T. Puig

Growth, nanostructure and vortex pinning in superconducting YBa2Cu3O7 thin films based on trifluoroacetate solutions

Chemical solution deposition (CSD) is a very competitive technique to obtain epitaxial films and multilayers of high quality with controlled nanostructures. Based on the strong attractiveness from the cost point of view, the production of long length coated conductors based on the CSD approach is being extensively developed. The trifluoroacetate route (TFA) is the most widely used route to achieve epitaxial YBa2Cu3O7 (YBCO) layers with high critical currents, however a deep understanding of all the individual consecutive processing steps, as well as their mutual influence and relationship, is required to achieve superconducting materials with high performance. In this work, we review advances in the knowledge of all the steps relevant to the preparation of YBCO thin films based on TFA precursors as a CSD methodology: solution preparation and deposition, pyrolysis processes, intermediate phase evolution, nucleation and growth phenomena, microstructural evolution and its influence on percolating supercurrents, as well as vortex pinning by natural existing defects. Finally, we discuss the open issues still existing in the TFA approach, particularly that of film nanostructuration, and we provide a future outlook for this outstanding methodology.

The influence of growth conditions on the microstructure and critical currents of TFA-MOD YBa2Cu3O7 films

The influence of three processing parameters, temperature, gas flow rate and water pressure, on the YBa2Cu3O7 film growth on LaAlO3 single-crystal substrates from trifluoroacetate precursors has been investigated and the optimal film processing conditions to achieve high critical currents have been determined. We have found that the growth conditions maximizing the critical current density are those where the nucleation of a-axis oriented grains is minimized, as determined by μ-Raman spectroscopy. Under these conditions the normal state resistivity is very near to that of single crystals because a vanishingly small film porosity is achieved. Transmission electron microscopy analysis of films quenched from the growth temperature gives some hints for understanding the mechanism linking the film porosity with the concentration of a-axis grains. A cross-linked influence of different processing parameters, such as temperature and water pressure, or water pressure and gas flow, has been demonstrated. The optimal growth temperatures are 790–830 °C, but at these growth temperatures, the critical current density is still dependent on the gas flow rate and water pressure. The optimal processing ranges are a compromise between two different competing phenomena influencing the quality of the films: inhomogeneous film formation due to HF gas stagnancy at small nominal growth rates (low gas flow rate or water pressure) and perturbed crystallinity at high gas flow rates or water pressures.

AC susceptibility of grains and matrix for high-Tc superconductors

Abstract Several 123-YBCO superconducting samples cut from the same pellet have been studied by measuring AC susceptibility at 77 K as a function of the applied field amplitude Hm. Two contributions from inter- and intragranular supercurrents to the susceptibility are clearly observed with Hm up to 30 kA/m. The partial susceptibilities for the matrix, χm and χm, come from the intergranular supercurrents and show a systematic sample thickness dependence. Although Kims critical-state model explains the essential features of these susceptibilities and can be used to determine Jc as a function of local internal field Hi, the actual Jc(Hi) is more complex, with a concave segment at low fields. The partial susceptibilities for the grains, χg and χg, do not have sample thickness dependence, and the maximum χg is much lower than predicted by the critical-state model. This is shown to be related to the bee-waist shape of the hysteresis loop, which is due to the existence of a lower critical field. The lower critical fields of the grains (Hc1g) and the matrix (Hc1m), and the effective volume fraction of the grains (⨍g) are determined on the basis of the critical-state model. The lower limit for Hc1g is found to be around 4 kA/m, but Hc1m cannot be detected for Hm as low as 40 A/m. The results have been compared with some published weak-link models. A grain-cluster model is proposed for solving the problem of over high ⨍g.

Nanostructural control in solution-derived epitaxial Ce1?xGdxO2?y films

A novel mechanism based on aliovalent doping, allowing fine tuning of the nanostructure and surface topography of solution-derived ceria films, is reported. While under reducing atmospheric conditions, non-doped ceria films are inherently polycrystalline due to an interstitial amorphous Ce(2)C(3) phase that inhibits grain growth, a high quality epitaxial film can be achieved simply by doping with Gd(3+) cations. Gd(3+) [Formula: see text] Ce(4+) substitutions within the lattice are accompanied by charge-compensating oxygen vacancies throughout the volume of the crystallites acting as an efficient vehicle to reduce the barrier for grain boundary motion caused by interstitial Ce(2)C(3). In this way, the original nanostructure is self-purified by pushing the amorphous Ce(2)C(3) phase towards the free surface of the film. Once a full epitaxial cube-on-cube oriented ceria film is obtained, its surface morphology is dictated by the interplay between faceting on low energy {110} and/or {111} pyramidal planes and truncation of those pyramids by (001) ones. The development of the latter requires the suppression of their polar character which is thought to be achieved by charge compensation between the dopand and oxygen along [Formula: see text] directions.

Intermediate phase evolution in YBCO thin films grown by the TFA process

The YBCO thin film growth process from TFA precursors involves a complex reaction path which includes several oxide, fluoride and oxyfluoride intermediate phases, and the final microstructure and properties of the films are strongly influenced by the morphological and chemical evolution of these intermediate phases. In this work we present a study of the evolution of the intermediate phases involved in the TFA YBCO growth process under normal pressure conditions and we show that the oxygen partial pressure during pyrolysis of the TFA precursors is an important parameter. The Cu phase after the TFA pyrolysis can be either CuO, Cu2O or a mixture of both as the oxygen partial pressure is modified. The kinetics evolution of the intermediate phases has been determined for films pyrolysed in oxygen and nitrogen atmospheres and it is concluded that non-equilibrium phase transformations influence the reaction path towards epitaxial YBCO films and its microstructure. The intermediate phase evolution in these two series of films is summarized in kinetic phase diagrams.

Anisotropy and strength of vortex pinning centers in YBa2Cu3O7−x coated conductors

An experimental powerful methodology is proposed to evaluate and quantify the anisotropy and strength of the different pinning contributions of YBa2Cu3O7−x coated conductors by combining angular dependent in-field critical current measurements in the whole temperature range. A clear separation between isotropic and anisotropic pinning centers and a further classification into weak and strong pinning centers are performed. These analyses envision to establish a correlation between defect microstructure and critical currents which is essential for artificial engineering high-performance nanostructured coated conductors.

High quality YBa2Cu3O7 thin films grown by trifluoroacetates metalorganic deposition

Chemical solution growth of epitaxial YBa2Cu3O7 thin films on single crystalline substrates has been investigated using trifluoroacetate precursors. The concentration of the starting solution was selected to achieve a final film thickness of 250 nm. First, it is shown that high quality films can only be achieved if an homogeneous nanocrystalline film is obtained after the spin coating deposition and pyrolysis steps. Secondary phases such as BaCuO2, Y2BaCuO5 and CuO remain after the high temperature growth process, when macrosegregation is detected after these initial processing steps. A local degradation of texture associated with macrosegregation is detected by μ-Raman spectroscopy. The influence of growth temperature on the film quality has been analysed and the reaction times have been optimized at each temperature according to the reaction kinetics. In-situ fluoride analysis and μ-Raman spectroscopy have been used to determine the advancement of the formation reaction. The most apparent microstructural modification of these thin film samples with optimized annealing times has been found to be an enhanced porosity for low processing temperatures. The influence of porosity on the normal state resistivity and the critical currents has been evidenced. Optimized processing parameters lead to samples with very high critical currents (Jabc = 3.2 × 106 A cm−2 at 77 K and 2.7 × 107 A cm−2 at 5 K) which demonstrates the capability of the trifluoroacetate metalorganic deposition method for thin film and coated conductor preparation.

Critical current enhancement in YBCO–Ag melt-textured composites: influence of microcrack density

Abstract A strong increase of the critical current density of YBa 2 Cu 3 O 7 (YBCO) melt-textured composites has been observed by adding Ag 2 O particles in the precursor mixture while the concentration of Y 2 BaCuO 5 (Y211) precipitates remains constant. Critical current density enhancement factors as high as 200% at 5 K ( J c ab (5 K, 0 T)∼2.5×10 6 A/cm 2 ) and 1000% at 77 K and 2 T ( J c ab (77 K, 2 T)∼2.2×10 4 A/cm 2 ) have been reached in samples with 20 wt.% of Ag 2 O. Critical current measurements at 77 K for H ∥ ab also confirm the increase of the J c enhancement factor with the magnetic field (∼100% at 0 T and 140% at 2 T). The improvement of the critical currents in the YBCO–Ag melt-textured composites is correlated with the reduction of the density of microcracks parallel to the ab plane, as observed by scanning electron microscopy (SEM). Results are interpreted in terms of a release of the current limiting factors and an improvement of flux pinning properties by preexisting defects.

Simultaneous inductive determination of grain and intergrain critical current densities of YBa2Cu3O7−x coated conductors

An inductive methodology simultaneously enabling the determination of grain- and intergrain critical current densities of YBa2Cu3O7−x coated conductors is developed. This noninvasive method is based on the identification of a clear peak in the reverse branch of the magnetization loop at a positive magnetic field, as a signature of the electromagnetic granularity inherent to these materials. A quantitative evaluation of the return magnetic field at the grain boundaries allows us to understand the existence of this magnetization peak and quantify the grain critical current density. This methodology is envisaged to sort out granularity effects from vortex pinning effects on coated conductors.

Influence of porosity on the critical currents of trifluoroacetate-MOD YBa/sub 2/Cu/sub 3/O/sub 7/ films

The influence of porosity on the superconducting properties have been investigated on YBa/sub 2/Cu/sub 3/O/sub 7/ thin films deposited on LaAlO/sub 3/ [100] substrates by the so-called Trifluoroacetate (TFA) route. Micro-Raman spectroscopy have been used to determine the concentration of c-axis grains /spl delta/ in different samples and their influence on the final film porosity as observed from SEM imaging. This has been compared with measurements of resistivity and critical currents in the same samples. We prove that this /spl delta/ fraction is the main parameter controlling the porosity and hence the normal-state resistivity of the thin films. The optimization of the microstructure of these YBa/sub 2/Cu/sub 3/O/sub 7/ TFA films allow to have high critical currents : J/sub c/ = 3 /spl times/ 10/sup 6/ A/cm/sup 2/ at 77 K.