Structure and Superconducting Properties of Cd0.8Ba2(Y0.7Ca0.4)Cu3.5Oy

A new Cd-containing superconductor with nominal composition ofCd_0.8Ba₂(Y_0.7Ca_0.4)Cu_3.5O _y was synthesized and investigated. The obtained Cd and Ca-doped 123 phase exhibits an orthorhombic (T _c=80 K) or tetragonal (T _c=65 K) modification depending on the reaction atmosphere. It was shown that the combined Cd and Ca substitution facilitates the 123 phase formation. The results of the EDX analysis, as well as the comparison of the obtained lattice parameters with those of undoped, Cd-doped, and Ca-doped 123 have shown that both Cd and Ca enter the 123 phase and form a new Cd–Ba–Y–Ca–Cu–O superconducting compound.     

A new family of superconductors containing carbonate group

Three new oxycarbonate superconductors recently obtained in our laboratory are described. (1) Sr₂CuO₂(CO₃)_1–x (BO₃) _x (T _c = 35 K) was synthesized under ambient pressure, providing a new method for carrier doping on the layered copper oxycarbonate system. (2) Ca _n (Ca, Sr)₂Cu _n+1(CO₃)O _y (n = 1, 2, 3) was synthesized under high pressure. Superconductivity was achieved by substituting (BO₃)^3– for a part of (CO₃)^2–. (3) A new Hg system HgBa₂Sr₂Cu₂(CO₃)O₆₊ was synthesized.T _c obtained from the magnetic susceptibility is about 66 K.     

Synthesis Conditions and Superconductivity in 123-Type Superconductors

We have synthesized REBa₂Cu₃O_7–, where RE = Y, Sm, Gd, and SM(123):Ag under the identical conditions and characterized R – T and SEM–EDAX measurements by XRD. It is observed for sample SmBa₂Cu₃O_7– with = 0.3 that substitution of 10% Ag in place of Cu reduces T _c by 13 K along with the enhancement of normal-state resistivity by almost 200 times. When the T _c of the samples were optimized, it was found that the normal-state resistivity decreases by the substitution of Ag along with a decrease in T _c.     

Superconductivity of Ba1 ? xKxBiO3 (0.35 < x < 1) Synthesized by the High Pressure and High Temperature Technique

Ba_{1 – x} K _x BiO₃ (BKBO) samples with 0.35 < x < 1 were synthesized by the high pressure and high temperature technique. XRD analysis showed that the BKBO samples were single phase for the whole range of the potassium doping concentration. The change of superconducting transition temperature, T _c, as well as lattice parameters have been investigated upon doping concentration. As the K doping concentration (x) increases from x = 0.37, T _c decreases from 30.4 K to almost zero at x = 0.74. However, in some BKBO samples without including any barium in the starting composition (x = 1), which is denoted as KBO samples, superconductivity is observed with T _c as high as 9 K with partial substitutions of Bi at the K site. Depending on the synthesis condition of the KBO samples, T _c and lattice parameters were different from sample to sample. Compared with other superconducting bismuthates, the evolution of T _c by potassium doping in the cubic BKBO system is discussed in terms of its electronic band structure.     

Microstructural and superconductive studies of Ag-YBa2Cu3O7?x composites

Composites of Ag-YBa₂Cu₃O_7–x were synthesized and carefully characterized for crystal structure and microstructure by X-ray diffraction, optical microscopy, SEM, TEM, and EDAX techniques in order to investigate the effect of Ag additions on the superconducting properties of 123 compounds. The a.c. susceptibility data show thatT _c (onset) of 123+Ag composites vary between 90.2 and 91.8 K. TheJ _c values we measured for 123 material without silver were in the range of earlier reported values for the pure 123 material. Whereas there is a relatively small increase in the critical current for the YBCO/Ag₂O ratio of 3, the variation of the grain size of the composites shows that theseJ _c changes are due to slight variations in the grain size rather than any dramatic effect of Ag inclusions as speculated earlier.     

Structural Studies of the Superconducting La2.5Y0.5CaBa3(Cu1?xFex)7Oz (0 ≤ x ≤ 0.1) Perovskite System by Neutron Diffraction

We have investigated the effect of Fe substitution on the structural and superconducting properties of La_2.5Y_0.5CaBa₃(Cu_1–x Fe _x )₇O _z system by Rietveld refinement of the neutron diffraction patterns of three samples with x = 0.02 (labelled B₁), x = 0.06 (B₂), and x = 0.10 (B₃) along with X-ray diffraction, resistivity, AC susceptibility, and oxygen-content measurements. Samples B₁, B₂, and B₃ are superconducting with T _c ^R=0 values of 73, 62, and 41 K, respectively. Neutron diffraction studies confirm (i) the formation of a single phase tetragonal structure (space group P4/mmm) for all three samples, (ii) Ca and Y ions substitution at the La site concomitantly displaces La onto Ba sites, and (iii) increasing x from 0.02 to 0.10 increases oxygen content (the amount of oxygen per unit cell), as well as Cu(1)— O(4) and Cu(1)— O(1) bond lengths whereas Cu(2)— O(4) bond length decreases with corresponding decrease in T _c to 41 K due to increasing occupancy of Fe ions at Cu(2) site. The change in bond lengths with oxygen content are essentially the same as those of Fe content (x). Present studies establish a correlation between the bond lengths (Cu(1)— O(1), Cu(1)— O(4), and Cu(2)— O(4)) and the measured T _c values of three samples.     

Effect of Bi/Pb ratio and annealing temperature onTc and formation of high-Tc phase in Bi-Pb-Sr-Ca-Cu-O superconductor

We studied the effect of Bi/Pb ratio and annealing temperature onT _c and formation of the high-T _c ; phase in Bi-Pb-Sr-Ca-Cu-O superconductor by the three-step reaction process. The optimum Bi/Pb ratio is about 1.80.3 and the optimum annealing temperature is about 845–855°C. It is found that a variate high-T _c phase existed at the higher annealing temperature. The zero-resistance temperature of the variate high-T _c phase decreased when the annealing temperature increased, although the phase is isostructural with the 110 K phase.     

Superconductivity and Ferromagnetism of the Ru-1232 Compounds in the (Ru1?xNbx)Sr2(GdCe1.8Sr0.2)Cu2Oz System

The Ru-1232 compounds have been synthesized in the (Ru_1–xNb _x )Sr₂(GdCe_1.8Sr_0.2)Cu₂O _z system, and effects of Nb substitution for Ru on superconductivity and ferromagnetism of the Ru-1232 compounds have been investigated. First, X-ray powder diffraction study shows that nearly the single 1232 phase samples can be obtained in the x composition range from 0.0 to 0.3. Then, from the electrical resistivity study, it is found that each of the samples shows resistivity dropping phenomenon at two temperatures of T _c ^l and T _c ^h, which originates from superconductivity of the Ru-1232 phase and the Ru-1222 one, respectively. Both of the starting temperatures are lowering with increasing Nb content x. Lastly, from the magnetic susceptibility study, it is found that superconducting transition temperature T _c is 20 K for the Ru-1232 sample with x = 0.0 and the ferromagnetic transition temperature T _m is about 90 K. This study also shows that both of the values of T _c and T _m become low with increasing x from 0.0 to 0.3.     

Effect of Ca Substitution on the Superconductivity of La2.5Y0.5CaBa3(Cu0.88Fe0.12)7Oz

The structural and superconducting properties of single-phase La_2.5–y Y_0.5Ca_1+y Ba₃ (Cu_0.88Fe_0.12)₇O _z (LYCaBCuFe) (y= 0.0–1.0) compounds with triple perovskite structure are investigated using X-ray diffraction, resistivity, a.c. susceptibility, and oxygen content measurements. Increasing Ca substitution for La resulted in a decrease in unit cell axes and volume. T _c ^R=0 shows a marginal increase from 31 K to 37 K for y = 0.0–0.21 and thereafter it decreases with increasing y leading to zero T _c ^R=0 at y 0.84. This shows that the suppression of T _c from 80 K to 31 K by Fe doping at x = 0.12 La_2.5Y_0.5CaBa₃(Cu_1–x Fe _x )₇O _z cannot be compensated by appropriate hole doping with Ca in LaYCaBCuFe.     

A Comparative Study of High-Field Diamagnetic Fluctuations in Deoxygenated YBa2Cu3O7-x and Polycrystalline (Bi–Pb)2Sr2Ca2Cu3O10

We studied three single crystals of YBa₂Cu₃O_7-x, (Y123) with superconducting transition temperature, T_c=62.5, 52, and 41 K, and a highly textured polycrystalline specimen of (Bi–Pb)₂Sr₂Ca₂Cu₃O₁₀ (Bi2223), with T_c=108K. Isofield magnetization data were obtained as a function of temperature, with the magnetic field applied parallel to the c axis of each sample. The reversible magnetization data for all samples exhibited a rounded transition as magnetization tended toward zero. The reversible data were interpreted in terms of two-dimensional diamagnetic lowest-Landau-level (LLL) fluctuation theory. The LLL scaling analysis yielded consistent values of the superconducting transition temperatures T_c(H) for the various samples. The resulting scaling data were fit well by the two-dimensional LLL expression for magnetization obtained by Tesanovic and colaborators, producing reasonable values of κ but the fitting parameter ∂H_c2/∂T produced values that were larger than the experimentally determined ones. We performed simultaneous scaling of Y123 data and Bi2223, obtaining a single collapsed curve. The single curve was obtained after multiplying the x and y axis of each scaling curve by appropriate sample-dependent scaling factors. An expression for the two-dimensional x-axis LLL scaling was extracted from theory, allowing comparison of theoretical values of the x-axis scaling factors with the experimental values. The comparison between the values of the x-axis produced a deviation of 40% which suggests that the hypothesis of universality of the two-dimensional LLL fluctuations is not supported by the studied samples. We also observe that Y123 magnetization data for temperatures above T_c obbey a universal scaling obtained for the diamagnetic fluctuation magnetization from a theory considering non-local field effects. The same scaling was not obbeyed by the corresponding magnetization calculated from the two-dimensional LLL theory.     

Superconductor-Insulator Transition in Composite Granular (1?n)Gd123-nPr123 and (1?m)Gd123-mPrBa123

Granular composite samples of GdBa₂Cu₃O_7– (Gd123), PrBa₂Cu₃O_7– (Pr123), and Pr_0.5Ba_0.5Ba₂Cu₃O_7– (PrBa123) have been prepared by the solid state reaction technique. The characterization of samples has been done by SEM and XRD measurements. We have investigated the effect of Pr123 and PrBa123 insulating grains on the superconductor-insulator transition and the normal state resistivity of the (1–n)Gd123-nPr123 and (1–m)Gd123-mPrBa123 systems. The dominant diffusion of Pr ions onto the neighboring Gd123 grains in (1–n)Gd123-nPr123 causes high rate of suppression of superconductivity similar to the chemical-doped GdPr123 system. For (1–m)Gd123-mPrBa123 system, the suppression rate is slower and we have superconducting sample with T_c^mid = 41 K for the second phase of m = 0.6 sample. Comparison of the superconductor-insulator and metal-insulator transitions in the granular samples and the chemical substituted GdPr123 indicates optimization of the superconducting state in (1–n)Gd123-mPrBa123 relative to (1–n)Gd123-nPr123 and GdPr123 systems. The more stable characteristic of PrBa123 relative to Pr123, when they are mixed with Gd123 grains, makes PrBa123 more suitable for any superconductor-insulator application. The mechanism of suppression of superconducting state for Pr123 has been discussed by comparison of experimental results against the hole filling and hole localization models presented for the insulating Pr123.     

Current progress in ternary LREBa2Cu3Oy materials and their application

The J_c and H_irr values at 77 K of ternary light-rare-earth compounds, LREBa₂Cu₃O_y “LRE-123”, are usually high enough to serve in various applications. Several sources of vortex pinning can be in these composites tailored to fit the needs of the particular application. The list comprises LRE/Ba solid solution, oxygen vacancies, large particles of secondary phases, twin planes, nanoscale lamellas, etc. By means of the latter defects one can achieve a very high irreversibility field. Refinement of secondary phase particles and the optimal choice of their amount enhance the electromagnetic performance in a broad temperature range, up vicinity of T_c, allowing levitation at liquid oxygen, 90.2 K. An optimum content of MoO₃ doubles the self-field super-current at 77 K, H||c-axis. Altogether, the pinning tailoring in ternary LRE-123 materials provides a flexible and reliable way to fit the electromagnetic performance with the needs of sophisticated high-temperature and high-magnetic-field applications.     

Effects of iodine intercalation into Bi-based copper oxide superconductors

We have investigated the stage-1 iodine-intercalation compounds, whose host materials are Bi₂Sr₂Ca_1–x Y _x Cu₂O₈ (Bi-2212 phase) and Bi_1.6Pb_0.5Sr_1.9–x La _x Cu_1.05O₆ (Bi-2201 phase) with variousx values. In the Bi-2212 phase, it has been found that the change inT _c through the stage-1 iodine intercalation is due to two effects; a change of the two-dimensionality and an increase in the carrier number. The former effect decreasesT _c by about 10 K independent of the carrier number of the host sample. The latter effect shifts thex dependence ofT _c to largerx values by about 0.08, taking account of oxygen release from the host samples during the intercalation process. This result is clear evidence for the occurrence of both the change of two-dimensionality and the increase in carrier number about 0.04 per CuO₂ unit due to the charge transfer through the stage-1 iodine intercalation. In the Bi-2201 phase,T _c decreases by about 10 K through the stage-1 iodine intercalation.     

Enhancement of Pinning Role by Nonstoichiometry in YBa2Cu3O7?y Superconductors

Considerably improved flux pinning and critical current density J c values have been achieved in Y-deficient Y-123 superconductors by directional solidification in air. In comparison with the regular Y-123 composition, Y-deficient one also has an orthorhombic structure and Y-123 main crystal phase remains in it. Whereas with the shortage of Y, Y_1–x Ba₂Cu₃O_7–y can be regarded as (YBa₂Cu₃)_1–x O_7–t(Ba₂Cu₃) _x O _t–y or (YBa₂Cu₃O_7–z )( _x ^YO _z–y ), so there may develop several kinds of microstructure defects as pinning sites in the system, such as highly dense, fine-scale, and faultlike defects, as well as localized superstructure, which are able to induce the increasing in flux pinning and J c values in higher external magnetic fields. This kind of simple nonstoichiometric route could lead to a commercial technique for flux-pinning enhancement in Y-123 bulk materials.     

Stability of the low-temperature tetragonal phase in La2?xBaxCuO4 and related compounds

In La_2–x Ba _x CuO₄ (LBCO), the structural transition to a low-temperature tetragonal phase below 60 K and suppression of superconductivity are observed when the carrier density isp 1 /8 per copper. The replacement by divalent ions smaller than Ba²⁺ suppresses the static deformation of the lattice. We have found that the variationsT _d2 and superconducting transition temperatureT _c are quantitatively characterized by the averaged ionic radius at the La site or lattice parameters. This aspect of substitution could be regarded as the effect of chemical pressure, since similar variations have been reported on applying hydrostatic pressure. In La_2–x–y Nd _y (Ba, Sr) _x CuO₄,T _d2 increases with increasingy in a wide range ofp whileT _c is suppressed only at p l /8. The structural transition atT _d2 here should be ascribed mainly to the crystallochemical origin.     

Interplay of low and highT c phases in Bi-Sr-Ca-Cu-O superconductor

In the Bi-Sr-Ca-Cu-O system stringent conditions of heat-treatment lead to the formation of a mixture of both the low and highT _c phases and obtaining a single-phase material becomes extremely difficult. This study reports preparation of samples with single superconducting transitions at ∼ 75 K and ∼ 108 K; the compositions of which correspond ton=2,3 in the series Bi₂Sr₂Ca _n−1Cu _n O_{4 + 2n} . X-ray diffraction studies show that the lowerT _c material is a relatively pure phase while the higherT _c phase only co-exists with the lowerT _c phase. The most obvious effect of doping the system with lead is to make the reaction take place faster and thereby increase the volume fraction of the 110K phase.     

Enhancement ofT c (∼ 103 K) in calcium-free Tl2Ba2CuO x (2201) compound

EnhancedT _c in calcium-free Tl compounds of the series Tl _m Ba₂Ca _n−1Cu _n O _x (2201) has been reported. Three different starting compositions (2201, 1201 and 2202) were studied extensively with varying conditions of preparation. Under optimized conditions (sintering temperature 970°C and duration 3–10 min) the highestT _c(onset) ranges from 103 K to ∼ 115 K andT _c (zero) ∼ 95 K was found. XRD studies showed the transformation of all the three nominal compositions into 2201 phase with differentT _cs.     

Effect of Cd Addition on Superconducting Fluctuations and Mechanical Properties of Bi1.82Pb0.36Sr2Ca2Cd x Cu3O y System

A study was made of the effect of Cd additions on the superconducting and mechanical properties of Bi_1.82Pb_0.36Sr₂Ca₂ Cd_xCu₃O_y (x = 0.0, 0.15, 0.25, 0.35 and 0.55). Characterization of the Cd-samples using XRD, DTA, and SEM techniques, has confirmed that remarkably formation of low-T _c phase (2212) by the addition of Cd up to 0.35. High-resolution electrical resistivity ρ (T) data on the composition of Cd = 0.35 have been taken for investigating critically the superconducting fluctuations. Using the Aslamazov and Larkin (AL) and Lawrence and Doniach (LD) models of excess conductivity. Excess conductivity analysis shows that this composition (Cd = 0.35) is 2D in the temperature range 137.8–163.7 K and a 3D one below 137.8 K. Thus, a crossover from 2D to 3D is observed at 137.8 K. Sample microhardness and density are greatly improved by Cd-additions (0.35). This trend is probably due to the intercalation of cadmium between superconducting grains in compositions may provide a plastic-flow region that allows relaxation of undesirable stresses resulting from the grain anisotropy of superconductors.     

Superconducting Properties of the 3-K Phase of Sr2RuO4 near Hc2

The superconducting transition temperature, T _c , of the impurity-free, intrinsic Sr₂RuO₄ is as high as 1.50 K. However, we recently showed that T _c is remarkably increased up to 3 K in the Sr₂RuO₄–Ru eutectic system, in which plate-like microdomains of Ru metal are embedded in the primary-phase Sr₂RuO₄. The phase diagram of the anisotropic upper critical field of the 3-K phase indicates that H _c2 for the field parallel to the RuO₂ plane is strongly suppressed at low temperatures. We argue that the reorientation of the Cooper-pair spin direction near the Sr₂RuO₄–Ru interface may be responsible for this suppression. In addition, we observed unusual hysteresis in the out-of-plane resistivity, _c , at low temperatures and near H _c2, only when the field was applied parallel to the RuO₂ plane.