Formation of the (Bi, Pb)2Sr2Ca2Cu3O10+δphase: reaction mechanism and kinetics

In order to elucidate the formation mechanism of the Bi, Pb(2223) phase, extensive investigations have been performed by means of combined differential thermal analysis and thermo-gravimetric measurements, X-ray diffraction as well as scanning electron microscopy and energy dispersive X-ray microanalysis.Starting from co-precipitated oxalate powders, the transformations leading to the formation of the Bi, Pb(2223) phase were studied. Based on these investigations the Bi,  Pb(2223) phase formation process, involving the Bi, Pb(2212), Ca₂PbO₄and alkaline-earth cuprate phases as precursors has been separated into elemental steps. A new model for the formation mechanism of the Bi, Pb(2223) phase will be presented.The Bi, Pb(2223) phase formation kinetics has been studied using the Avrami relation for isothermal phase transformations. The analysis of the Bi, Pb(2223) phase evolution revealed a marked change of the Avrami exponent during the course of the Bi, Pb(2223) phase formation after about 12 hours sintering at 857 ° C.The activation energy for the formation of the Bi, Pb(2223) phase has been determined under various experimental conditions. The nominal composition of the precursor powders, the temperature at which they were calcined as well as the size of their constituents were found to have a significant influence on the value of the activation energy.     

Effects of Ni and Co doping on the physical properties of tetragonal FeSe0.5Te0.5 superconductor

Isoelectronic Tellurium (Te) substitution for Selenium (Se) in the tetragonal phase of FeSe (β-FeSe) increases the superconducting transition temperature (T_c) by applying a negative pressure on the lattice. However, the normal state resistivity increases and shows semi-metallic behavior for samples with higher Te concentration. With increasing Te concentration, the T_c increases and reaches a maximum for FeSe_0.5Te_0.5 and then decreases with further increase of Te. We have investigated the effect of Cobalt (Co) and Nickel (Ni) doping in FeSe_0.5Te_0.5 in the nominal composition range Fe_1?xTM_xSe_0.5Te_0.5 (TM = Co (x = 0.05, 0.1, 0.15, 0.2) and Ni (x = 0.05, 0.1)). Both Co and Ni doping suppress T_c and drives the system to metal–insulator transition. The in-plane (‘a’) and out-of-plane (‘c’) lattice constants decrease with increasing dopant concentration.     

Composition-dependent metal-insulator transition in perovskite CaXPb(1−X) TiO3 (CPT) ceramic

Ceramic compositions of a complex perovskite Ca_XPb(_1?X)TiO₃ (CPT) systems with x=0.6, 0.7 and 0.8 were prepared by mechanical mixing of their oxides (CaTiO₃ and PbTiO₃). The structure of the (CPT) ceramics was characterized by X-ray diffraction (XRD) The ceramics transform gradually from orthorhombic phase (pseudo cubic phase) to cubic phase by increasing pb content percent. The dc resistivity ρ(t) versus temperature (range 300–525 K) for x=0.6, 0.7 and 0.8. The ρ.T/curves reveal that samples exhibit a metallic behaviour at low temperature and undergo a metal-semiconductor transition with increasing temperature at T_p=373 K, 343 K and 333 K, for x=0.6, 0.7 and 0.8, respectively. The nature of conduction mechanism is studied in semiconductor region by studying the current–voltage temperature characteristics. The current–voltage characteristics were interpreted in terms of Poole–Frenkel type of conduction mechanism.     

Influence of Sr substitution on thermoelectric properties of La1−xSrxFeO3 ceramics

Perovskite La_1−xSr_xFeO₃ (0.10 ⩽ x ⩽ 0.20) ceramics have been synthesized by the conventional solid-state reaction technique. Their electrical resistivity, Seebeck coefficient and thermal conductivity have been measured. It has been found that the increase of Sr content reduces significantly both the electrical resistivity and the Seebeck coefficient, but slightly increases the high-temperature thermal conductivity. An adiabatic hopping conduction mechanism of small polaron is suggested from the analysis of the temperature dependence of the electrical resistivity. Seebeck coefficients decrease with increasing temperature, and saturate at temperature above 573 K. The saturated value of Seebeck coefficient decreases with increasing of Sr contents, from 200 μV/K for x = 0.10 to 100 μV/K for x = 0.20. All samples exhibit lower thermal conductivity with values around 2.6 W/m K. The highest dimensionless figure of merit is 0.031 at temperature 973 K in La_0.88Sr_0.12FeO₃.     

Synthesis and superconductivity properties of Ba1−xKxBiO3

Ba_1?xK_xBiO₃ with x from 0.315 to 0.6 were successfully synthesized by molten salts method and characterized by XRD and magnetic susceptibility measurements. It is found that Ba_1?xK_xBiO₃ powders could directly be precipitated from KOH melts. Superconductivity has been observed in all samples and the highest superconducting transition temperature was found to be T_c = 30.6 K with x = 0.4. The lattice constant linearly depended on the potassium content in accord with the equation of a = 4.3548–0.1743x, and the decrease of the mole ratio of Bi³⁺/Bi⁵⁺ resulted in the increase of the potassium content, which suggested the disproportionation of Bi valence.     

Superconductivity in CeO1−xFxFeAs with upper critical field of 94 T

We have successfully synthesized Ce based oxypnictide superconductors with fluorine doping (CeO_1?xF_xFeAs) by a two step solid state reaction method. Detailed XRD and EDX confirm the crystal structure and chemical compositions. We observe that an extremely high H_c2(0) of 94 T can be achieved in the x = 0.1 composition. This increase in H_c2(0) is accompanied by a decrease in transition temperature (38.4 K in x = 0.1 composition) from 42.5 K for the x = 0.2 phase. The in-plane Ginzburg–Landau coherence length is estimated to be ～27 Å at x = 0.2 suggesting a moderate anisotropy in this class of superconductors. The Seebeck coefficient confirms the majority carrier to be electrons and strong dominance of electron–electron correlations in this multiband superconductor.     

Synthesis and critical current density promotion for Nb-doped 2212-BPSCCO HTc-superconducting materials

Although BPSCCO superconducting regime has very low stability under high oxygen pressures as reported in the literature, we managed to synthesize relatively pure 2212-BPSCCO and their Nb-doped samples having general formula Bi_1−xNb_xPbSr₂CaCu₂O₈, where x = 0.1, 0.2, 0.4 and 0.6 mole, respectively, at moderate oxygen pressure (∼30 bar). The superconducting measurements proved that the best recorded T_c ∼ 69 K was for the undoped 2212-BPSCCO, while the lowest T_c ∼ 58 K was recorded for the maximum doped sample x = 0.6 mole indicating that superconductive transition temperatures T_cs decrease regularly with increasing Nb-dopant concentration from x = 0.1 to 0.6, respectively. The lattice parameter c exhibited a slight length compression as Nb-dopant ratio increases from 0.1 to 0.6 mole, respectively. From SE-microscopic analysis, the average grain size was estimated and found in between 0.44 and 1.6 μm which is considered relatively high to that reported in the literature. The measured J_c’s values were found to be enhanced remarkably as Nb-dopant concentration increases.     

New investigation for Tc depression by Ca in Y1−xCax:123 superconducting systems

Two similar sets of the series Y_1?xCa_xBa₂Cu₃O_Y (0.00 ? x ? 0.50) are prepared by two different heat treatments at the final process of calcinations. The first set is quenched in air down to room temperature (ssq); while the second is left in the furnace and slowly cooled to room temperature (sss). After that, the samples are separately sintered in two different oxygen purity (99.99% Hp and 93% Lp, respectively) to obtain four different sets called ssqHp, sssHp, ssqLp and sssLp. Then, the considered samples are tested by XRD, SEM, resistivity and microhardness (VHN) techniques. It is found that c-parameter for ssqHP and sssLP samples increases slightly with Ca doping; while orthorhombic distortion remains nearly invariant. Interestingly, unlike for ssqHp and sssLp samples, the OD decreases continuously with Ca doping in sssHp and ssqLp samples; while c-parameter increases. SEM micrographs indicate that Ca generally improve the link between superconducting grains for all set of samples. The oxygen content is gradually decreased by Ca for all set of samples and generally follow the relation, y = 6.93 ? 0.5x. The effective Cu valence slightly decreases, as compared to pure samples, but stays nearly independent of Ca content for all the series. The relative decrease in critical temperature T_c by Ca is more in ssqHp and sssLp samples, when compared with those of sssHp and ssqLp samples. Although, an approximately linear increase in VHN with various Ca is obtained, the relative increase is more in ssqHp and sssLp samples with respect to sssHp and ssqLp samples. These results indicate that substitution of Ca at Y site leads towards oxygen vacancies predominantly created in CuO₂ planes (CuO chains) of ssqHp and sssLp (sssHp and ssqLp) based samples, and far from overdoping.     

The effect of chemical pressure in rutheno-cuprates

We have studied the effect of negative chemical pressure in the RuGd_1.5(Ce_0.5?xPr_x)Sr₂Cu₂O_10?δ with Pr content of 0.0 ? x ? 0.2. This is also investigated using the bond length results obtained from the Rietveld refinement analysis. The c parameter and cell volume increase with x for 0.0 ? x ? 0.15. The width of the resistivity transition also increases with Pr concentration, indicating higher inhomogeneity and oxygen deficiency. The difference in the ionic valences of Pr^3+,4+ and Ce⁴⁺ causing different hole doping, the difference in the ionic radii, and oxygen stoichiometry affect the superconducting transition. The magnetoresistance shows a cusp around 135 K which lies between the antiferromagnetic and ferromagnetic transition temperatures, which is probably due to the presence of a spin glass region. There exist two magnetic transition temperatures for 0.0 ? x ? 0.2 which respectively change from T_M = 155 K to 144 K and from T_irr = 115 K to 70 K. The magnetization versus applied magnetic field isotherms at 77 K and 300 K show that the remanent magnetization and coercivity are lower for samples with higher Pr content.     

Growth,structure and physical properties of single crystals of pure and Pb-doped Bi-based high Tc superconductors

Single crystals of (Bi_1−xPb_x)₂Sr₂Ca₂Cu₃O_10+δ (x = 0 and 0.16) (sizes up to 3 × 2 × 0.1 mm³) have been grown by means of a newly developed “vapour-assisted travelling solvent floating zone” technique (VA-TSFZ). Post-annealing under high pressure of O₂ (up to 10 MPa at T = 500 °C) was applied to enhance T_c (up to 111 K) and improve the homogeneity of the crystals (ΔT_c ⩽ 1 K). The structure of both Pb-free and Pb-doped Bi-2223 was refined for the first time from single crystal X-ray diffraction (XRD) data. The unit cell of the average structure is pseudo-tetragonal with a = 5.4210(7), b = 5.4133(6) and c = 37.010(7) Å, and a = 5.395(1), b = 5.413(1) and c = 37.042(11) Å, for the Pb-free and the Pb-doped phase, respectively. An incommensurate modulation in the direction of one of the short cell vectors has been defined (q ∼ 0.21 a¹), however, the structure can be conveniently described in a supercell with a fivefold volume (a = 27.105(4) Å). With respect to the “non-modulated” structure, one additional oxygen atom for ten initial O was found to be inserted into the BiO layers. The superconducting anisotropy of Bi-2223 was found to be ∼50, from measurements of the lower critical field. The anisotropy of Bi-2223 is significantly reduced compared to that of Bi-2212, and this accounts for the enhanced irreversibility fields in Bi-2223. Furthermore, Bi-2223 has a higher critical current density, and a reduced magnetic relaxation rate compared to Bi-2212, which are both signatures of more effective pinning in Bi-2223 due to its reduced anisotropy.     

Suppression of superconductivity in Zn-doped SmFeAsO0.8F0.2 system

A series of SmFe_1?xZn_xAsO_0.8F_0.2 samples with x = 0, 0.05, 0.1, 0.2 and 0.4 have been successfully synthesized using a solid state method. The lattice parameters are found to increase with increasing Zn doping content. The superconductivity has been definitely suppressed by Zn doping at Fe site with the transition temperature T_c being reduced from 52.5 K to 23.3 K for the sample of x = 0.05, and to 18.2 K for the sample of x = 0.1. For the samples with x > 0.1, the superconducting transition vanishes, and, at the meantime, the spin-density-wave anomaly recovers at 140 K. The metal to semiconductor transition is also observed in the SmFe_1?xZn_xAsO_0.8F_0.2 system. The behavior of SmFe_1?xZn_xAsO_0.8F_0.2 is very different from that of R_EFeAsO (R_E = rare earth metal), which reveals a very strong electron correlation in SmFe_1?xZn_xAsO_0.8F_0.2.     

Electronic property and structure of double-doping Y1−2xPrxCaxBa2Cu3O7−δ with 0 ⩽ x ⩽ 0.14

Equal amount Pr and Ca double-doping Y_1?2xPr_xCa_xBa₂Cu₃O_7?δ with 0 ? x ? 0.14 have been investigated by X-ray diffraction, resistivity, and X-ray photoemission spectroscopy (XPS). The deviation of the linearly decreasing of T_c vs. x curve was observed when x < 0.10. The resistivity and the temperature coefficient of resistivity also exhibit abnormal behaviors around x = 0.10. It is revealed that the conductivity behavior of Y_1?2xPr_xCa_xBa₂Cu₃O_7?δ with low Pr content (x < 0.10) is different from that of the relative high Pr content (x > 0.10), which suggests a change of Pr valence with the Pr content. XPS measurement shows that the relative amount of Pr³⁺ and Pr⁴⁺ is closely related to the total Pr content x. The valence of Pr is close to +3 when x < 0.10 and increases towards +4 when x > 0.10, which implies a different mechanism for depression of superconductivity of Pr content x < 0.10 from that of Pr content x > 0.10 in Pr doping Y-123.     

Yttrium doped La1−xYxO0.9F0.1FeAs superconductors: Hall and thermopower studies

The effect of yttrium substitution at the lanthanum site on the superconducting properties of La_1?xY_xO_0.9F_0.1FeAs (‘x’ = 0, 0.10, 0.20, 0.30, 0.50 and 0.60) oxypnictides has been studied. Powder X-ray diffraction studies confirm single phases till x = 0.1 beyond which minor amount of Y₂O₃ is observed. The temperature dependence of resistivity measurements confirm the superconducting transition temperature (T_c) of 34.8 (±0.05) K and corresponding Meissner transition at 34.3 K in the ‘x’ = 0.3 composition which is higher than that reported for the parent phase (LaO_0.9F_0.1FeAs (T_c = 28 K)). Further increase in the concentration of yttrium leads to broadening and suppression of the superconducting transition. The value of H_c2 at zero temperature is estimated to be about 60.5 T. The Seebeck coefficient (S) shows a negative sign indicating that the major contribution to the conductivity is by electrons. The Hall coefficient (R_H) also remains negative throughout the temperature range supporting the thermopower results. The lattice parameters (a and c) decreases and the charge-carrier density increases with yttrium doping.     

Superconductivity in bulk T′-(La,Sm)2CuO4 prepared via a molten alkaline hydroxide route

We have synthesized La_2?xSm_xCuO₄ (0 ? x ? 2.0) with the Nd₂CuO₄ structure via a molten alkaline hydroxide route at temperatures as low as 400–480 °C. After reduction heat treatment in vacuum at 600–750 °C for removal of excess oxygen atoms at the interstitial apical site, superconductivity with T_c = 20–24 K was observed in the samples with x = 0.05–1.0. The superconducting volume fraction is nearly 100% for x = 0.3–0.7. Our results demonstrate that La_2?xSm_xCuO₄ with no nominal carrier doping is a bulk superconductor.     

Antiferromagnetic ordering in the double perovskites La2−xSrxCoRuO6

The electric transport and magnetic susceptibility of double perovskites La_2?xSr_xCoRuO₆ have been studied over a temperature range up to 800–1000 K. The crystal and magnetic structure has been determined by neutron diffraction on two samples of the series, x=0.6 and 1.4, which represent the electron- and hole-doped systems with respect to “ideal” single-valent insulator x=1. The study shows that spins in both the Co and Ru f. c. c. like sublattices exhibit a long-range ordering of the antiferromagnetic type II (T_N=60 K for x=0.6 and T_N=60–80 K for x=1.4).     

Synthesis and characterization of (Bi,Cu)Sr2(RE,Ca)Cu2Oz (RE: Y or rare-earth element)

Samples with nominal compositions of x = 0–0.1 in (Bi_(1+3x)/3Cu_(2?3x)/3)Sr₂(RE_1?xCa_x)Cu₂O_z ((Bi,Cu)-“1-2-1-2”; RE: Y or rare-earth element) were synthesized by a solid-state reaction method and characterized by means of X-ray diffractometry (XRD). It is confirmed that the (Bi,Cu)-“1-2-1-2” forms only when RE = Y, Dy and Ho. Single- or nearly single-phase samples are obtained for x = 0–0.05 and the Ca-free composition of this compound is determined to be (Bi_1/3Cu_2/3)Sr₂RECu₂O_z. Since ionic radii of Y, Dy and Ho are very close to each other and this seems to be an essential factor for the stability of the (Bi,Cu)-“1-2-1-2”.     

Phase formation and dielectric study of Bi doped BaTi0.75Zr0.25O3 ceramic

Perovskite types Ba_1−xBi_2x/3Ti_0.75Zr_0.25O₃ (with x = 0.0, 0.025, 0.05) ceramics have been prepared through solid state reaction route. The room temperature XRD study suggests that all the compositions have single phase cubic symmetry with space group Pm-3m. Temperature dependent dielectric studies of the ceramics have been investigated in the frequency range of 50 Hz–1 MHz. The densities of the samples are determined using Archimedes’ principle and found to be ∼98% of X-ray density. The dielectric study revealed diffuse phase transition of second order. A broad dielectric anomaly coupled with the shift of dielectric maxima toward a higher temperature with increasing frequency indicates the relaxor-type behavior in the ceramics. The diffusivity increases with increase in Bi contents in the studied composition range. The transition temperature decreases with increase in Bi contents due to the decrease in grain size.     

Dielectric,optical and structural properties of Bi4V2−xSrxO11−δ (0.05≤x≤0.20)

Composition Bi₄V_2−xSr_xO_11−δ (0.05≤x≤0.20) is synthesized by melt quench technique followed by heat treatment at 800 °C for 12 h. These compounds are characterised by X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, UV–visible spectroscopy, impedance spectroscopy and scanning electron microscopy. X-ray diffraction patterns of all the samples show γ-phase stabilization at room temperature except x=0.05 heat treated sample. The optical band gap of all the samples is observed in semiconducting range. The lowest and the highest optical band gap is 2.39 eV and 2.57 eV for x=0.10 heat treated and x=0.20 quenched samples, respectively. The highest value of dielectric constant is obtained ~10⁷ with very low dielectric loss for x=0.15 and 0.20 samples at ~350 °C and below 10 Hz. The grain size increases with dopant concentration leads to increase the dielectric constant.     

Effect of Cr substitution on the superconducting and magnetic properties of RuSr2Eu1.5Ce0.5Cu2O10−δ

In this paper we investigate the properties of polycrystalline series of Ru_1?xCr_xSr₂Eu_1.5Ce_0.5Cu₂O_10?δ (0.0 ? x ? 0.40) by resistivity, XRD and dc magnetization measurements. EuRu-1222 is a reported magneto superconductor with Ru spins magnetic ordering at temperatures near 100 K and superconductivity occurs in Cu–O₂ planes below T_c ? 40 K. The exact nature of Ru spins magnetic ordering is still being debated and no conclusion has been reached yet. In this work, we found the superconducting transition temperature T_c = 20 K from resistivity and dc magnetization measurements for pristine sample. DC magnetization measurements exhibited ferromagnetic like transition for all samples.     

On the superconductivity and structural properties of YBa2Cu3 − xCdxO7 − y

A series of superconducting cuprates with the nominal composition YBa₂Cu_3 − xCd_xO_7 − yand the effect of Cd substitution on Cu sites in this compound is presented. X-ray powder diffraction patterns for these cadmium cuprates with reduced diamagnetism indicate an orthorhombic unit cell like-perovskite structure for (0 ≤ x ≤ 0.15), while for higher Cd concentration, i.e.x = 1.0 the material is polyphasic. The observed superconducting transition temperature of the samples is nearly the same ([formula] K), except for (x = 1.0) whereT_cdrops to 72 K and a transition from metallic to semiconducting behavior of the normal state of the resistivity is observed. Such a decrease inT_cfor higher Cd concentration could be attributed to the presence of the green phase in this composition.