Thermoelectric power and irreversibility field of (Hg,Tl)2Ba2Can−1CunOy (n=2–5) superconductors

We have measured the thermoelectric power, S, and the irreversibility field, H_irr, of the superconducting samples of (Hg,Tl)₂Ba₂Ca_n−1Cu_nO_y (n=2–5). S values for the (Hg,Tl)-22(n−1)n above their T_c's drastically increase with increasing n. Judging from the S values at room temperature, the n=2 and 3 samples are located in the overdoped region, the n=4 is in the almost optimally doped and the n=5 is in the underdoped region. H_irr values for the n=4 and 5 samples are higher than those for the as-synthesized and annealed n=3 samples. It is considered that the enhancement in H_irr is due not only to the increase of hole concentration but to the increase in the number of CuO₂ sheets.     

Trapping mechanism of superconductivity suppression induced by Pr substitution in the Ho1−xPrxBa2Cu3O7−δ system

Pr concentration dependence of the superconducting transition temperature T_c in the Ho_1−xPr_xBa₂Cu₃O_7−δ system is determined from measurements of DC electrical resistance. This dependence coincides with that for the parallely studied Y_1−xPr_xBa₂Cu₃O_7−δ reference system. Both systems have the same value of the critical concentration x_c=0.58, in accordance with nearly equal ionic radii of Ho³⁺ and Y³⁺ ions. It has been shown that the T_c(x) curve can be described with a single mechanism based on a decreasing number of sheet holes trapped by Pr^IV-ions, if one takes also into account that the number of these ions changes with x.     

Ramans study of Y1−xPrxBa2Cu3O7−δ and YB2Cu3−xZnxO7−δ single crystals

Single crystals with known T_c values of Y_1−xPr_xBa₂Cu₃O_7−δ (Y---Pr1:2:3) and YBa₂Cu_3−xZn_3−xZn_xO_7−δ (Y---Zn1:2:3) systems are studied by Raman measurements. The Raman spectra for (Y---Pr1:2:3) single crystals show that the frequencies of Ba and O_z modes increase as the Pr content increases. The results are consistent with the hole-localization scheme proposed for the suppression of superconductivity in the polycrystalline Y---Pr1:2:3 systems. On the other hand, in the Y---Zn1:2:3 system, all the Raman modes do not change in frequencies. However, the FWHM of the Cu(2) mode increases with the decrease of T_c, indicating strong scattering of charge carriers by the substituted Zn ions in the CuO₂ planes. The induced disorder in the CuO₂ planes may be related with suppression of T_c in the Y---Zn1:2:3 system. Thus, the suppression mechanism in the Y---Zn1:2:3 systems seems to be different from that in the Y---Pr1:2:3 systems.     

Nax/2Bi1−x/2MoxV1−xO4 and Bi1−x/3MoxV1−xO4 New Scheelite-related phases

New Scheelite-related solid solutions of the compositions Na_x/2Bi_1−x/2Mo_xV_1−xO₄ (0≤x≤1) and Bi_1−x/3 Mo_xV_1−xO₄(0≤x≤0.2) have been synthesised by the substitution of Na and Mo at the A and B sites respectively of the ABO₄ type ferroelastic BiVO₄. The phases were characterised using chemical analysis, powder X-ray diffraction, scanning electron microscopy, EDAX, and Raman spectroscopy. While almost a continuous solid solution is obtained for the series Na_x/2Bi_1−x/2Mo_xV_1−xO₄, the absence of Na at the A-site results only in a narrow stability region for the other series, Bi_1−x/3 Mo_xV_1−xO₄ where 0≤x≤0.2. Raman spectra of selected samples at room temperature also suggest that vanadium and molybdenum atoms are disordered at the tetrahedral sites.     

Phonon Raman scattering in Nd1+xBa2−xCu3O7−δ and Pr1+xBa2−xCu3O7−δ single crystals

The polarized Raman spectra of Nd_1+xBa_2−xCu₃O_7−δ (−0.023≤x≤0.107) and Pr_1+xBa_2−xCu₃O_7−δ (0.01≤x≤0.15) single crystals have been investigated. It was found that the Cu(2) A_g mode softens by 6 cm⁻¹ in Nd 1:2:3 and 4 cm⁻¹ in Pr 1:2:3 as x increases. These frequency shifts cannot be explained by the change in the relevant bond lengths due to Nd(Pr)-substitution for Ba. The variations with x of the two low frequency modes may be affected by change of their hybridization and/or change of their force constants. The linewidths of Ba mode in Pr 1:2:3 are broader than those in Y 1:2:3. This result suggests that the Pr substitution on Ba sites occurred even in a very small value of x. In x(yy) geometry the relative intensity of the Ba and O(4) modes in Nd 1:2:3 is greater than those in Pr 1:2:3. The difference between Nd 1:2:3 and Pr 1:2:3 in the relative intensity of the Ba and O(4) modes may be produced by the chains.     

Magnetic properties of the Bi1.95Sr2.05−xLaxCuOy (Bi-2201) superconducting phase

We have investigated the reversible mixed-state magnetization M of three lanthanum substituted Bi_1.95Sr_2.05−xLa_xCuO_y (Bi-2201) ceramic samples having different critical temperatures T_c ranging from 20.0 to 35.5 K. As for the Bi₂Sr₂CaCu₂O_8+δ (Bi-2212) phase, we found that anisotropy of Bi-2201 is large. A manifestation of this anisotropy is the field independent magnetization M^* observed at a temperature T^*. In the framework of the London model, and including thermal fluctuations of vortices, we found for the temperature dependence of the penetration depth λ_ab(T) = λ_ab(0)[1 − (T/T_c0)ⁿ]^−1/2, with n 1.7 and λ_ab (T = 0) 4000 Å. The estimated upper critical fields μ₀H_c2,c are of the order of 10 T. We observe a peculiar negative slope M/T at low temperature and sufficiently high external magnetic field. This feature seems to be a characteristic of the Bi-2201 phase. However, we do not know whether it is associated with the superconducting mixed-state. A small amount of magnetic impurities could also be responsible for this behavior. Finally, the behavior of the reversible magnetization of the Bi-2201 samples investigated, which are situated at the optimal and in the overdoped region, did not indicate any unusual temperature dependence for the upper critical field H_c2,c.     

Quantum critical point, scaling and universality in high Tc(CaxLa1−x)(Ba2−c−xLac+x)Cu3Oy

Using charge transport in sintered ceramic samples it is observed that at all doping, including non superconducting overdoped samples, there exists a temperature in which below it dR/dT < 0. This suggests that either the quantum critical point is not necessarily inside the superconducting dome or that the CuO₂ plane is never overdoped. Data relating experimental Cooper pair density, conductivity and T_c suggest that Homes’ relation might need a more specific definition of the conductivity σ.     

Realization and properties of ramp-type YBa2Cu3O7−δ/Au/Nb junctions

All-thin-film ramp type Josephson junctions between YBa₂Cu₃O_7−δ and Nb have been fabricated. This procedure allows connections between high-T_c and low-T_c superconductors at different crystal sides of the high-T_c superconductor on one chip, which is of great interest for novel phase devices. A thin Au layer is incorporated as a chemical barrier to avoid oxygen transfer from the YBa₂Cu₃O_7−δ to the Nb. Critical current densities up to 600 A/cm² are obtained at T=4.2 K, with typical R_nA values of 0.8 μΩ cm². The variation of the magnetic field dependence of the critical current with the angle between the junction barrier and the YBa₂Cu₃O_7−δ crystal axes is explained by considering a predominant d_x²−y² order parameter symmetry of the YBa₂Cu₃O_7−δ. The successful fabrication of these junctions allows the implementation of novel superconducting electronics, such as complementary Josephson circuitry or proposed qubit concepts, using the unconventional order parameter symmetry of the high-T_c superconductor.     

Temperature dependence of the critical current in YBa2Cu3O7−δ and Bi2Sr2Ca1Cu2O8 Josephson junctions

We have studied the stationary Josephson effect on YBa₂Cu₃O_7−δ (T_c=90 K) and Bi₂Sr₂Ca₁Cu₂ O₈ (T_c=80 K and 87 K for two samples of different origin) ceramic based junctions. The temperature dependence of the critical current near T_c has been found as I_c≈(T_c-T) for the Y-Ba-Cu-O samples indicating that they should be classified as S-N-I-N-S type junctions. The I-V curves of the Bi-Sr-Ca-Cu samples show the typical behaviour of S-I-S structures. Using Ambegaokar-Baratoff's theory for Bi₂Sr₂Ca₁Cu₂O₈, the temperature dependence of the superconducting state gap Δ(T) was calculated and it was evaluated that 1.452Δ(0)/k_BT_c3.5.     

Magnetization study of polycrystalline YBa2AlxCu(3−x)O7−δ (x = 0.05, 0.10 and 0.20) compounds

Superconductivity in polycrystalline YBa₂Al_xCu_(3−x)O_7−δ materials was characterized by dynamic AC and quasistatic DC magnetometry. Intragranular persistent current density and low-loss intergranular critical current density were deduced using DC and AC techniques, respectively. Addition of aluminum produced modest increases in the intragranular persistent current for x < 0.2, but drastically reduced the intergranular critical current density for x = 0.2. The critical temperature T_c for superconductivity decreased only 4% for Al content up to x = 0.2.     

Influence of fluctuations on thermal conductivity of high-Tc YBa2Cu3O7−δ superconductor

To study a behavior of the thermal conductivity near T_c specific heat and thermal diffusivity of the YBa₂Cu₃O_7−δ high-T_c ceramics were simultaneously measured. Close to T_c = 92.30 K the thermal diffusivity and the thermal conductivity discovered minima and the specific heat – maximum. Quantitative analysis of the influence of thermodynamical fluctuations showed the same power laws with Gaussian exponent equal to 0.5 and existing of crossover from the 3D Gaussian to 3D XY critical behavior in the specific heat and thermal conductivity at the approach to T_c. To explain the minimum in thermal conductivity at T_c we propose a mechanism of scattering of phonons on the superconducting fluctuations.     

Effective Ru moment in RuSr2Eu2−xCexCu2O10 from high-temperature magnetic susceptibility

We have made high-temperature (250 K<T<800 K) DC susceptibility measurements in the compounds RuSr₂Eu_2−xCe_xCu₂O₁₀ for x=0.6,0.8, and 1.0 in order to determine the Ru effective magnetic moment. After carefully subtracting all contributions to the magnetic susceptibility except that of the Ru ions, we have been able to fit the Ru susceptibility with a law χ_Ru=χ₀+C_Ru/(T−Θ_Ru). We have found that the Ru effective moment falls between the values expected for Ru⁵⁺ in spin states and . We have also found a dependence of μ_eff(Ru) and Θ_Ru with the Ce content x.     

Raman study of HgBa2Can−1CunO2n+2+δ (n=1,2,3,4 and 5) superconductors

Polarized micro-Raman scattering measurements have been performed on the five members of the HgBa₂Ca_n−1Cu_nO_2n+2+δ (n=1,2,3,4 and 5) high-T_c superconductor family using different laser frequencies. Local laser annealing measurements were carried out to investigate the variation of the Raman spectra with the excess oxygen content, δ. A systematic evolution of the spectra, which display mainly peaks near 590, 570, 540 and 470 cm⁻¹, with increasing number of CuO₂ layers has been observed; its origin has been shown to lie in the variation of the interstitial oxygen content. In addition to confirming that the 590 cm⁻¹ mode represents vibration of apical oxygens in the absence of neighboring excess oxygen, the 570 cm⁻¹ mode, which may be composed of some finer structures, has been assigned to the vibration of the apical oxygen modified by the presence of the neighboring excess oxygens. The 540 and 470 cm⁻¹ modes may represent the direct vibration of excess oxygens. The implication of possible different distribution sites of excess oxygens is discussed. All other observed lower-frequency modes are also assigned.     

Crystal structure, superconductivity and magnetic properties of the superconducting ferromagnets Gd1.4−xDyxCe0.6Sr2RuCu2O10 (x=0–0.6)

The structural, electrical and magnetic properties of the superconducting ferromagnets, Gd_1.4−xDy_xCe_0.6Sr₂RuCu₂O₁₀ (x=0–0.6) are systematically investigated as a function of Dy doping and temperature. These compounds are characterized by high temperature superconductivity (T_c ranging from 20 to 40 K depending upon the Dy content) co-existing with weak ferromagnetism with two magnetic transitions (T_M2 ranging from 95 to 106 K and T_M1 around 120 K). Doping with Dy gives no significant structural changes except for a minor change in the c/a ratio. However the superconducting transition temperature is significantly suppressed and magnetic ordering temperature enhanced on Dy doping. These effects are described and discussed.     

Superconductivity and crystallographic properties of La2 − xMxCuO4 − δ (M = Na, K)

Superconductivity and crystallographic properties of La_{2 − x}M_xCuO_{4 − δ} (M = Na, K) are studied. In the La_{2 − x}M_xCuO_{4 − δ} system, superconductivity is detected for x 0.2. Oxygen content analysis shows that the system has more oxygen vacancies than the La_{2 − x}Sr_xCuO_{4 − δ} system. These oxygen vacancies may reduce the hole concentration, and high Na-doping is needed to produce superconductivity. In the La_{2 − x}K_xCuO_{4 − δ} system, superconductivity is observed for the first time. Resistivity and magnetic susceptibility measurements show that T_c(onset) is 40 K and the Meissner volume fraction is about 4% for x = 0.7. The system changes from orthorhombic to a tetragonal K₂NiF₄ structure at x ≈ 0.3 and only tetragonal samples show superconductivity.     

Characterization of nonstoichiometric nickel manganite spinels NixMn3−x□3δ/4O4+δ by temperature programmed reduction

Cation deficient spinels Ni_xMn_3−x□_3δ/4O_4+δ (0≤x≤1) have been prepared by thermal decomposition of mixed oxalates Ni_x/3Mn_(3−x)/3(C₂O₄)·nH₂O in air at 623 K. They have been characterised by temperature programmed reduction (TPR) under H₂, the reaction being followed by gravimetric and powder X-ray diffraction measurements. It has been shown that TPR proceeds in several steps. The first steps correspond to the loss of nonstoichiometric oxygen leading to the formation of a stoichiometric oxide. During the following stages the manganese cations are reduced, causing the spinel structure to be destroyed, and the formation of solid solution of NiO in a cubic MnO. Subsequently, Ni²⁺ cations undergo a reduction to metallic nickel, and, finally, a mixture of nonstoichiometric MnO_1−δ and metallic nickel is formed. These oxides contain a high level of vacancies which vary with the nickel content with a maximum of δ≈1 near x=0.6. This nonstoichiometry is ascribed both to the presence of Ni³⁺ and excess of Mn⁴⁺.     

Layer dependence of the superconducting transition temperature of HgBa2Can−1CunO2n+2+δ

High-pressure methods have been used to synthesize multiphase compositions in the Hg---12{n−1}n homologous series. The phase assemblages were examined by optical, electron diffraction and X-ray diffraction techniques, and their stoichiometries verified by electron microprobe. Transport and magnetic susceptibility measurements were combined with the results of the phase analysis to establish superconducting transition temperatures for both as-prepared and O₂- or Ar-annealed materials. It was found that the transition temperature peaks at T_c = 134 K for N = 3 and then decreases abruptly for n>4, reaching T_c<90 K for n7.     

Thermal transport in the oxygenated magnetic superconductor, Eu1.5Ce0.5RuSr2Cu2O10+δ

The thermal conductivity and thermopower are reported for a hole doped Eu_1.5Ce_0.5RuSr₂Cu₂O_10+δ sample that has been annealed at 1100 K under an oxygen pressure of 54 atm. At T_c=45 K superconductivity and weak ferromagnetism coexist (T_m=180 K). Weak features in the thermopower, S(T), and thermal conductivity, κ(T), are observed both at T_m and at T^*=140 K. The thermopower begins to decrease sharply toward zero at T_c, and there is an extremely sharp increase of about 30% in the thermal conductivity at T_c. This “first order” transition may be related to the sudden appearance of a spontaneous vortex phase at T_c. A small shoulder is observed in κ(T) in the temperature range T=5–13 K.     

Preparation and characterization of Y1−xPrxBa2Cu3O7−δ single crystals

We present a reliable method for growing single crystals of Y_1−xPr_xBa₂Cu₃O_7−δ high-T_c superconductors in ZrO₂ crucibles. This method results in crystals with greatly improved superconducting properties compared to crystals grown with the previously reported methods which use Al₂O₃ crucibles. We describe techniques for crystal growth in both Al₂O₃ and ZrO₂ crucibles using an excess of BaCo₃ and CuO as the flux. The crystals were characterized by means of DC magnetic-susceptibility measurements, electrical-resistivity measurements, and electron microprobe analysis. The effects of Al contamination on the conditions for crystal growth and on the superconducting properties of the crystals are found to be quite significant.     

Electrical and structural properties of epitaxially grown Y1Ba2Cu3O7 − x and Y2Ba4Cu8O16 − x thin films using the BaF2 method

Thin films of Cu, Y and BaF₂ are co-condensed in ultrahigh vacuum onto SrTiO₃ (1 0 0)-substrates at room temperature without any additional oxygen supply. It is found that the temperature of the ex situ fluorine-oxygen exchange reaction in flowing wet oxygen essentially determines whether the Y₁Ba₂Cu₃O_{7 − x}-phase (T_ex = 850°C) or the Y₂Ba₄Cu₈O_{16 − x}-phase (T_ex = 800°C) forms or any mixture of both phases in between. Small-angle X-ray diffraction verifies the strictly epitaxial growth of the superconducting phases. The variation of the composition around the ideal 1,2,3-stoichiometry affects only the superconducting and normal conducting properties which are measured using the four-probe Montgomery method. The values of the normal state resistivity and its temperature dependence are discussed in combination with a reduced cross section of the conduction paths in the films.