Superconductivity at differentTc in CdBa2Ca2Cu3Oy

A Cd analogue of the Tl and Hgn =3 series with nominal composition CdBa₂Ca₂Cu₃O_y has been synthesized. The samples were superconducting according to magnetic susceptibility measurements. The critical temperature was 103 or 107 K depending on the preparation conditions. The EDX analysis revealed the presence of Cd-1111, Cd-1121, and Cd-2333 as minor phases. The observed diamagnetic effects were attributed to the differentT _c of these phases.     

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.     

Synthesis and Processing of Doped Hg1Ba2Ca2Cu3Oy Superconductors

A series of quenching experiments were conducted to understand the sequence of reactions that occur during the synthesis of doped Hg1223, (Hg, A)Ba₂Ca₂Cu₃O _y , A = Re, Bi, and Pb (HgA1223). The formation and decomposition of the intermediate phases during the high-temperature reaction were followed as a function of temperature. HgA1223 phase forms over a wide range of temperatures, 750–950°C, 750–880°C, and 840–880°C for A = Re, Pb, and Bi, respectively. At T<750°C, HgA1212 phase forms for A = Re and Pb. Based on the results of quenching experiments, heat treatment conditions were optimized for the synthesis of pure HgA1223 phase using commercial BaCaCuO precursor powders. A reduced-temperature annealing stage after the high-temperature reaction helps in grain growth and improves the microstructural characteristics of HgA1223 samples. Control of Hg pressure during the reaction is crucial for achieving phase purity, grain growth, and texture in the final products. A novel approach for the control of Hg pressure during the synthesis of HgA1223, which consists of using CaHgO₂ as an external Hg source, is reported. HgA1223 samples synthesized using the new synthesis protocol exhibit improved microstructural and superconducting properties.     

Charge Density Variations or Stripes in YBa2Cu3O6+y

For many years it was believed that NMR on the YBa₂Cu₃O_6+y family of superconductors does not support charge density variations or stripes. We discuss the NMR data of YBa₂Cu₃O_6+y (y > 0.63) and show that large charge density variations are actually necessary in order to explain the data.     

Substitution of Cu by Fe in the superconducting ceramic oxide EuBa2Cu3Oy: Structure, electrical conductivity, and microwave response

A series of EuBa₂(Cu_1–x Fe _x )₃O_y (0.0x0.15) ceramics were prepared and examined by thermogravimetric analysis, X-ray powder diffraction, electrical resistance measurements, and a magnetically modulated microwave absorption technique. The oxygen content (y=6.98±0.03), determined by thermogravimetric analysis in a reducing atmosphere, was independent of the iron concentration forx0.12. The introduction of iron into the EuBa₂Cu₃O _y lattice, via substitution into copper sites, effects a progressive decrease in the superconducting transition temperature with increasing iron concentration. Normal-state conductivity similarly progresses from a low resistivity and negative temperature coefficient behavior, to a semiconducting-like response at the high iron concentrations. X-ray powder diffraction measurements indicate that material containing 6% iron and above is tetragonal, yet it remains superconducting with up to at least 12% iron.     

Charge-transfer in YBa2Cu3Ox

The charge-transfer hypothesis is shown to be inconsistent with data for YBa₂Cu₃O_x: (i) The two-step behavior ofT _c(x) (with jumps from zero to 60 K and then to 90 K) is not reflected as a similar, statistically significant two-step behavior in the bond-valence-sum charge of cuprate-plane Cu ions (as once believed), (ii) as a consequence of the law of conservation of charge, the derivatives of the layer charges with respect to oxygen contentx for both the Ba-O layers and the charge-reservoir Cu-O chains have the opposite signs to those predicted, and (iii) the charge-transfer observed for superconducting YBa₂Cu₃O_x is not sufficient to produce superconductivity, as demonstrated by insulating PrBa₂Cu₃O_x, which has virtually the same layer charges.     

Nanostripes in GdBa2Cu3Ox high-Tc superconductors

High-T_c superconductors with light rare earth (LRE) elements instead of Y exhibit nanoscale stripe structures on the surface as observed by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) scans. Within the GdBa₂Cu₃O_x (GdBCO) system exhibiting relatively high critical current densities, nanoclusters arranged in a stripe-like fashion are observed in undoped material, while adding of nanoparticles (ZnO₂, ZrO₂) leads to the formation of nanostripes as observed in other LRE superconductors. The nanostripes in doped GdBCO exhibit periodicties between 20 and 50 nm and corresponding step heights of 0.3–0.8 nm. Using polarized light microscopy and electron backscatter diffraction (EBSD) analysis, we determined the direction of the nanostripes with respect to the known twin structure.     

Microstructural study of YBa2Cu3O7/SrTiO3/YBa2Cu3O7 heteroepitaxial trilayer films grown on (100) SrTiO3 substrates

Detailed transmission electron microscopic study has been carried out on heteroepitaxial YBa₂Cu₃O₇/SrTiO₃/YBa₂Cu₃O₇ trilayer thin films grown on (100)SrTiO₃ substrates prepared by DC and RF magnetron sputtering. The microstructural results showed the existence of somea-axis-oriented YBCO grains 20–90 nm wide in thec-axis-oriented YBCO matrix. Some of thea-axis grains in the lower YBCO thin film layer have protruded into the above SrTiO₃ layer, which may cause short circuit between the two YBCO superconducting layers. This is unsuitable for the application of trilayer thin films for microelectronic devices. The defects on the surface of the substrates would also influence the growth quality of the YBCO thin films.     

Superconductivity at 103 K in CdBa2(Ca0.7Y0.3)Cu2Oy

A cadmium analogue of the mercury system with nominal composition CdBa₂(Ca_1–xY_x)Cu₂O_y has been synthesized. Thex=0 samples contain about 12 vol.% of the 1212 phase but are not superconducting. Thex=0.3 samples are superconducting atT _on = 103 K. The EDX analysis of 18 microcrystals shows a broad cationic distribution of the different components. The observed broad superconducting transition is attributed to the variousT _c of the different microcrystals.     

Partial substitution of Li for Cu in superconducting YBa2Cu3Oy

0.33–33% of the Cu in superconducting YBa₂Cu₃O _y has been replaced by Li (i.e.,x=0.01–1 in single-phase or nominal YBa₂Cu_3–x Li_xO_y). X-ray diffraction powder patterns remain the same as for YBn₂Cu₃O _y , with identical patterns up to about 17% substitution (i.e.,x=0.5). At higher percentages an additional phase appears. Electrical conductivity measurements indicate a small elevation ofT _c at low Li content. Starting at about 5% Li (x=0.15),T _c declines progressively and its width increases asx is raised.     

The As-prepared surfaces of C-axis-oriented Nd1Ba2Cu3Oy thin films characterized using scanning probe microscopes

Recently, superconducting Nd₁Ba₂Cu₃O_y (Ndl23) thin films with high superconducting transition temperature (T _c) have been successfully fabricated at our institute employing the standard laser ablation method. In this paper, we report the results of surface characterization of the Nd123 thin films using an ultrahigh vacuum scanning tunneling microscope/spectroscopy (UHV-STM/STS) and an atomic force microscope (AFM) system operated in air. Clear spiral pattern is observed on the surfaces of Nd123 thin films by STM and AFM, suggesting that films are formed by two-dimensional island growth mode. Contour plots of the spirals show that the step heights of the spirals are not always the integer or half-integer number of thec-axis parameter of the structure. This implies that the surface natural termination layer of the films may not be unique. This result is supported byI-V STS measurements. The surface morphology of the Nd123 thin films is compared with that of thec-axis-oriented Y₁Ba₂Cu₃S_y thin films. Surface atomic images of the as-prepared Nd123 thin films are obtained employing both STM and AFM. STS measurements show that most of the surfaces are semiconductive. The results of STS measurements together with the fact that we are able to see the surface atomic images using scanning probe microscopes suggest that exposure to air does not cause serious degradation to the as-prepared surfaces of Nd123 thin films.     

Investigations of Bi substitution in NdBa2Cu3Oy

Attempts to substitute Bi for Nd in orthorhombic NdBa₂Cu₃O _y , prepared in air or oxygen at about 950°C led instead to formation of Ba₂NdBiO₆, a new cubic compound witha=0.8703 nm. The possibility was then explored of preparing superconducting (Nd_1–x Bi _x )Ba₂Cu₃O _y , by first forming the tetragonal phase at 880–950°C in nitrogen or argon followed by reheating in oxygen or air at 250–500°C in order to insert the additional oxygen required to yield the orthorhombic form while avoiding oxidation of Bi³⁺ to Bi⁵⁺. X-ray diffraction studies, electrical conductivity measurements, and thermogravimetric analysis of products indicate that Bi does not enter the NdBa₂Cu₃O _y , lattice in either the tetragonal or the orthorhombic phase. Ba₂NdBiO₆ clearly forms on reheating in oxygen or air even at low temperatures, and evidence is presented that a poorly crystallized oxygen-deficient form of this compound is already present prior to the reheating.     

Fluctuation conductivity in Li-doped YBa2Cu3O7?x

The paraconductivity of Li-doped YBa₂Cu₃O_7–x was measured. We have found that the character of the fluctuation changes as lithium content increases: instead of a crossover from 2D to 3D behavior (D is the dimensionality), as we have observed for a low doping level, a double crossover to the 2D percolative and 3D percolative regimes becomes manifest by increasing the lithium content.     

Raman scattering studies of ultrathin-layer YBa2Cu3O7/PrBa2Cu3O7 superlattices

We present Raman scattering studies ofc-oriented ultrathin-layer superconducting (YBa₂Cu₃O₇) _m /(PrBa₂Cu₃O₇) _n superlattices. For the superlattice with (m=2,n=1) sequence, Raman spectra reveal a new line in the spectral region around 320 cm^–1. It is interpreted as a mode representing a combination of IR optical phonons of the Y-sublayers with an admixture of aB _1g type Raman active vibration in the Pr sublayers. This new line, which is similar to those from the interior of the Brillouin zone of the original lattice, does not exhibit superconductivity-induced self-energy effects, although its counterpart in the pure substance does. No additional line is found in the (m=1,n=2) superlattice in the same region, supporting our interpretation for the (m=2,n=1) sample.     

Energy Scales in the High-Tc Superconductor YBa2Cu3O6+x

The optical conductivity sum rule is used to examine the evolution of the spectral weight N() in both the normal and superconducting states of optimally and underdoped YBa₂Cu₃O_6+x along the a axis. Differences in N() above and below T _c allow the strength of the superconducting condensate _s to be determined. In the optimally-doped material, _s is fully formed at energies comparable to the full superconducting gap maximum (0.1 eV), while in the underdoped material the energy scale for convergence is considerably higher (0.6 eV). This difference is discussed in terms of normal-state properties.     

High Critical Current Density YBa2Cu3Ox Tapes Using the RABiTs Approach

Progress in the fabrication of epitaxial, high-J _c, biaxially aligned YBCO thick films on Rolling-assisted biaxially textured substrates (RABiTs) is reported. RABiT substrates comprise a biaxially textured metal substrate with epitaxial oxide buffer layers suitable for growth of superconductors. Oxide buffer layers have been deposited using three techniques: laser ablation, electron-beam evaporation, and sputtering. Epitaxial YBCO films grown using laser ablation on such substrates have critical current densities approaching 3 × 10⁶ A/cm² at 77 K in zero field and have field dependences similar to epitaxial films on single crystal ceramic substrates. Critical current densities in excess of 0.2 MA/cm² have been obtained on stronger, nonmagnetic substrates. In addition, samples with J _e of 12.5 kA/cm² at 77 K have been fabricated. The highest strain tolerence obtained so far is 0.7% in compression and 0.25% in tension. Deposited conductors made using this technique offer a potential route for the fabrication of long lengths of high-J _c wire capable of carrying high currents in high magnetic fields and at elevated temperatures.     

Electronic Raman scattering of superconducting YBa2Cu3Oy single crystals

TheA _1g andB _1g low-energy Raman continua of YBa₂Cu₃O _y (Y123) single crystals, withy=7.0, 6.99, and 6.93, have been investigated. It is found that the peak frequency of theA _1g continuum is equal to 310±10 cm^–1 and independent of oxygen concentration fory in the above range. The central frequency of the broad peak in theB _1g continuum, however, shifts from about 470 cm^–1 fory7.0 to 550 cm^–1 fory6.93. Thus, a relatively small change in oxygen concentration results in a significant redistribution of the states contributing to theB _1g continuum. Assuming the low-energy portions of the continua are electronic in origin, the Raman spectra have been calculated and the results compared to the experimental spectra. It is suggested that the Raman continua arise, at least in part, from scattering across a spin fluctuation-induced pseudogap.     

Stabilization of the 108 K superconducting phase in the Bi0.7Pb0.3SrCaCu1.8Oy system

Samples having the nominal composition Bi_0.7Pb_0.3SrCaCu_1.8O _y , were prepared by a solid-state reaction and characterized by energy-dispersive x-ray microanalysis, resistivity measurements, and magnetically modulated microwave absorption (MAMMA). Longer annealing times resulted in more homogeneous samples having a single superconducting transition to zero resistance at 108 and 105 K at 0.1 and 1 mA, respectively. The MAMMA measurements clearly show differences in sample homogeneity with different annealing times.     

Direct Peritectic Growth of c-Axis Textured YBa2Cu3Ox on a Flexible Metallic Substrate

Previous work in the development of YBa₂Cu₃O _x (YBCO) superconducting wires and tapes has been focused on the deposition of YBCO on buffered metallic substrates. Although such an approach has proved successful in terms of achieving grain texturing and high transport current density, critical issues involving continuous processing of long-length conductors and stabilization of the superconductor have not yet been entirely settled. We have developed a novel process, the so-called direct peritectic growth (DPG), in which textured YBCO thick films have been successfully deposited directly onto a silver alloy substrate. No buffer layer is employed in the film deposition process. The textured YBCO grains have been obtained through peritectic solidification over a wide range of temperatures and times. The substrate materials have not demonstrated any observable reaction with the YBCO melt at the maximum processing temperature near 1010°C. The transport J _c has reached a respectable value of 10⁴ A/cm² at 77 K and zero magnetic field. Based on the experimental results in this work, we show that the DPG method offers an effective alternative for the fabrication of long-length YBCO conductors. Also reported is a physical explanation of the texturing mechanism on the metal substrate.     

Crystal-chemical anomalies in nonsuperconducting PrBa2Cu3O7

Studies of the crystal chemistry of nonsuperconducting PrBa₂Cu₃O₇ indicate that this compound is strictly isostructural with its superconducting RBa₂Cu₃O₇ (R = Y, rare earth) analogs. Crystallographically, Pr is present in the trivalent state according to the structural trends exhibited by the RBa₂Cu₃O₇ series as a function of R³⁺ ionic radius. The sole structural anomaly attributable to the presence of Pr³⁺ in the YBa₂Cu₃O₇ structure is a next-next-nearest neighbor effect and consists of an unusually short axial Cu-O distance, i.e., a short bond length between the in-plane copper and the chain oxygen. The correlation of this anomaly with the nonmetallic/nonsuperconducting properties of PrBa₂Cu₃O₇ supports a variety of literature reports, both theoretical and experimental, suggesting that the apical oxygen in the YBa₂Cu₃O₇ structure plays a critical role in mediating the appearance of superconductivity. The mechanism by which the f-electrons in Pr³⁺ (f ²) interact with the Cu-O manifold to produce the nonmetallic behavior of PrBa₂Cu₃O₇ remains unknown; however, superconductivity is turned back on for Nd³⁺ (f ³), immediately next to Pr and just slightly smaller. Careful comparative studies of superconducting NdBa₂Cu₃O₇ and nonmetallic PrBa₂Cu₃O₇ are needed to elucidate the critical difference in the behavior of the f-electrons and may shed light on the fundamental mechanism of high-temperature superconductivity in copper oxides.