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.     

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.     

NMR study of local hole distribution, spin fluctuation and superconductivity in Tl2Ba2Ca2Cu3O10

⁶³Cu, ¹⁷O and ²⁰⁵Tl NMR have been performed in the high-T_c superconductor Tl₂Ba₂Ca₂Cu₃O₁₀ whose T_c(max) is 127 K. The hole densities at Cu and oxygen sites in the CuO₂ plane have been extracted from the nuclear quadrupole frequency ν_Q. The striking feature is that the Cu holes are significantly transferred to oxygen site due to strong hybridization between Cu and oxygen. From an analysis of T₁ and T_2G, it has been found that the spectral weight of the spin fluctuation is transferred to higher energy compared to YBa₂Cu₃O₇, while the magnetic correlation length ξ does not differ much. Thus, it is suggested that the higher T_c is due to higher characteristic energy of spin fluctuations, i.e. the superconductivity is spin fluctuation mediated. The superconducting properties are consistently explained by a d-wave superconductivity model with a finite density of states (DOS) at the Fermi level. We show that the disorder of the Ca/TlO layer caused by the partial inter-substitution of Tl and Ca is responsible for the potential scattering to produce such a DOS. It is found that if such a potential scattering were absent, T_c would go up to 132 K which is quite close to the record T_c realized in the Hg based compound.     

The nuclear contribution to the specific heat of single crystals of YBa2Cu3O7 and Bi2Sr2CaCu2O8

Specific heat data below 1 K of Bi₂Sr₂CaCu₂O₈ and YBa₂Cu₃O₇ are analyzed. For YBa₂Cu₃O₇ the nuclear specific heat, C_N, amounts to 38T⁻² μJ/mol K. C_N for Bi₂Sr₂CaCu₂O₈ exceeds that of YBa₂Cu₃O₇ by a factor of 15. The nuclear quadrupolar specific heat contribution alone is insufficient to explain the data for YBa₂Cu₃O₇, while lack of NQR data does not allow such a comparison in Bi₂Sr₂CaCu₂O₈ to be made. The contribution to C_N from nuclear spins coupled via the contact hyperfine interaction with correlated magnetic spins (in the CuO₂ plane) is derived as a function of the correlation length. This contribution can be treated independently from the quadrupolar term. We show that the excess specific heat in YBa₂Cu₃O₇ likely originates in a few percentage of an impurity (oxygen deficient) phase with a strong hyperfine field on the Cu nuclei.     

Giant pressure effect in oxygen deficient YBa2Cu3Ox

The pressure effect on T_c of polycrystalline and single crystalline YBa₂Cu₃O_x investigated as a function of oxygen content x by ac-susceptibility measurements under helium pressure. In the overdoped region x> 6.93 the single crystals show a negative dT_c/d p, as expected from the charge transfer model. For optimally doped samples with x = 6.93 we find dT_c/d P = 0.4 K/GPa which points to pressure effects on T_c aside from charge transfer. In the underdoped region x < 6.93 the dT_c/d p values obtained from the experiment depend strongly on the storage temperature of the sample during the experiment. When the samples are stored at temperatures well below 240 K throughout the entire experiment including pressure application and pressure release, dT_c/d p increases to approx. 7 K/GPa at x = 6.7 but with a further decrease of the oxygen content the dT_c/d p drops to approx. 2 K/GPa at x = 6.4. These effects are intrinsic to the YBa₂Cu₃O_x structure and can be explained by considering the anisotropic structure of YBa₂Cu₃O_x. The decrease of the c-axis lattice parameter results in a charge transfer to the CuO₂-planes mainly [1], whereas the compression of the a- and b-axis lattice parameter is known to produce different pressure effects which are responsible for the peak in dT_c/d p at x = 6.7 [2]. When pressure is changed at room temperature oxygen ordering effects occur which cause a relaxation of T_c to the equilibrium value T_c(p) at this pressure with a time constant depending on the oxygen content x. A decrease x results in a peak effect in dT_c/d p at x = 6.7 again, which is enhanced to approx. 12 K/GPa. If the oxygen content is decreased further, dT_c/d p first drops to 5 K/GPa at x = 6.6, but the increases to values of more than 20 K/GPa for x < 6.42. These giant pressure effects at low oxygen contents are mainly caused by a reversible T_c increase (dT_c/d p)_O due to pressure induced oxygen ordering via oxygen motion between unit cells.     

Phase diagrams of YBa2Cu4O8 and YBa2Cu3.5O7.5 in the pressure range 1 bar≤PO2≤3000 bar

The P-T-x phase diagram of the pseudobinary system (Y-Ba-Cu-O)-O₂ has been further investigated in the oxygen pressure range between 1 and 3000 bar. The stability ranges of the phases YBa₂Cu₄O₈ (124), YBa₂Cu_3.5O_7.5−x (123.5) and YBa₂Cu₃O_7−x (123) have been determined. Long duration experiments showed that the 123 phase is not stable at least down to 7 bar≤P≤20 bar oxygen and 900°C. It is not clear whether at lower pressures and temperatures the 123 phase is thermodynamically stable or metastable due to low reaction rates. In the presence of excess CuO, the 124 is the stable phase. The melting of 124 pellets at P_O2=2800 bar shows that even at this pressure the 124 compound melts incongruently. Using the phase diagram data we could change the T_c of 123.5 from 16 to 70 K by varying systematically the nonstoichiometry. Due to a narrow homogeneity range the T_c of 124 remained constant but is different for powder pellets (81 K) and for crystals (70 K), probably due to the influence of the flux. Single crystals of both 124 and 123.5 with dimensions up to 4 mm were grown from the flux under high oxygen pressure.     

Intercalation thermodynamics and chemical diffusion of oxygen in the solid solution YBa2Cu3−xCoxO6+δ

The equilibrium oxygen content as a function of the temperature and oxygen pressure was measured for the solid solution YBa₂Cu_3−xCo_xO_6+δ, where x=0, 0.2, 0.4, 0.6, 0.8, by using coulometric titration in the temperature range 600–850°C and oxygen pressures between 10⁻⁵ and 1.0 atm. The change in the partial molar enthalpy and entropy of the intercalated oxygen was determined at different oxygen and cobalt contents. The oxygen chemical diffusion was studied by thermogravimetric relaxation in the oxygen-controlled atmosphere. The thermodynamic data were employed to determine how the chemical diffusion coefficient, the thermodynamic factor and the random-diffusion coefficient depend on oxygen content in specimens with different cobalt concentration. The oxygen intercalation thermodynamics and diffusivity results provide evidence of ordering phenomena on a microscopic scale in the basal plane of the tetragonal solid solution YBa₂Cu_3−xCo_xO_6+δ. A model for the oxygen diffusion is suggested to explain the large difference between the random and tracer diffusion coefficients in YBa₂Cu₃O_6+δ     

Superconductivity, Ca content and oxygen deficiency of Ga(Sr,Ca)2(Yb,Ca)Cu2O7

Superconducting transition temperature (T_c), Ca content and oxygen deficiency are studied on GaSr_1.8Ca_0.2Yb_1−xCa_xCu₂O₇ (x≤0.35). Superconducting samples with T_c=52 K are prepared after the annealing at 20 MPa of oxygen. The T_c is reduced through a slight oxygen loss accompanied by annealing in air above 650°C. The oxygen loss suggests the presence of short Cu–O chains in the GaO₄ slab. The formal valence of planar Cu required for the appearance of superconductivity depends on oxygen and Ca contents. The critical formal Cu valences are 2.105 and 2.125 for the samples annealed in air at 600°C and at 835°C, respectively. The values are higher than those of usual high-T_c superconductors. This can be explained by a high concentration of localized holes in the CuO₅ slab.     

Anomalies of ultrasonic velocity in high-Tc ceramics YBa2Cu3Oy and BiSrCaCu2Oy

Ultrasonic longitudinal velocity and adsorption have been measured in ceramic superconductors YBa₂Cu₃O_y with various porosity and also in BiSrCaCu₂O_y. A velocity drop of about 400 ppm was found at T_c only in the measurements on cooling. The magnitude of the velocity drop is anomalously large compared with the value expected from the thermodynamics. A hysteresis of velocity with respect to temperature was observed in all the samples studied. It is suggested that some structural change at pore size level is responsible for this phenomenon.     

Phase equilibria at low oxygen partial pressure in the Y---Ba---Cu---O system

The phase equilibria around YBa₂Cu₃O_7−x (123) and YBa₂Cu₄O₈ (124) phases at low oxygen partial pressure (1 atm) were investigated by X-ray diffraction and thermal analysis. The coexistence of 123 and 124 phase was confirmed under 1 atm oxygen pressure. By using the high temperature X-ray diffraction method, the univariant reaction YBa₂Cu₃O_7−x+Cu₂OY₂BaCu₂O₂+O₂ was identified. The oxygen partial pressure dependence of several univariant reactions has been investigated and the existence of two invariant reactions of L+O₂YBa₂Cu₃O_7−x+ BaCuO₂+CuO+Cu₂O and L+Y₂BaCuO₅+O₂YBa₂Cu₃O_7−x+CuO+Cu₂O was deduced to occur at 1103 K under 0.0032 atm O₂ and at 1143 K under 0.0085 atm O₂, respectively.     

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.     

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.     

Zero-field current-voltage characteristics in high-temperature superconductors

We have observed the anomalous magnetization of Bi₂Sr₂CaCu_2−xNi_xO₈ (x = 0 and 0.02) single crystals. Anisotropy decreases with iodine intercalation although it expands the space between CuO₂ layers. Iodine intercalation seems to suppress the magnetization anomaly for Ni = 1% crystals, but not for Ni = 1% substituted crystals. We have discussed these results in terms of the increase of anisotropy by Ni substitution and the dimensional crossover of flux lines. Effects of both oxygen concentration and substitution of a magnetic element for the Cu site on the anisotropy of Bi₂Sr₂CaCu₂O₈ crystals show the same tendency as the case of the YBa₂Cu₃O₇ superconductor.     

Peak effect and oxygen ordering in YBa2Cu3O7−δ single crystals

We have investigated the second magnetization peak in pure YBa₂Cu₃O_7−δ single crystals with various oxygen contents (6.91<7−δ<6.97) and degrees of oxygen vacancy ordering, as achieved by low (1 bar) and high (100 bar) oxygen pressure annealing. Although the position of the peak changes drastically with oxygen stoichiometry, no dependence on the distribution of oxygen vacancies has been found for temperatures below 70 K. For T>70 K, however, ordering effects become important as demonstrated by the disappearance of the peak for the high pressure annealed samples. These results suggest that while at low temperatures, pinning of the vortex system by clusters or a more homogeneous distribution of oxygen vacancies is similar, at elevated T, the former are much stronger pinning sites leading to larger hysteresis and the presence of the peak.     

Crystal structure of YBa2Cu3O7−x thin films prepared by pulsed laser deposition with substrate bias voltage

The crystal structure of YBa₂Cu₃O_7−x thin films has been investigated by cross-section transmission electron microscopy. The samples were deposited on MgO (100) substrates at 670°C with substrate bias voltages of ±300 V. For the unbiased case, c-axis, a-axis and (103) oriented domains normal to the substrate surface were observed. In this film, the c-axis oriented domains are dominant, but the crystal often exhibits a longer c-lattice constant than that of the YBa₂Cu₃O_7−x system, so extra cationic layers are inserted in the YBa₂Cu₃O_7−x intrinsic stacking sequence. For the case of −300 V, rotated domains were dominant in the entire film; however, c-axis oriented domains also grow from the substrate surface. Small-angle semicoherent grain boundaries between them were observed. In the case of +300 V, all the grains show c-axis oriented YBa₂Cu₃O_7−x. The degree of preferential orientation of the grains is reduced at negative bias voltage of −300 V and the structure defects are reduced by applying a positive bias of +300 V.     

Electron concentration in YBa2Cu3O6.9 single crystals determined from field electron emission spectroscopic measurements

Results of field electron emission spectroscopic investigations of YBa₂Cu₃O_6.9 single crystal specimens oriented perpendicular to the c-axis are presented. It is shown that the shift of the total energy distribution of field-emitted electrons from YBa₂Cu₃O_6.9 along the energy scale with increasing electric-field strength at the surface of the specimen is due to the penetration of the electric field into the subsurface region of the YBa₂Cu₃O_6.9 specimen. The electron concentration in YBa₂Cu₃O_6.9 found from spectroscopic measurements is n=(2−4) × 10²¹ cm⁻³. Field electron emission spectroscopy and microscopy of YBa₂Cu₃O_6.9 allows one to draw the conclusion that the electron concentration in the bulk of the material does not change with cooling of specimens from 300 K to 115 K.     

Origin of intrinsic Josephson coupling in the cuprates and its relation to order parameter symmetry: An incoherent hopping model

Experiments on the cuprate superconductors demonstrate that these materials may be viewed as a stack of Josephson junctions along the direction normal to the CuO₂ planes (the c-axis). In this paper, we present a model which describes this intrinsic Josephson coupling in terms of incherent quasiparticle hopping along the c-axis arising from wave-function overlap, impurity-assisted hopping, and boson-assised hopping. We use this model to compute the magnitude and temperature T dependence of the resulting Josephson critical current j_c(T) for s- and d-wave superconductors. Contrary to other approaches, d-wave pairing in this model is compatible with an intrinsic Josephson effect at all hole concentrations and leads to j_c(T) T at low T. By parameterizing our theory with c-axis resistivity data from YBa₂Cu₃O_7−δ (YBCO), we estimate j_c(T) for optimally doped and underdoped members of this family. j_c(T) can be measured either directly or indirectly through microwave penetration depth experiments, and current measurements on Bi₂Sr₂CaCu₂O₈ and La_2−xSr_xCuO₄ are found to be consistent with s-wave pairing and the dominance of assisted hopping processes. The situation in YBCO is still unclear, but our estimates suggest that further experiments on this compound would be of great help in elucidating the validity of our model in general and the pairing symmetry in particular.     

Anomalous changes in CuO2 plane in YBa2Cu4O8 under pressure

We report the results of an atomistic simulation study of the pressure-induced structural changes in YBa₂Cu₄O₈ from 0 to 20 GPa. It is found that the crystal has similar compressibilities in the a- and b-directions over the whole pressure range, whereas in the c-direction there are quite different compressibilities at different pressures. Our results suggest that there exists a correlation between the charge transfer and the change in the Cu(2)---O(1) bond length, but we do not support the suggestion of a direct dependence of T_c on the length of this bond. However, we predict that there are anomalous changes in the CuO₂ plane with pressure, which we propose may lead to a charge carrier redistribution on in-plane copper and in-plane oxygens, which in turn may be related to the optimum carrier concentration in the CuO₂ plane.     

Effect of oxygen on superconductivity and structure of Bi-system superconductor

A systematic study of the effects of oxygen content and distribution in 2223 single-phase Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_10+δ s superconductor has has been carried out using a combination of quenching in air and low-temperature annealing in nitrogen. With decreasing oxygen content a maximum was observed in T_c, accompanying the increase in room-temperature resistivity. Also the effect of oxygen redistribution has been studied by low-temperature annealing in nitrogen, which allows no oxygen content change. After this annealing, in T_c, the room temperature resistivity and the c-axis parameter an apparent change occurred as compared to the original quenching states. From tge measurement of in situ resistivity which increased gradually during low-temperature annealing, it seems that a metastable phase was formed by oxygen diffusion. The interchange of oxygen atoms between Bi₂O₂ and CuO₂ planes and the possible ordering of oxygen vacancies were proposed to explain the relevant experimental phenomena.     

Synthesis and structural characterisation of YSr2Cu3−xMxO7±y (M = Fe, Ti, Al, Co, Ga, Pb; 0.5 < x < 1), and the non-existence of the parent phase YSr2Cu3O7

The possibility of synthesising phases of general composition YSr₂Cu_3−xM_xO_7±y has been examined for a wide variety of metals M. Single phase tetragonal products (typically a = 3.83 Å, c = 11.5 Å) can be synthesised provided that the concentration of M is sufficiently large (x > 0.5), and M has a preference for the Cu(1) sites (the four-coordinate sites) of the YBa₂Cu₃O₇, structure. Neutron diffraction has demonstrated that a high degree of disorder exists in the (001) planes containing the M cations and, in particular, significant oxygen displacements are found. The non-existence of the unsubstituted variant YSr₂Cu₃O₇ is explained in terms of the high degree of compressive stress on the Cu(1) sites which could exist in such a material.