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.     

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.     

Synthesis and Characterization of Ml2-Intercalated Bi-2212 Cuprates (M=Mn,Fe, Co,Cu, Zn)

Abstract

A series of new layered cuprates with the composition MI_2+xBi₂Sr₂CaCu₂O_8+y (x=0.6–0.9; M=Mn, Fe, Co, Cu, Zn) have been synthesized by the reaction of Bi₂Sr₂CaCu₂O₈ with each transition metal under an atmosphere of iodine at 400°C. The new cuprates, lamellar in shape, are crystallized in a tetragonal unit cell with the lattice parameters of a = 5.393–5.402 Å and c = 43.32–43.96 Å. A structure model for these cuprates are proposed in which the monoiodide anions are intercalated in the Bi₂O₂ layer to form a bilayer accompanying 3d metal cations. All of the intercalated cuprates are non-superconducting to be as high as 0.74–2.52 MΩ · cm in resistivity at room temperature.     

Resistance and Current Density Studies on Plasma Sprayed Coatings of Bi(Pb)?Ca?Sr?Cu?O Superconducting Materials

Plasma spraying is a potential technique for forming flexible tapes from brittle high T_c oxides. It is possible to obtain superconducting Bi(Pb) Ca Sr Cu O coating by suitable heat treatment schedule after spraying. In an effort to get maximum transport current densities (J_c) of the coating, the content of lead and sintering time have been optimised. A J_c value of 200 Amp/cm² is obtained in Bi_1.4Pb_0.6 · Ca₂Sr_1.9Cu₃O_y specimen coated on silver sprayed Fe[(Ag)/Fe] substrate. Remarkable improvement in J_c values up to 694 Amp/cm² is obtained in the same specimen coated on Ca₂Sr_1.9Cu₃O_y sprayed Fe[Ca₂Sr_1.9Cu₃O_y)/Fe] substrate. The observed decrease in J_c(B) curves with increase in magnetic field shows the presence of weak coupling between the grains.     

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.     

Crystal and magnetic structures of the Bi1 ? xSrxFeO3 ? δ and Bi1 ? xAxFe1 ? xMnxO3 (A = Sr, Ca) solid solutions

Bi_{1 − x} Sr _x FeO_{3 − x/2} (I), Bi_{1 − x} Sr _x Fe_{1 − x} MnxO₃ (II), and Bi_{1 − x} Ca _x Fe_{1 − x} Mn _x O₃ (III) solid solutions have been obtained. Their magnetization has been measured by X-ray and neutron diffraction and M?ssbauer spectroscopy. According to the M?ssbauer spectroscopy data, iron ions are in the trivalent state in system I. Near the concentration x ≈ 0.2, rhombohedral distortions (sp. gr. R3c) are transformed into tetragonal (P4/mmm). The symmetry of system II changes at x > 0.2 (R3c → R3c), whereas orthorhombic distortions (R3c → Pbnm) arise in system III at x > 0.2. The magnetic structure is antiferromagnetic (of G type). The samples of systems II and III exhibit weak ferromagnetism at x > 0.2 due to the Dzyaloshinski-Moriya interaction.     

Effect of the oxygen pressure during annealing on Tc and lattice parameter c of Bi-2212 single crystals

The influence of oxygen partial pressure (p_o2 = 10⁻⁴–1.5 · 10² atm) during annealing on the T_c and lattice parameter c of Bi-2212 single crystals has been investigated. Antibate correlation between non-monotonous alteration of the c parameter and T_c with the increase in oxygen content has been revealed.     

Crystal structure and superconductivity of Bi-2223

The crystal structure of the Bi₂Sr₂Ca₂Cu₃O_{10 + x} high-temperature superconductor is investigated by the X-ray Rietveld method. The results obtained are used to analyze the structural features of the bismuth high-temperature superconductors in respect to their superconducting properties. The refinement of the structure of the Bi-2223 compound in the four-dimensional space group A2aa (a00) 000 (Z = 4) with the vector q ～ 0.21a* does not reveal any indication of a modulated structure of the Bi-2212 type. The lattice parameters are 5.411(3), 5.409(1), and 37.082(1) Å. The agreement factors are R _wp = 8.10% and R _p = 5.49%. The results obtained are consistent with the notion that bismuth high-temperature superconductors are supercon-ductors with a more distorted crystal structure as compared to other representatives of high-temperature superconductors with critical temperatures T _c > 100 K. These distortions primarily manifest themselves in the segregation of the Bi and O ions of the “charge block” with the formation of zigzag chains that are characteristic of the structure of Bi₂O₃ and are stimulated in particular by defects in the calcium layer.     

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.     

Iodine Intercalation of Bi2Sr2Ca(n−1)CunOy(N=2,3) Superconductors by Using Reactants I2 or FeI2

Abstract

The change of superconductivity induced by intercalation is very interesting We have investigated on intercalation into Bi2212 single crystal and Bi2223 polycrystalline superconductors using FeI₂ or I₂ as reactant. The iodine intercalation by using FeI₂ as a reactant into Bi2223 phase is reported for first time as long as we know. In iodine intercalation into Bi2212 by using FeI₂ as reactant, the critical tem T_Conset in out-of-plane measurement has suddenly decreased on X=0.95. Similar changes of T_Conset with higher X have been observed independent of directions and reactants. T_Conset of I_xBi₂Sr₂CaCu₂O_y intercalated by FeI₂ is a little lower than one of I_xBi₂Sr₂CaCu₂O_y intercalated by I₂. This is likely due to the change of hall concentration induced by reduction of host In iodine intercalation into Bi2223, the smaller change of T_Conset with increasing amount of intercalant is likely due to the number of CuO₂ planes between ntercalant layers.     

The (Bi,Pb)4Sr3Ca3Cu4Ox glass–ceramics: Disordered metal and superconductor

The (Bi_0.8Pb_0.2)₄Sr₃Ca₃Cu₄O_x glass, annealed under proper conditions, is transformed into a granular metal and superconductor. Oxide superconductors of the bismuth family crystallize as a result of annealing: (Bi,Pb)₂Sr₂CuO_x (2201, T_c = 10 K), (Bi,Pb)₂Sr₂CaCu₂O_x (2212, T_c = 85 K) and (Bi,Pb)₂Sr₂Ca₂Cu₃O_x (2223, T_c = 100 K). (Bi_0.8Pb_0.2)₄Sr₃Ca₃Cu₄O_x glass–ceramic samples were obtained by annealing an amorphous solid at temperatures between 650 °C and 870 °C. The temperature dependence of resistivity in annealed samples was measured with the conventional four-terminal method in the temperature range from 3 K to 300 K. The (Bi_0.8Pb_0.2)₄Sr₃Ca₃Cu₄O_x glass–ceramics may be considered as a disordered metal and superconductor. The material has high resistivity and a high, usually negative, temperature coefficient of resistivity (TCR). Its granular and disordered character is also reflected in its superconducting properties. The normal-state and superconducting properties are correlated.     

Strontium-based Mercury Cuprates with Perovskite-like Crystal Structures

Conditions of synthesis, structure, and temperatures of superconducting transitions of strontium-based mercury cuprates Hg—Sr—Me—Cu—O (Me = Ca, La, Ce, Sm, Ho) with perovskite-like crystal structure are described. The samples belong to two homological series: HgSr₂ (Ln, Ce)_n–1CunO_2n + _{2 + δ} with the Hg—O bond directed along <110> and (Hg, Cu) Sr₂Ln_n–1Cu_nO_{2n + 2 + δ} with the (Hg, Cu)—O bond directed along <100>. The variation of composition leads to rotation of the Hg—O bond along the hk0 direction and consequently to the increase of T_c from 28 K to 81 K. An anomaly of the resistivity was observed around 200 K for most of the investigated samples, independent of their content and phase composition.     

Thermoelectric properties of Tl‐doped Bi2Se3 single crystals

The single crystals of the ternary system based on Bi_2‐xTl_xSe₃ (nominaly x = 0.0‐0.1) were prepared using the Bridgman technique. Samples with varying content of Tl were characterized by the measurement of lattice parameters, electrical conductivity σ_⊥c , Hall coefficient R_H (B∥c), and Seebeck coefficient S (ΔT ⊥c). The measurements indicate that by incorporating Tl in Bi₂Se₃ one lowers the concentration of free electrons and enhances their mobility. This effect is explained in terms of the point defects in the crystal lattice – formation of substitutional defects thallium on the site of bismuth Tl_Bi and the decrease of concentration of selenium vacancies V_Se⁺². We also discuss the temperature dependence of the power factor σS² of the samples. Upon the thallium doping we observe a significant increase of the power factor compare to the parental Bi₂Se₃. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermal expansion in the AgGa(S1−xSex)2 solid solutions from X-ray diffraction data

The lattice parameters a and c as well as the axial thermal expansion coefficients in the AgGa(S_1-xSe_x)₂ solid solutions with chalcopyrite-type structure were determined as a function of temperature in the range from 80 to 700 K and composition x using an X-ray powder diffractometry technique. It is found that the thermal expansion coefficients were anisotropic and for all the solid solutions the thermal expansion coefficients along the tetragonal c-axis were negative whereas those along the a-axis and the volume coefficients were positive. The directions in which the crystal thickness does not change as temperature varies, were found. The composition dependences of these coefficients were non-linear.     

Microstructural,thermal, and electrical properties of Bi1.7V0.3Sr2Ca2Cu3Ox glass‐ceramic superconductor

A glass‐ceramic Bi_1.7V_0.3Sr₂Ca₂Cu₃O_x superconductor was prepared by the melt‐quenching method. The compound was characterized by scanning electron microscopy, x‐ray diffraction, differential thermal analysis, current‐voltage characteristics, transport resistance measurements, and Hall effect measurements. Two main phases (BSCCO 2212 and 2223) were observed in the x‐ray data and the values of the lattice parameters quite agree with the known values for 2212 and 2223 phases. The glass transition temperature was found to be 426 °C while the activation energy for crystallization of glass has been found to be E_a = 370.5 kJ / mol. This result indicates that the substitution of vanadium increased the activation energy for the BSCCO system. An offset T_c of 80 K was measured and the onset T_c was 100 K. The Hall resistivity ρ_H was found to be almost field‐independent at the normal state. A negative Hall coefficient was observed and no sign reversal of ρ_H or R_H could be noticed. The mobility and carrier density at different temperatures in the range 140‐300 K under different applied magnetic fields up to 1.4 T were also measured and the results are discussed. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

The influence of low-temperature annealings on the structural and superconducting properties of Bi 2212 and Bi 2201 whiskers

The influence of post-growth short-term low-temperature annealings (O₂, 400°C, 5–15 min) on the composition, crystal structure, and superconductivity of Bi₂Sr₂CaCu₂O_{8 + δ} and Bi₂Sr₂CuO_{6 + δ} oxycuprate whiskers freely grown in gas cavities has been investigated. The optimal conditions for growth in closed gas cavities in a flux and post-growth annealing in oxygen were found, making it possible to obtain high-quality superconducting Bi 2212 and Bi 2201 whiskers in a wide doping range (from heavily underdoped to optimally doped) with a small rocking curve half-width (～0.1^°–0.2^°) and narrow superconducting transition (ΔT = 1.5–2 K).     

Rapid quenching and glass formation in chalcogenide glasses: Preparation and properties of Ge–As–Te glasses over an extended composition ranges

In Ge–As–Te system, the glass forming region determined by normal melt quenching method has two regions (GFR I and GFR II) separated by few compositions gap. With a simple laboratory built twin roller apparatus, we have succeeded in preparing Ge_7.5As_xTe_92.5−x glasses over extended composition ranges. A distinct change in T_g is observed at x = 40, exactly at which the separation of the glass forming regions occur indicating the changes in the connectivity and the rigidity of the structural network. The maximum observed in glass transition (T_g) at x = 55 corresponding to the average coordination number (Z_av) = 2.70 is an evidence for the shift of the rigidity percolation threshold (RPT) from Z_av = 2.40 as predicted by the recent theories. The glass forming tendency (K_gl) and ΔT (=T_c−T_g) is low for the glasses in the GFR I and high for the glasses in the GFR II.     

Structure of phases of the sillenite family in the Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-V<Subscript>2</Subscript>O<Subscript>5</Subscript> system

X-ray diffraction studies of sillenite Bi₂₄V₂O₄₀ single crystals grown by the hydrothermal method are performed for a separate crystal and powdered crystals. It is found that the composition of the two specimens is described by the (Bi_{24 − x} ▭ _x )[Bi _y ³⁺V_1−y ⁵⁺]₂ O₄₀ general formula with completely populated oxygen sites but differs in the content of vacancies at the bismuth site (this was established for the first time) and the Bi: V ratio at the tetrahedral site. The structural models of all the vanadium-containing sillenites reported in the literature are considered, and the possibility that Bi atoms are located at the centers of BiO₄ tetrahedra is established.     

Nanostructured crystals of fluorite phases Sr1 ? xRxF2 + x (R are rare-earth elements) and their ordering: IV. Study of the optical transmission spectra in the 2–17-μm wavelength range

Transmission spectra of two-component crystals of Sr_1−x R _x F_2+x (R = Y, La-Lu; 0 ≤ x ≤ 0.5) in the 1–17-μm wavelength range were studied. The spectral characteristics of these crystals and of single-component crystals of MF₂ (M = Ca, Sr, or Ba) and RF₃ (R = La-Nd) were compared. The transmission cutoff of Sr_1−x R _x F_2+x crystals is shifted to shorter wavelengths with increasing x. The same tendency is observed with the increasing atomic number R of rare-earth elements for two isoconcentration series of Sr_1−x R _x F_2+x (x ∼ 0.10 and 0.28). This tendency is pronounced at large x. The transmission cutoff of Sr_1−x R _x F_2+x crystals can be varied in the range of from 10.7 to 12.2 μm by changing their qualitative (R) and quantitative (x) composition. Hence, these crystals can be assigned to multicomponent fluoride optical materials with controlled optical characteristics. The Sr_1−x R _x F_2+x crystals, where R = Ce-Sm, were shown to be promising materials for the design of selective optical filters in the 2–10-μm spectral range.