prepared by the coprecipitation method. The effect of Co substitution for Mn on the crystal structure, electrical conductivity and thermal expansion properties were investigated. By X-ray powder diffraction, the crystal structure was found to change from hexagonal symmetry of Y_0.8Sr_0.2MnO₃ to orthorhombic of Y_0.6Sr_0.4Mn_1–y Co _y O₃. The differences in the structure of the unsubstituted Y_1–x Sr _x MnO₃ (0.2 x 0.4) are attributed to the average ionic radii of the cations and the amounts of Mn⁴⁺ present. The results of electrical conductivity analysis can be described by the small polaron hopping conductivity model. With Co substitution, the activation energy increases, possibly due to an increase of Jahn–Teller distortion, at an extent higher than the increase of the concentration of charge carriers; thus, the electrical conductivity decreases. In addition, the relative densities of the materials reached 94% with sintering at 1350°C for 12 h and had higher concentration of the available lattice sites, thus showing higher conductivity, than that with sintering at 1300°C for 6 h, which achieved 70% relative density. It is also found that the thermal expansion coefficient (TEC) increases as the Sr and Co content of Y_1–x Sr _x Mn_1–y Co _y O₃ increases and those with Co content of y = 0.2 exhibit TEC compatibility with YSZ.     

Preparation of Bi2Sr2CaCu2O8 + x-Matrix Composites Containing Fine Strontium Calcium Indate Inclusions via Glass Crystallization

The crystallization of glass with a composition of Bi₂Sr₂CaCu₂O_{8 + x} + 0.25Sr_0.6Ca_0.4In₂O₄was studied in air between 400 and 800°C. Below 700°C, crystalline phases were formed in the following sequence: (Sr,Ca)_0.9Bi_1.1O_2.55, Cu₂O, Bi-2201, (Sr,Ca)In₂O₄, (Sr,Ca)₃Bi₂O₆, and Bi-2212. Above 700°C, the predominant phases were Bi-2212 and (Sr,Ca)In₂O₄. The introduction of In into Bi–Sr–Ca–Cu–O was shown to reduce the glass-forming capability of this system, without suppressing Bi-2212 formation. The Bi₂Sr₂CaCu₂O_{8 + x} + 0.25Sr_0.6Ca_0.4In₂O₄composites prepared by annealing the precursor glass contained 0.2- to 0.4-m inclusions and possessed enhanced superconducting properties.     

Boron Substitution for Bi in Sr-Free Bi-2212 Superconductor of Bi<Subscript>2</Subscript>Pr<Subscript>0.5</Subscript>Ca<Subscript>2.5</Subscript>Cu<Subscript>2</Subscript>O<Subscript><Emphasis Type="Italic">z</Emphasis></Subscript>

Possibility of boron substitution for Bi and the substitution effect on superconductivity is investigated for the Bi-2212 phase of Bi-Sr-Ca-Cu-O. From X-ray diffraction study, it is found that samples in the (Bi_2−x B _x )Sr₂CaCu₂O _z system are mainly of the single 2212 phase in a composition range of 0.0≤x≤0.6, and both of the lattice parameters a and c change with increasing x up to 0.6. From measurements of the magnetic susceptibility and the electrical resistivity, the superconducting transition temperature is found to increase up to 0.6 with increasing x. These results are considered to show that boron is substitutable for Bi up to x=0.6 in the (Bi_2−x B _x )Sr₂CaCu₂O _z system and that the boron substitution causes the number of hole-carriers to decrease in this system.