Pinning,thermally activated depinning and their importance for tuning the nanoprecipitate size and density in high Jc YBa2Cu3O7−x films

YBa₂Cu₃O_7?x (Y123) films with quantitatively controlled artificial nanoprecipitate pinning centers were grown by pulsed laser deposition (PLD) and characterized by transport over wide temperature (T) and magnetic field (H) ranges and by transmission electron microscopy (TEM). The critical current density J_c was found to be determined by the interplay of strong vortex pinning and thermally activated depinning (TAD), which together produced a non-monotonic dependence of J_c on c-axis pin spacing d_c. At low T and H, J_c increased with decreasing d_c, reaching the very high J_c ～ 48 MA/cm² ～20% of the depairing current density J_d at 10 K, self-field and d_c ～ 10 nm, but at higher T and H when TAD effects become significant, J_c was optimized at larger d_c because longer vortex segments confined between nanoprecipitates are less prone to thermal fluctuations. We conclude that precipitates should extend at least several coherence lengths along vortices in order to produce irreversibility fields H_irr(77 K) greater than 7 T and maximum bulk pinning forces F_p,max(77 K) greater than 7–8 GN/m³ (values appropriate for H parallel to the c-axis). Our results show that there is no universal pin array that optimizes J_c at all T and H.     

Effects of nanoscale defects on critical current density of (Y1−xEux)Ba2Cu3O7−δ thin films

In pulsed laser deposition of YBa₂Cu₃O_7?δ films, defect introduction into the films tends to anisotropically improve the pinning along the H||c direction due to the columnar growth mode of the process. In Eu-substituted samples, however, even though an increase in critical current density (J_c) in the H||c direction was observed for low fields (H = 0.2 T), the improvement was more notable for the H||ab-plane at both low and higher fields. Herein we present detailed TEM microstructural studies to understand these new trends in J_c(H), which are markedly different than flux pinning increases achieved with other methods, for example, with nanoparticle additions. Threading dislocations, observed in the Eu-substituted samples along the c-axis, account for J_c enhancement with H||c at low field. The enhanced ab-planar pinning in the Eu-substituted samples is attributed to the extensive bending of the {0 0 1} lattice planes throughout the film, and the crystal lattice defects with excess Cu–O planes, that were effective in increasing the J_c for H||ab at both low and high fields.     

Quick screening for new flux pinning materials in YBCO films with the combinatorial-PLD method

An effective way to improve the superconducting properties in REBa₂Cu₃O_y (REBCO) films under a magnetic field is to dope artificial pinning centers (APC). The pinning performance depends on the content of the APC materials. Usually, the optimal APC content is explored by preparing films one at a time from the REBCO target using different APC material content, which is an extremely time-consuming process.The combinatorial-PLD (C-PLD) method allowed us to prepare films that continuously changed in composition across a single substrate. In this study, we used the C-PLD method to prepare BaSnO₃ (BSO)-doped YBCO films. The films were deposited on SrTiO₃ substrate using a fourth-harmonic Nd:YAG laser. From the results of the J_c–B curves at 77 K and B//c, the film that contained 3.2 vol.% of BSO exhibited the best pinning performance in this study. We showed that the C-PLD method was efficient for quick screening of the optimal APC content with only one deposition. We also used the C-PLD method to explore new APC materials, and proved that it can quickly evaluate the new APC materials Ba₃Cu₃In₄O₁₂ and BaTbO₃.     

Preparation of solution-based YBCO films with BaSnO3 particles

The YBCO films with BaSnO₃ (BSO) particles were prepared on LAO (0 0 1) substrates by metal organic deposition using trifluoroacetates (TFA-MOD) via introducing SnCl₄ powders into the YBCO precursor solution. It was found that with the increase of the SnCl₄ contents, the slower decomposition and higher temperature for nucleation during the reaction were requested compared to that of pure YBCO film. The YBCO films with different contents of Sn with dense surface and well c-alignment were obtained under optimized heat treatment, and the BaSnO₃ phases were detected by XRD analysis. Litter effect of BSO particles on the T_c and J_c values of YBCO films was found. All YBCO films with BSO particles had T_c values over 90 K and J_c values over 1 MA/cm². A significant enhancement of J_c was observed for YBCO films with BSO particles compared to that of pure YBCO film by the field dependence of J_c values. The best property was obtained for YBCO film with 6 mol.% Sn at 77 K under magnetic field. The results showed that the J_c value of YBCO film with 6 mol.% Sn was enhanced by a factor of 2 in 2 T, and over a factor of 10 beyond 4 T compared to that of pure YBCO film.     

High performance GdBa2Cu3O7−z film preparation by non-fluorine chemical solution deposition approach

Biaxially textured GdBa₂Cu₃O_7?z (GdBCO) films with T_c above 93 K have been prepared on (0 0 l) LaAlO₃ substrate by self-developed non-fluorine polymer-assisted chemical solution deposition (PA-CSD) approach. The GdBCO films show smooth and crack-free morphology. Many nanoscale particles with homogeneous distribution are observed in the GdBCO films, which have not been observed yet in the YBa₂Cu₃O_7?z (YBCO) films prepared by the same processing technique. Besides a high J_c (77 K, 0 T) of 2.28 MA/cm², the optimized GdBCO films show a better J_c–B behavior and an improved high-field J_c, compared to the YBCO films.     

Thickness dependence of Ic and Jc of LTG-SmBCO coated-conductor on IBAD-MgO tapes

We have reported SmBa₂Cu₃O_y (SmBCO) films on single crystalline substrates prepared by low-temperature growth (LTG) technique. The LTG-SmBCO films showed high critical current densities in magnetic fields compared with conventional SmBCO films prepared by pulsed laser deposition (PLD) method. In this study, to enhance critical current (I_c) in magnetic field, we fabricated thick LTG-SmBCO films on metal substrates with ion-beam assisted deposition (IBAD)-MgO buffer and estimated the I_c and J_c in magnetic fields.All the SmBCO films showed c-axis orientation and cube-on-cube in-plane texture. T_c of the LTG-SmBCO films were 93.1–93.4 K. J_c and I_c of a 0.5 μm-thick SmBCO film were 3.0 MA/cm² and 150 A/cm-width at 77 K in self-field, respectively. Those of a 2.0 μm-thick film were 1.6 MA/cm² and 284 A/cm-width respectively. Although I_c increased with the film thickness increasing up to 2 μm, the I_c tended to be saturated in 300 A/cm-width. From a cross sectional TEM image of the SmBCO film, we recognized a-axis oriented grains and 45° grains and Cu–O precipitates. Because these undesired grains form dead layers, I_c saturated above a certain thickness. We achieved that I_c in magnetic fields of the LTG-SmBCO films with a thickness of 2.0 μm were 88 A/cm-width at 1 T and 28 A/cm-width at 3 T.     

Studies on structural and magnetic properties of Co-doped pyramidal ZnO nanorods synthesized by solution growth technique

Large-area arrays of highly oriented Co-doped ZnO nanorods with pyramidal hexagonal structure are grown on silica substrates by wet chemical decomposition of zinc–amino complex in an aqueous medium. In case of undoped ZnO with an equi-molar ratio of Zn²⁺/hexamethylenetetramine (HMT), highly crystalline nanorods were obtained, whereas for Co-doped ZnO, good quality nanorods were formed at a higher Zn²⁺/HMT molar ratio of 4:1. Scanning electron microscope (SEM) studies show the growth of hexagonal-shaped nanorods in a direction nearly perpendicular to the substrate surface with a tip size of ～50 nm and aspect ratio around 10. The XRD studies show the formation of hexagonal phase pure ZnO with c-axis preferred orientation. The doping of Co ions in ZnO nanorods was confirmed by observation of absorption bands at 658, 617 and 566 nm in the UV–vis spectra of the samples. The optical studies also suggest Co ions to be present both in +2 and +3 oxidation states. From the photoluminescence studies, a defect-related emission is observed in an undoped sample of ZnO at 567 nm. This emission is significantly quenched in Co-doped ZnO samples. Further, the Co-doped nanorods have been found to show ferromagnetic behavior at room temperature from vibrating sample magnetometer (VSM) studies.     

Influence of Zr and Ce doping on electromagnetic properties of (Gd,Y)–Ba–Cu–O superconducting tapes fabricated by metal organic chemical vapor deposition

(Gd,Y)Ba₂Cu₃O_x tapes have been fabricated by metal organic chemical vapor deposition (MOCVD) with Zr-doping levels of 0–15 mol.% and Ce doping levels of 0–10 mol.% in 0.4 μm thick films. The critical current density (J_c) of Zr-doped samples at 77 K, 1 T applied in the orientation of H 6 c is found to increase with Zr content and shows a maximum at 7.5% Zr doping. The 7.5% Zr-doped sample exhibits a critical current density (J_c) of 0.95 MA/cm² at H 6 c which is more than 70% higher than the J_c of the undoped sample. The peak in J_c at H 6 c is 83% of that at H 6 a–b in the 7.5% Zr-doped sample which is more than twice as that in the undoped sample. Superconducting transition temperature (T_c) values as high as about 89 K have been achieved in samples even with 15% Zr and 10% Ce. Ce-doped samples with and without Ba compensation are found to exhibit substantially different J_c values as well as angular dependence characteristics.     

Intrinsic pinning properties of FeSe0.5Te0.5

The intrinsic pinning properties of FeSe_0.5Te_0.5, which is a superconductor with a critical temperature T_c of approximately 14 K, were studied through the analysis of magnetization curves obtained using an extended critical state model. For the magnetization measurements carried out with a superconducting quantum interference device (SQUID), external magnetic fields were applied parallel and perpendicular to the c-axis of the sample. The critical current density J_c under the perpendicular magnetic field of 1 T was estimated using the Kimishima model to be equal to approximately 1.6 × 10⁴, 8.8 × 10³, 4.1 × 10³, and 1.5 × 10³ A/cm² at 5, 7, 9, and 11 K, respectively. Furthermore, the temperature dependence of J_c was fitted to the exponential law of J_c(0) × exp(?αT/T_c) up to 9 K and the power law of J_c(0) × (1 ? T/T_c)ⁿ near T_c.     

Thermal diffusivity measurement of YBa2Cu3O7−x thin film with a picosecond thermoreflectance technique

The thermal diffusivity of YBa₂Cu₃O_7?x (YBCO) film was measured using the optical pump–probe method. A theoretical finite-difference model was employed to calculate the diffusivity value, and the best fit for the c-axis oriented YBCO film showed an average thermal diffusivity of 0.25 ± 0.05 mm² s^?1. The obtained result is compared to previous reports measured using various methods.     

Effects on Jc of pinning center morphology for multiple-in-line-damage in coated conductor and bulk,melt-textured HTS

The properties of discontinuous aligned pinning centers (PCs) created by high-energy heavy-ions are compared for bulk melt-textured and coated conductor HTS. Properties of PCs, which increase J_c (pinning potential and entanglement), and negative properties which decrease J_c (e.g., decreased T_c and percolation paths) are evaluated. Mechanisms are proposed to explain the very large increases in J_c resulting from multiple-in-line-damage (MILD) compared to continuous columnar pinning centers (CCPC). In particular, a mechanism which results in fluxoid entanglement, even for parallel (unsplayed) PCs, is discussed. The same mechanism is found to also account for restoration of much of the pinning potential expected to be lost due to the gaps in MILD PCs. It also accounts for the fact that at high fluence, J_c increases as fluence is increased, instead of decreasing as expected. The very low self-field in coated conductor permits separation of the negative and positive effects of PCs. It is found that parameters developed to quantify the negative effects in bulk melt-textured YBCO, by 63 GeV U²³⁸ ions, successfully describe damage to 2.1 μm thick coated conductor by 1 GeV Ru⁴⁴ ions. Coated conductor at 77 K and self-field is generally known to have J_c about 100 times that of melt-textured YBCO. However, at 77 K and applied field of 1 T, when both forms of HTS are processed with comparable numbers of near-optimum MILD PCs, the difference in J_c is reduced to a factor of 1.3–2. Whereas J_c for melt-textured YBCO increased sharply, by a factor of up to 16.8 for high-fluence MILD PCs, J_c in coated conductor increased by a smaller factor of 2.5–3.0. Nevertheless, 2.1 μm thick coated conductor, with near-optimum MILD PCs, exhibits J_c = 543 kA/cm² at 77 K and applied field of 1.0 T, and I_c = 114 A/cm-width of conductor. This is the highest value we find in the literature. The phenomenology developed indicates that for optimum MILD PCs in coated conductor, J_c ～ 700 ± 70 kA/cm² should be achievable at 77 K, 1.0 T.     

The epitaxial growth of BaSnO3 buffer layer on IBAD-MgO template and its effects on GdBa2Cu3O7−δ film: A preliminary study

We report a successful fabrication of c-axis oriented GdBa₂Cu₃O_7−δ (GdBCO) films on the BaSnO₃ (BSO) buffer layers on ion-beam assisted deposition (IBAD)-MgO template by pulsed-laser deposition (PLD). The (0 0 l) growth and in-plane textures of BSO buffer layers were found sensitive to the substrate temperature (T_s). With increasing the BSO layer thickness up to ∼165 nm, in-plane texture (Δ? ∼ 6.2°) of BSO layers was almost unaltered while completely c-axis oriented BSO layers were obtainable from samples with the thickness below ∼45 nm. On the BSO buffer layers showing in-plane texture of 6.2° and RMS surface roughness of ∼8.6 nm, GdBCO films were deposited at 780–800 °C. All GdBCO films exhibited Δ? values of 4.6–4.7°, T_c,zero of ∼91 K, and critical current density (J_c) over 1 MA/cm² at 77 K in a self-field. The highest J_c value of 1.82 MA/cm² (I_c of 51 A/cm-width) was achieved from the GdBCO film deposited at T_s of 790 °C. These results support that BSO can be a promising buffer layer on the IBAD-MgO template for obtaining high-J_c GdBCO coated conductors.     

Embedding of insulating nano-inclusions in Y-123 superconductor as pinning centers: The influence of size

The optimization of flux line pinning in superconductors is one of the most efficient ways to improve the transport properties of these materials. The generation of effective artificial pinning centers in a controlled way and with optimal dimensions can contribute to the enhancement of pinning capability and to the improvement of the critical current densities J_c. In this work, we examined the effectiveness of an insulating inclusion in a type II superconductor as a pinning center with a size close to the penetration depth λ instead of the coherence length ξ. To this effect, insulating nano-pinning centres (100–150 nm) have been successfully embedded into superconducting YBa₂Cu₃O_7?d (Y-123) matrix by slightly doping with nano-particle alumina dispersions. Two alumina nano-particle dispersions with mean size diameters of about 130 nm and 150 nm which are considerably larger than the coherence length ξ of Y-123 were used. A systematic study of the relationship of J_c(H,T) with different amounts of D₁ and D₂-nanoalumina additions was performed to determine the optimum nano-particle doping contents. The results indicate that slight inclusions of D₁ or D₂-nanoalumina can effectively enhance the flux pinning capability of samples. The best flux pinning was observed in the sample with 10^?2 wt.% D₁-alumina and 3 × 10^?2 wt.% D₂-alumina. The present work suggests that the use of sufficiently large insulating inclusions in the nanometer sub-scale can stabilize the flux-line lattice. It also shows that the optimal size for an insulating inclusion, acting as a pinning center in bulk material, is more likely related to λ than to ξ.     

Homoepitaxial growth of MOD-YBCO thick films on evaporated and MOD templates

We have prepared metal organic deposition (MOD)-YBCO thick films by repeating the coating-pyrolysis-crystallization procedure onto ～100-nm-thick evaporated and MOD templates. Surface morphology of the template was found to strongly affect the homoepitaxial growth of MOD-YBCO layers on the template; namely, the epitaxial growth of MOD-YBCO on the evaporated template was much easier than that on the MOD template. A 220-nm-thick epitaxial MOD-YBCO film was successfully prepared on the 100-nm-thick evaporated-YBCO template to obtain a 320-nm-thick YBCO film, which exhibited J_c = 2.44 MA/cm² and I_c = 78 A/cm. The I_c value has significantly increased from 37 A/cm for the evaporated-template.     

30 mm wide process of GdBCO PLD/clad-type textured metal substrates

Gd₁Ba₂Cu₃O_x (GdBCO) coated conductors using bi-axially textured clad-type substrates have been developed for high temperatures superconducting (HTS) power cables. In this project, large amount of coated conductors (CCs) are necessary for the several tests of basic properties of HTS power cables and the fabrication of a 15 m long 3-in-one HTS model cable. In order to ensure an adequate amount and properties of coated conductors, the stable manufacturing technology and the high production rate at each process are required.In this report, we have newly installed a high power laser of 300 W for the PLD system, resulting in improvement of the manufacturing stability and the deposition rate for GdBCO film. In addition, we have optimized target–substrate distance in PLD process, and the uniformity of I_c distribution across 30 mm wide tapes were remarkably improved. Furthermore, the surface morphology of buffer layers were enhanced by optimizing the deposition condition using electron beam (EB) evaporation method, and the maximum I_c value for a short sample has achieved 497 A/cm at 77 K in the self-field. Based on these progresses, we are currently developing the stable manufacturing process for long CCs with over 400 A/cm.     

Energy storage properties of antiferroelectric 0.92NaNbO3-0.08SrZrO3 film on (001)SrTiO3 substrate

The present study demonstrates the fabrication of an antiferroelectric 0.92NaNbO₃-0.08SrZrO₃ film deposited on a SrRuO₃ coated (001)SrTiO₃ single crystal substrate by pulsed laser deposition. In the 0.92NaNbO₃-0.08SrZrO₃ film, the domain with its c-axis aligned with the out-of-plane direction contributed to the stabilization of an antiferroelectric phase under the high electric field. The film had an energy storage density of 2.9 J cm⁻³ and storage efficiency of 67% at room temperature, which kept at 2.5 J cm⁻³ and 50% at high temperature of 150 °C.     

The effect of pinning centers in Zn-doped CuBa2Ca3Cu4O12−y high-temperature superconductors

CuBa₂Ca₃Cu₄O_12−y (Cu:1234) high-temperature superconductors (HTS) doped with up to 2% Zn were grown using the high-pressure synthesis technique. Magnetization loops of the samples were measured at various temperatures between 5 and 77.3 K and magnetic fields up to 14 T. Critical current densities J_c of the samples were estimated using the critical state model. The results show that Zn-induced pinning centers increase J_c of Cu:1234 several times, depending on field and temperature. From the experimentally determined field-temperature region in which a higher Zn concentration lead to a higher J_c, we suggest the existence of a cross-over from quite efficient, extended (in the c-axes direction) pinning centers to point-like (inefficient) pinning centers at a certain temperature, depending on field. This effect can be attributed to the fact that, unlike other HTS, in Cu:1234 there is a second critical temperature T_c2 of about 70–80 K (in zero field, and 50–60 K in 15 T), related to the over-doping of pyramidal basal plane (outer CuO₂ plane).     

Novel clays: Solid-state synthesis,characterization and cation exchange selectivity

Several novel swelling mica-type clays have been synthesized by solid-state processes. Synthetic clays of ideal compositions such as Na₂Si₆Al₂Mg₆O₂₀F₄ · xH₂O (Na-2-mica), Na₃Si₅Al₃Mg₆O₂₀F₄ · xH₂O (Na-3-mica) and Na₄Si₄Al₄Mg₆O₂₀F₄ · xH₂O (Na-4-mica) have been prepared and characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and ²⁷Al and ²⁹Si solid-state magic angle spinning nuclear magnetic resonance (MASNMR) spectroscopy. Powder XRD showed that all syntheses yielded water swollen micas with c-axis spacing of ∼1.2 nm except in the case of Na-2-mica which also showed a small peak of anhydrous mica phase with a c-axis spacing of 0.96 nm. Solid-state ²⁷Al MASNMR spectroscopy revealed that almost all the Al is present in the tetrahedral environment of the different micas. Solid-state ²⁹Si MASNMR spectroscopy revealed different Si (Al) nearest neighbor environments depending upon the composition of the various micas. Selective cation exchange studies were performed on the various micas using 0.5 N NaCl solution containing 12.9 ppm Sr²⁺ or 8.12 ppm of La³⁺. The results showed, for the first time, that Na-3-mica has a high selectivity for the trivalent cation tested. The previously reported high selectivity of these synthetic micas for the divalent cations has been confirmed. These selective cation exchange studies are of relevance in cation separations from drinking and waste waters.     

Flux pinning and superconducting properties of melt-textured NEG-123 superconductor with TiO2 addition

We studied the effect of TiO₂ doping on flux pinning and superconducting properties of a melt-grown (Nd_0.33Eu_0.33Gd_0.33) Ba₂Cu₃O_y + 35 mol% Gd₂BaCuO₅ (70 nm in size) composite (NEG-123) processed in Ar–1% O₂ atmosphere. As indicated by similar, sharp superconducting transitions, the small quantities of TiO₂ used in our experiments did not deteriorate superconducting properties of the NEG material. Transmission electron microscopy (TEM) analysis found 20–50 nm Ti-based particles in the NEG-123 matrix. However, we have not observed the clouds of <10 nm sized particles in the NEG-123 matrix, as in the case of recently reported NEG-123 composites doped by Mo and Nb nanoparticles. Nevertheless, quite a good J_c–B performance in the 0.1 mol% Ti-doped sample, namely 550 kA/cm² at the self-field and at the secondary peak field (4.5 T) was achieved at 65 K, while 320 kA/cm² was obtained at zero-field at 77 K, and 50 kA/cm² at 90.2 K. The pinning effectiveness decreased with increasing Ti content above 0.2 mol%. The analysis of the pinning force showed that higher concentration of Ti (>0.2 mol%) increased the amount of normal pins (δl pinning), indicated by the Fp(h) peak shift from h = 0.42–0.36. The maximum pinning effect in a broad field range could be achieved by optimizing Ti content and adding sub-micron Gd-211 particles.     

Flux pinning in columnar-structured and single crystalline MgB2 films

We have investigated the flux pinning effect of columnar grain boundary in columnar-structured and single crystalline MgB₂ films. The MgB₂ films with columnar structure showed much higher J_c than that of single crystalline thin film, and sample having smaller grain size had a higher J_c in high magnetic fields. At 5 K, the MgB₂ film with grain size of 460 nm showed an abnormal double-peak behavior in pining force density, F_p(B), caused by competition of different types of pinning sites, such as planar defects and point defects. Field dependences of F_p in columnar-structured films suggest that the columnar grain boundary is a strong pinning source in the MgB₂ film and it plays a crucial role in enhancing J_c over a wide range of magnetic fields and temperatures.