电化学法涂层导体CeO_2缓冲层外延生长研究

电化学沉积法制备高温超导YBa2Cu3O7-δ涂层导体缓冲层具有工艺简单、设备要求低、易于连续化批量制备等优点。采用电化学沉积法,在双轴织构的Ni-5at.%W(Ni-5W)金属基带上成功制备出了具有良好c轴取向的CeO2缓冲层薄膜。利用X射线衍射、极图、扫描电子显微镜和原子力显微镜等对上述氧化物薄膜的织构、表面形貌等进行表征。重点研究了薄膜厚度、退火温度、退火时间等工艺对薄膜外延生长及其表面形貌的影响,结果表明:电化学沉积方法制备的CeO2缓冲层具有很好的双轴织构、表面平整、均一,粗糙度低,表现出良好的缓冲层性质。结合金属有机化学溶液超导层的制备技术,本工作展示了一条全化学法制备第二代高温超导带材的技术路线,具有很好的应用前景。     

Degradation characteristics of YBCO coated conductors due to fault-current in power cable applications

In high temperature superconductor applications used in electric power devices, YBCO coated conductors may be subjected to short-circuit fault-currents that are 10–30 times the normal operating current. These over-currents cause heat generation, resulting in I_c degradation of the YBCO coated conductor. Therefore, it is necessary to fully investigate the degradation characteristics of YBCO coated conductors. We previously conducted preliminary experiments on the degradation of YBCO sample tapes resulting from the over-current pulse drive.     

Japanese efforts on coated conductor processing and its power applications: New 5 year project for materials and power applications of coated conductors (M-PACC)

Five years of Japanese national project (FY2003–FY2007) was ended last spring with remarkable success. The national project was originally aimed for development of coated conductors which have high superconductivity performance and long length enough to fabricate high temperature superconducting (HTS) electric power devices. Preliminary research and development of HTS electric power devices were carried out as well. A series of R&D results will be summarized and reviewed in this paper.The new 5 years Japanese national project has started last June (FY2008–FY2012) to develop HTS electric power applications including SMES, cables and transformers and to develop/produce coated conductors satisfying the requirements from the respective power devices. Collaborative R&D efforts by national laboratories, universities and private companies have been started with the supports of NEDO and METI.The accomplishment of the previous project will be summarized and the plans and goals of the new project will be presented in this paper.     

Evaluation of delamination properties of coated conductors by means of MELT method using epoxy resin

Coated conductors (CCs) are prospective for application to electric power conductors due to not only better cost performance but also high J_c–B properties compared with Bi₂Sr₂Ca₂Cu₃O₁₀ (BSCCO) tapes. However, CCs are composed of multi-layered thin films and metal substrate, and post-treatments are essential to putting CCs to practical use, which are slitting and/or making thin film multi-filaments. For this reason, CCs delaminate between multi-layers. The delamination prevents CCs from functioning as superconducting wire, and therefore there is a need to evaluate delamination toughness of CCs quantitatively.     

Potential of Nd:YAG pulsed laser deposition method for coated conductor production

A Nd:YAG laser is environmentally safe and economical with no poisonous or hazardous gases and no expensive gases. We prepared Y123 films by using the fourth harmonic Nd:YAG pulsed laser deposition (PLD) method and optimized the deposition conditions on MgO single crystalline substrates and IBAD-MgO substrates for Y123 coated conductor. We found that the optimal deposition conditions acquired bi-axially aligned Y123 films on both substrates with T_c ∼ 90 K and J_c > 1 MA/cm² at 77 K in self-field. For obtaining high I_c, we fabricated thick Y123 films on both substrates and the maximum I_c per 1 cm in width reached 186 A/cm-width on the IBAD-MgO substrate. Interestingly, there were no a-axis oriented grains within the films up to 1.8 μm thick. This might be an especial feature of the Nd:YAG-PLD method. We believe that the Nd:YAG-PLD method is promising method for RE123 coated conductor production.     

Mechanical and electrical characteristics of silver stabilizer layer prepared by using nano silver paste for coated conductor

Mechanical and electrical properties of silver stabilizer layer of coated conductor, which was prepared using nano silver paste as starting materials, have been investigated. Nano silver paste was coated on YBCO (Y₁Ba₂Cu₃O_7−δ) film by a dip coating method with a speed of 25 mm/min. Coated film was dried in air and heat treated at 400–700 °C in a flowing oxygen atmosphere. Adhesion strength between YBCO and silver layer was measured by Tape test (ASTM D 3359). The hardness and electrical conductivity of the sample were measured by pencil hardness test (ASTM D 3363). Surface and volume resistance were measured by using LORESTA-GP (MITSUBISHI). The sample heat treated at 500 °C showed poor adhesiveness of 1B but it is clearly enhanced to 5B when samples were heat treated at higher than 600 °C. The silver layer heat treated at 700 °C showed a high hardness value of higher than 9H and a volume resistance of 1.417 × 10⁻⁷ Ω mm at room temperature. SEM observations showed that a dense silver layer was formed with a thickness of about 2 μm. Dip coated silver layer prepared by using nano silver paste showed superior electrical and mechanical characteristics which is comparable to those that sputter deposited Ag layer.     

Development of buffer layers on 30 mm wide textured metal substrates for REBCO coated conductors

We have been studying REBa₂Cu₃O_x (RE: rare earth elements) coated conductors on clad-type substrates. We developed coated conductors on the 10 mm wide clad-type tape, and succeeded in obtaining the maximum critical current of 380 A/cm with the 2.0 μm thick GdBa₂Cu₃O_x superconducting film. At present, we are trying to widen the tape width from 10 mm to 30 mm in order to increase production throughput. We report our recent progress on scaling-up of the buffer layers and their properties.     

Charge fluctuation,charge ordering,and zero-gap state in organic conductors

We have carried out a series of measurements of angular dependence of solid-state NMR spectrum using single crystal samples on various organic molecular conductors, in order to investigate the natures of the electronic states at low temperatures. We confirmed a charge ordered insulating state in α-(BEDT-TTF)₂I₃ and large charge disproportionation in the metallic state of this salt. In another charge ordered system, θ-(BEDT-TTF)₂RbZn(SCN)₄, we observed unusual NMR line broadening, proportional to resonance shift, in the metallic state above the transition. We found that this broadening is due to charge disproportionation, or more correctly, due to the inhomogeneity of local susceptibility at nuclear sites and analyzed its dynamics. We observed similar broadening in various organic molecular conductors as well, such as θ-(BEDT-TTF)₂CsZn(SCN)₄, an exotic Bechgaad salt, (TMTSF)₂FSO₃, and λ-type BETS salts, λ-(BETS)₂(Fe,Ga)Cl₄. We found the mechanism of CD in each system is different, respectively.     

Fractal analysis and atomic force microscopy measurements of surface roughness for Hastelloy C276 substrates and amorphous alumina buffer layers in coated conductors

In coated conductors, surface roughness of metallic substrates and buffer layers could significantly affect the texture of subsequently deposited buffer layers and the critical current density of superconductor layer. Atomic force microscopy (AFM) is usually utilized to measure surface roughness. However, the roughness values are actually relevant to scan scale. Fractal geometry could be exerted to analyze the scaling performance of surface roughness. In this study, four samples were prepared, which were electro polished Hastelloy C276 substrate, mechanically polished Hastelloy C276 substrate and the amorphous alumina buffer layers deposited on both the substrates by ion beam deposition. The surface roughness, described by root mean squared (RMS) and arithmetic average (R_a) values, was analyzed considering the scan scale of AFM measurements. The surfaces of amorphous alumina layers were found to be fractal in nature because of the scaling performance of roughness, while the surfaces of Hastelloy substrates were not. The flatten modification of AFM images was discussed. And the calculation of surface roughness in smaller parts divided from the whole AFM images was studied, compared with the results of actual AFM measurements of the same scan scales.     

Influence of tensile damage on V–I curve and critical current of DyBCO coated conductor

The coated conductors are subjected to mechanical and electromagnetic stresses in preparation and service. When the stress is high, the coated layer is damaged, resulting in loss of superconducting property. The present work was carried out to reveal the influence of tensile damage on V–I curve, critical current and n-value of DyBa₂Cu₃O_7−δ coated conductor. The changes of the V–I curve, critical current and n-value with increasing applied tensile strain were measured experimentally. The features of the shift of the V–I curve to the lower current range and increase in its curvature, and accordingly the decrease in critical current and n-value, with increasing applied strain, were detected. For analysis of the experimental results, the model of Fang et al, which treats with the voltage generation due to the current shunting under existent crack, was applied. The experimentally observed features were described satisfactorily.     

Current transport property in GdBCO coated conductor with artificial pinning centers in a wide range of temperature,magnetic field up to 27 T,and field angle

We have investigated current transport property in Gd₁Ba₂Cu₃O_7−δ coated conductor with artificial pinning centers in a wide range of temperature, magnetic field, B up to 27 T, and field angle. Due to the additional c-axis correlated pins, critical current density, J_c in B//c was enhanced and the improvement was observed in wide range of B. On the other hand, around B⊥c below 65 K, the angular dependence of n-value showed a valley-like behavior, although the J_c was increasing. In addition, the temperature dependence of the pinning force density defined as J_c × B was not scaled on an expected master curve. These results indicate the pinning in B⊥c is governed by different mechanism below 65 K and high magnetic field.     

Hydrostatic pressure study of the structural phase transitions and superconductivity in single crystals of (Ba1−xKx)Fe2As2 (x=0 and 0.45) and CaFe2As2

We studied the effect of hydrostatic pressure (P) on the structural phase transitions and superconductivity in the ternary and pseudo-ternary iron arsenides CaFe₂As₂, BaFe₂As₂, and (Ba_0.55K_0.45)Fe₂As₂, by means of measurements of electrical resistivity (ρ) in the 1.8-300 K temperature (T) range, pressures up to 20 kbar, and magnetic fields up to 9 T. CaFe₂As₂ and BaFe₂As₂ (lightly doped with Sn) display structural phase transitions near 170 and 85 K, respectively, and do not exhibit superconductivity in ambient pressure, while K-doped (Ba_0.55K_0.45)Fe₂As₂ is superconducting for T<30 K. The effect of pressure on BaFe₂As₂ is to shift the onset of the crystallographic transformation down in temperature at the rate of ~−1.04 K/kbar, while shifting the whole ρ(T) curves downward, whereas its effect on superconducting (Ba_0.55K_0.45)Fe₂As₂ is to shift the onset of superconductivity to lower temperatures at the rate of ~−0.21 K/kbar. The effect of pressure on CaFe₂As₂ is first to suppress the crystallographic transformation and induce superconductivity with onset near 12 K very rapidly, i.e., for P<5 kbar. However, higher pressures bring about another phase transformation characterized by reduced-resistivity, and the suppression of superconductivity, confining superconductivity to a narrow pressure dome centered near 5 kbar. Upper critical field (H_c2) data in (Ba_0.55K_0.45)Fe₂As₂ and CaFe₂As₂ are discussed.     

Ultrafast quasiparticle dynamics in heavy Ca-doped YBCO thin films

The dynamics of photoinduced quasiparticle in the Y_1−xCa_xBa₂Cu₃O_7−δ thin films is revealed by using the femtosecond reflection spectroscopy. For the case of x = 0.3, two distinct components have been clearly observed in the transient reflectivity change (ΔR/R). The positive component of ΔR/R appears well below T_c. Moreover, the divergent peak of temperature-dependent relaxation time (τ), which is believed to intimately relate to the opening of superconducting gap, shifts to lower temperature as increasing the Ca-doping in YBa₂Cu₃O_7−δ.     

The influence of impurity on the critical thickness of the CeO<Subscript>2</Subscript> buffer layer for coated conductors

The lattice parameters, band structure, density of state and elastic constant of RE-doped CeO₂ (RE=Sm, Gd, Dy), the buffer material for coated HTS conductors, are calculated using the plane-wave method with pseudopotentials based on the density functional theory (DFT) of first-principle. The rule and mechanism of the effect of rare earth impurity on the critical thickness of the CeO₂ buffer layer are investigated. It is found that, in the range of the calculation, the changes of the lattice volume V and elastic constant E* of CeO₂ with the impurity are mainly determined by the increased electrons δn _e of the system. The relationship of the elastic constant E* and increased electrons δn _e is established. It is indicated that the critical thickness of the CeO₂ single buffer layer doped with Sm, Gd, and Dy may be enhanced by 22%, 43% and 33%, respectively. Supported by the Youth Scientific Research Project of Southwest Jiaotong University (Grant No. 2007Q017), the National Natural Science Foundation of China (Grant No. 50588201), and the Ministry of Science and Technology of China (Grant No. 2007CB616906)     

High-speed deposition of RE123 film with large current capacity by hot-wall type PLD system

We have studied a hot-wall heating system to produce GdBa₂Cu₃O_y (GdBCO) films with large critical currents (I_c) at a high production rate by a pulsed-laser-deposition (PLD) method. GdBCO films fabricated at a production rate of 30 m/h under the optimized conditions, especially a distance of 95 mm between the target and the substrate (T–S), exhibited high critical current densities (J_c) of about 3 MA/cm² and I_c over 300 A at a thickness of 1–2 μm. Furthermore, long GdBCO tapes prepared by repeated depositions at each tape-passing speed of 80 m/h showed uniform I_c distribution along the longitudinal direction, because the hot-wall system enabled to stabilize temperature within a few degrees at 800 °C. A 170 m long tape with I_c over 600 A was successfully fabricated at a production rate of 16 m/h using a laser power of 360 W.     

Experimental search for universality of the specific heat in Ni-Cu ferromagnetic system. part I.

In these papers (Part I and Part 11) the results of a detailed experimental study of the specific heat near the Curie temperature are reported for the Ni-Cu ferromagnetic alloy system. The measuring technique and specimen preparation have allowed high enough resolution of specific heat for critical exponent analysis in the 0–10 weight per cent concentration range. A simple data analysis without higher corrections gives very unsatisfactory results in respect of symmetry (α = α′) and universal behaviour of specific heat. The problem of rounding and the regular background term to the specific heat is analyzed.     

MgB2 coated superconducting tapes with high critical current densities fabricated by hybrid physical-chemical vapor deposition

The MgB₂ coated superconducting tapes have been fabricated on textured Cu (0 0 1) and polycrystalline Hastelloy tapes using coated conductor technique, which has been developed for the second generation high temperature superconducting wires. The MgB₂/Cu tapes were fabricated over a wide temperature range of 460-520 °C by using hybrid physical-chemical vapor deposition (HPCVD) technique. The tapes exhibited the critical temperatures (T_c) ranging between 36 and 38 K with superconducting transition width (ΔT_c) of about 0.3-0.6 K. The highest critical current density (J_c) of 1.34 × 10⁵ A/cm² at 5 K under 3 T is obtained for the MgB₂/Cu tape grown at 460 °C. To further improve the flux pinning property of MgB₂ tapes, SiC is coated as an impurity layer on the Cu tape. In contrast to pure MgB₂/Cu tapes, the MgB₂ on SiC-coated Cu tapes exhibited opposite trend in the dependence of J_c with growth temperature. The improved flux pinning by the additional defects created by SiC-impurity layer along with the MgB₂ grain boundaries lead to strong improvement in J_c for the MgB₂/SiC/Cu tapes. The MgB₂/Hastelloy superconducting tapes fabricated at a temperature of 520 °C showed the critical temperatures ranging between 38.5 and 39.6 K. We obtained much higher J_c values over the wide field range for MgB₂/Hastelloy tapes than the previously reported data on other metallic substrates, such as Cu, SS, and Nb. The J_c values of J_c(20 K, 0 T) ∼5.8 × 10⁶ A/cm² and J_c(20 K, 1.5 T) ∼2.4 × 10⁵ A/cm² is obtained for the 2-μm-thick MgB₂/Hastelloy tape. This paper will review the merits of coated conductor approach along with the HPCVD technique to fabricate MgB₂ conductors with high T_c and J_c values which are useful for large scale applications.     

Incommensurate SDW in cuprates

The incommensurate antiferromagnetism (AF) in metallic underdoped cuprates is interpreted with several complementary approaches, unified by a consistent disambiguation of the copper and oxygen degrees of freedom. Collinear (with respect to the copper lattice) peaks in the neutron response at low frequency are due to the oxygen-dominated arcs, while the diagonal peaks at high frequency or low doping come from the copper-dominated vH points. The latter switch from collinear to diagonal as the frequency increases. The direct O–O overlap induces an AF which is weaker and thermodynamically preferred to the AF of strongly localized copper sites, and which coexists with Fermi arcs. A theoretical understanding of the strongly k-dependent$\mathbf{k}\mathrm{-}\mathrm{dependent}$ AF gap observed in ARPES and STM measurements is proposed.     

Development of cube textured Ni–5 at.%W alloy substrates for coated conductor application using a melting process

Biaxially textured Ni–5 at.%W substrates have been prepared by cold rolling, followed by three different annealing routes. In this paper, the processes of melting Ni and W metals, flat rolling, various annealing methods are described in detail. The Ni–5 at.%W tapes annealed under either high vacuum or flowing Ar (7% H₂) gas were characterized by X-ray pole figures, ODF, EBSD as well as AFM analysis. The texture analysis indicated that as fabricated tapes have a sharp cube texture formed after annealing at a wide temperature range of 800–1100 °C. The high quality of cube orientation on tapes was obtained after a two-step annealing (TSA), where the percentage of the cube texture component was as high as 93.5% within a misorientation angle smaller than 8° from EBSD analysis. Furthermore, it was also observed that the number of twin boundaries in this tape decreased with respect to that of tapes annealed both in vacuum and one-step gas annealing. From AFM on 1 μm² areas, it was concluded that the roughness (RMS) on the tape surface reached 0.98 nm.     

Meter-long CeO2/YSZ/Y2O3 buffer layers for YBCO coated conductors using DC reactive sputtering

This paper reports CeO₂/YSZ/Y₂O₃ buffer layers deposited on biaxially textured NiW substrates by DC reactive sputtering in a reel-to-reel system. The effect of partial pressure of water vapor (P_H2O) on surface morphology and orientation of the Y₂O₃ films was examined. The obtained CeO₂/YSZ/Y₂O₃ buffer layers exhibit a highly biaxial texture, with in- and out-of-plane FWHM values respectively in the range of 6.0–7.0° and 4.5–5.5°. Crystallographic consistency of CeO₂/YSZ/Y₂O₃ along meter length is excellent. Atomic force microscope observation (AFM) reveals a smooth, continuous and crack-free surface with a Root-mean-square roughness (RMS) lower than 10 nm.