Oxygen nonstoichiometry and phase transitions of the neodymium-rich Nd1+xBa2−xCu3Oz solid solution

On the basis of chemical, thermal analysis and Cu K-edge X-ray absorption measurements, oxygen content in the Nd_1+xBa_2−xCu₃O_z solid solution was determined between 1000°C in air and 400°C in oxygen for x=0.05–0.9 compositions. It has been observed that the oxygen nonstoichiometry Δz of the Nd_1+xBa_2−xCu₃O_7+x/2−Δz solid solution decreases 2–2.5 times for a large substitution (Δz≈0.3–0.33 for x=0.9), despite of the acclaimed higher total oxygen content. The difference in nonstoichiometry is explained by a higher average value of the copper oxidation state (ACV), which is vital for the solid solution with large x even at elevated temperatures (ACV≈2–2.05 for x>0.3 at 1000°C, PO₂=0.21 atm). On the contrary, the ACV after complete oxygenation is almost constant (about 2.25–2.3) for the whole series. The x-dependence of the oxygen content is not monotonous and structural phase transitions can be observed at x=0.3 and x=0.6, as confirmed by the X-ray diffraction and the Raman scattering spectroscopy. The first well-known transition is connected with the oxygen disorder due to the Nd substitution for Ba at random Ba-sites. In the present work, it is proved by the apical oxygen mode broadening in Raman spectra. Ordering of the Nd and Ba atoms with a subsequent orthorhombic distortion of the lattice may occur even at 1000°C in air due to the second transformation at x≈0.6. The invariable orthorhombicity of the Nd-rich solid solution with x>0.6 is not caused by the oxygen absorption as in the x=0.05 case. Existence of high- and low-temperature orthorhombic modifications of this solid solution has been observed for the first time. Finally, a tentative 3D (z–x–T) diagram is suggested for the Nd_1+xBa_2−xCu₃O_z solid solution up to 1000°C in air, including the new x=0.6–0.9 region.     

Unusual resistivity broadening in the mixed state of NdBa2Cu3O7−δ crystals grown by a crystal-pulling technique

In order to clarify the origin of a strong peak effect in the magnetization curve of NdBa₂Cu₃O_7−δ crystals, we investigated the superconductivity transition behavior of the in-plane resistivity in static magnetic fields up to 8 T. Comparing the results for the samples exhibiting and not exhibiting the peak effect, we found that the former (peak effect sample) shows lower resistivity above the vortex melting temperature. This implies that the pinning force is effective in the vortex liquid state. We also found that the normal state resistivity behaviors of some samples were unusual, indicating inhomogeneous current flow. These results suggest an existence of sheet-like pinning centers perpendicular to the conduction planes.     

Field induced flux pinning in Nd1+xBa2−xCu3O7−δ single crystal

The flux pinning behavior of a Nd_1+xBa_2−xCu₃O_7−δ (Nd123) single crystal, which exhibited a peak effect, has been studied by monitoring the time decay of the magnetic moment. The apparent pinning energy (U₀^*) was deduced from flux creep data on the basis of the Anderson-Kim model. The magnetic field dependence of U₀^* showed maxima at peak fields which depended on the temperatures, in a similar manner to those of critical current densities. In addition, the temperature dependence of U₀^* showed several features. To explain the increase in U₀^* with the field as well as its temperature and field dependence, we made a numerical calculation by introducing an additional pinning energy which increased with increasing field. The results are in good agreement with the experimental data, especially at temperatures above 60 K, where the contribution of field induced pinning centers is believed to be dominant.     

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.     

Effect of the RE ionic size on the REBa2Cu3O7−δ ceramics oxygenated at 250 bar

REBa₂Cu₃O_7−δ (RE=Ho, Y, Dy, Gd, Sm, Nd) ceramics have been oxygenated at 1 bar pressure (LP) and, subsequently, at 250 bar (HP). Despite the noticed slight uptake of oxygen (up to the value of 0.07), after the HP processing, the electrical resistivity (ρ) of all samples increased, what was attributed to the deterioration of the grain boundaries. The increase of ρ was much more pronounced and also accompanied by a change of ρ(T) characteristics into a semiconducting-like one in the case of 123 compounds based on REs which ionic size is large enough to form solid solutions of RE_1+xBa_2−xCu₃O_y type (i.e., RE=Gd, Sm, Nd). As shown in the literature, such 123s usually contain more structural defects. Thus, the observed effect may be attributed to the migration of the defects induced by the elevated pressure oxygenation. The defects could be trapped near the grain boundaries resulting in the deterioration of their electrical properties. The possible role of the oxygen-pressure-induced modifications of the impurity phases has been also discussed. The materials obtained in the HP process may be regarded as 3D arrays of superconducting grains coupled by the Josephson junction or weak links only, as was shown in a tunneling experiment.     

Crystal growth of superconductive PrBa2Cu3O7−y

Superconductive PrBa₂Cu₃O_7−y (Pr123) crystals have been grown successfully by the travelling-solvent floating-zone (TSFZ) method using 3.7–5.8% PrO, 27–37% BaO, and 60–69% CuO composition solution with the 0.1–0.4% oxygen mixed argon gas atmosphere. The grown crystals have been identified to be Pr123 by a precession camera, X-ray powder diffractions and scanning electron microscopy–X-ray energy dispersion spectroscopy (SEM-EDS). Some portion of the grown TSFZ crystal boules show bulk superconductivity below about 80 K after annealing in oxygen.     

Effect of oxygen partial pressure on the lower solubility limit of Nd1+xBa2−xCu3O7

The lower solubility limits of Nd_1+xBa_2−xCu₃O₇ (Nd123ss) in 1 bar, 0.2 bar, 0.01 bar, and 0.001 bar oxygen partial pressure (P_O2) were studed by differential thermal analysis (DTA) and X-ray diffraction (XRD). Large relative changes in stability with decreasing P_O2 explain why sharp superconducting transitions can be achieved in P_O2 ≤ 0.01 bar while processing in 0.2 to 1 bar P_O2 tends to produce broad transitions. While the lower solubility limits in 0.01 bar and 0.001 bar P_O2 remain at x = 0.00, the solubility limits in 0.2 bar and 1 bar P_O2 show a narrowing with decreasing temperature. Because of the narrowing of the solubility range in 1 bar P_O2, oxygen annealing of Nd123 initially processed in low P_O2 will result in precipitation of second phases which act as flux pinning centers.     

Effect of aliovalent ion substitution on the oxide ion conductivity in rare-earth pyrohafnates RE2−xSrxHf2O7−δ and RE2Hf2−x AlxO7−δ (RE=Gd and Nd; x=0, 0.1 and 0.2)

Oxide ion conductivity of the pure and aliovalent ion substituted rare-earth pyrohafnates in the series RE_2−xSr_xHf₂O₇ and RE₂Hf_2−xAl_xO₇ (RE=Gd and Nd; x=0–0.2) has been explored in the temperature range 400°C–700°C for the first time. It is seen that, conductivity is enhanced by doping 5 atom% Sr at the rare–earth site in these systems. Well defined impedance plots due to grain interior and grain boundary resistances were obtained in the Gd pyrohafnate with Sr substitution. The results of the conductivity variation for the pure, Sr and Al doped phases are explained on the basis of pyrochlore structure.     

(Tl, Pb, Cu)Sr2(Tl, Pb, Cu)2Cu2O8−δ: a nonsuperconducting Tl-1222 cuprate with both heavy atom single and oxygen depleted double layer motifs

An account is given of the synthesis and structural investigation of a newly discovered tetragonal (Tl, Pb, Cu)Sr₂(Tl, Pb, Cu)₂Cu₂O_8−δ compound (Tl-1222^* phase) with both (Tl, Pb, Cu)O single and oxygen depleted (Tl, Pb, Cu)₂O_x double layer motifs, space group I4/mmm, lattice parameters a=3.8405(2), c=29.2536(5) Å, and D_x=7.46 g cm⁻³. Micaceous and highly reflecting black single crystals of 1 mm×1 mm×3–5 μm size were obtained from a Tl₂O₃- and CuO-rich partial melt. The as-grown compound is nonsuperconducting. The very thin crystals are extremely liable to bend out of shape. Deterioration could not be observed within the period of a year under ambient conditions. The complex crystal structure has been solved using single crystals. We take note of the similarity of the unit cell dimensions to superconducting (Tl, Cu)₂Ba₂(Ca, Tl)Cu₂O₈ (Tl-2212 phase) with TlO double rocksalt layers, and compare crystal-chemical details of similar compounds. Apart from the possibility of obtaining superconducting properties by suitable doping, the mechanical properties of the new material are very attractive from the point of view of its use as highly scattering composite layers of an X-ray monochromator.     

AC and DC magnetic studies of critical currents in ceramics of the Ho1−xPrxBa2Cu3O7−δ system

AC magnetic susceptibility measurements were performed for ceramics of the Ho_1−xPr_xBa₂Cu₃O_7−δ system as a function of temperature, frequency, field amplitude and static magnetic field. From the measurements, temperature dependences of intergranular critical currents and corresponding pinning energies at grain boundaries were determined for different Pr concentrations. These critical currents strongly decrease with Pr doping. They are limited by superconductor–insulator–superconductor or superconductor–normal metal–superconductor junctions and for higher Pr concentrations additionally suppressed by flux creep. Also intragranular critical current at 4.3 K was determined as a function of Pr concentration from magnetic hysteresis loops. It is a monotonically decreasing function of Pr doping.     

Far-infrared spectra of Pb1−xMnxTe alloys

Far-infrared reflectivity spectra of Pb_1−xMn_xTe (0.0001x0.1) single crystals were measured in the 10–250 cm⁻¹ range at room temperature. The analysis of the far-infrared spectra was made by a fitting procedure based on the model of coupled oscillators. In spite of the strong plasmon–LO phonon interaction, we found that the long wavelength optical phonon modes of these mixed crystals showed an intermediate one–two mode behavior.     

Low temperature magnetocaloric effects in Dy1Ba2Cu3O7−δ and Y1Ba2Cu3O7−δ high-Tc single crystals

The heat release has been measured in high temperature superconductors during and after a change of the external magnetic field μ₀H_a ≤ 0.5 T applied parallel to the c-axis at 0.1 K ≤ T ≤ 0.45 K. Two Y123 and one Dy123 twinned single crystals were investigated. An analysis of the heat release based on the Bean model and on a model for thin superconductors in perpendicular geometry recently proposed by Brandt et al. has been carried out. During field sweep we measured ∝ H_a²dH_a/dt. This dependence can be understood within the Bean model for longitudinal geometry. The critical current densities obtained with this method are in good agreement with those from magnetization measurements. We also present measurements, and a first quantitative analysis, of dissipation due to the time relaxation of the flux line lattice after a field sweep. For the heat release a t⁻¹ dependence has been found which corresponds to a logarithmic time dependence of the magnetization. The normalized relaxation rate we obtained is in agreement with literature values.     

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.     

Influence of the doping level on the charge distribution among the inequivalent CuO2 layers in Tl2Ba2Ca2Cu3O10−δ : a NMR study

and NMR measurements in the normal and superconducting states of Tl₂Ba₂Ca₂Cu₃O_10−δ with different δ are reported. In the overdoped Tl2223 sample with T_c=117 K (T_c^opt=123 K) and δ₁<δ^opt different temperature dependencies of the Knight shift are revealed for inequivalent CuO₂ layers. For the inner CuO₂ layer with the square oxygen coordination of Cu the decrease of with temperature is more gradual. In going towards the underdoped Tl2223 with T_c=104 K and δ₂>δ^opt the changes of with temperature are found to be the same for both types of copper layers. The quadrupole coupling constants for copper and oxygen from different CuO₂ layers were obtained. From the variations with doping of the valence contribution to the electric field gradient at copper sites, we estimate both the hole numbers at Cu and oxygen sites and the real concentration of mobile hole carriers n_h in each of inequivalent CuO₂ layers. In the overdoped Tl2223 sample the charge density in the inner layer differs from the one in the outer plane (with five-fold oxygen coordination for Cu). Our results show that the inhomogeneity of the charge distribution disappears in the underdoped regime. The results are compared with calculations of the charge distribution among the CuO₂ planes in multilayered cuprates reported by Haines and Tallon [E.M. Haines, J.L. Tallon, Phys. Rev. B 45 (1992) 3127].     

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.     

Flux jump avalanches in torque studies of single crystal YBa2Cu3O7−δ

A series of avalanche-like jumps are observed in the mixed state of single crystal YBa₂Cu₃O_7−δ (YBCO) superconductors. Emerging as a saw-tooth pattern in torque vs. sample orientation in magnetic field, these jumps are discontinuous on our most resolute angular scale. While reminiscent of the classical flux jump instability, the present jumps are instead proposed to be associated with the layered nature of the material and twin boundary (TB) pinning, the combination of which promotes a crossover from a tilted to a kinked vortex structure.     

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.     

Properties of YBa2Cu3O7−δ/YBa2CoxCu3−xOy/YBa2Cu3O7−δ Josephson edge junctions with 0.1 x 0.3 and the effect of flux flow on their normal resistance

YBa₂Cu₃O_7−δ (YBCO) based SNS edge junctions with cobalt doped YBCO barriers were prepared and characterized. At 77 K, good junctions had RSJ-like I–V curves with excess current, magnetic suppression of I_c of about 50% or more, and clear microwave steps. The conductance values 1/R_N at 77 K of junctions with different barrier thickness and composition, were proportional to the junction areas A, but show little correlation with the thickness of the barriers t_B in the range of 15t_B100nm. The corresponding I_cR_N products were observed to scale as J^0.66±0.09_c, similar to what was found by others. At the same time, the measured values of R_N are much smaller than what is expected based on the dimensions of the junction and the resistivity of the barrier material. To explain all of this, we propose a model in which at high supercurrent densities, flux flow of Josephson vortices in the junction leads to R_N values which are lower than expected. This model predicts

Full-size image (1K)

, which fits the observed results very well.     

Ion-implantation-induced structural modifications in Y1Ba2Cu3O7−δ superconductor

Ion-implantation-induced structural modifications in Y₁Ba₂Cu₃O_7−δ superconductor are examined by a grazing angle X- ray diffraction technique. By employing a range of grazing angles from 0.3° to 10° it is shown that 100 KeV Ar⁺ inplantation of the superconductor leads to amorphization as well as modification of grain size and orientation at dose values lower than 10¹⁶ ions/ cm². At the dose of 5 × 10¹⁶ ions/ cm² the X-ray diffraction intensity is a factor of 6 less as compared to the original pellet, though the lines themselves are sharp. This shows coexistence of perovskite grains and amorphous matrix.