Extended abstract of a paper presented at Microscopy and Microanalysis 2009 in Richmond, Virginia, USA, July 26 – July 30, 2009

Microstructure evolution of YBa2Cu3O7−y (YBCO) films during the two heat-treatments in the advanced trifluoroacetates metalorganic deposition (TFA-MOD) process has been investigated by means of transmission electron microscopy. In the calcination process, precursor films including nanopores were formed through the shrinkage of the film after a remarkable increase of the thickness due to the thermal decomposition of metalorganic salts in the starting solution. During the crystallization process, the densification and shrinkage of the film occurred after agglomeration of nanopores and coarsening of unreacted phase particles such as Y2Cu2O5, CuO, and Ba–O–F in the precursor films. The YBCO films were then epitaxially grown with the remaining unreacted phase particles in the film, finally pores were generated again by a reaction of these unreacted particles to form YBCO accompanied by the volume reduction. It is important to control the densification of precursor films and coarsening of the unreacted phase particles in the crystallization process, to fabricate YBCO final films with fine crystallinity and high critical current values.

Extended abstract of a paper presented at Microscopy and Microanalysis 2006 in Chicago, Illinois, USA, July 30 – August 3, 2006

Interfacial structures of c-axis-oriented YBa2Cu3O7–y (Y123) and Nd1+xBa2–xCu3O7–y (Nd123) films were investigated by high-resolution transmission electron microscopy (HRTEM) in conjunction with geometrical lattice matching and molecular orbital calculations. These films were formed on MgO(001) substrates by liquid-phase epitaxy. Despite the similarity in lattice constants between Y123 and Nd123, the in-plane orientation relationship (OR) to the substrates is different: [100]film//[100]substrate(I) for Y123 and [110]film//[100]substrate(II) for Nd123. From the results of HRTEM observations and image simulations, it was found that the Y123 and Nd123 films are terminated by BaO and CuO-chain layers at the interfaces, respectively. For both the Y123/MgO and Nd123/MgO systems, the OR(I) is assessed to be the most favorable in point of geometrical matching and the OR(II) is the second among the rotational misorientations on the [001]film and [001]MgO. The molecular orbital calculations reveal that the interface with the OR(II) and the CuO-chain layer termination is preferable in terms of covalent bonding for both the systems. Consequently, we suggest that the preferential interfacial structures are delicately determined by a balance of the geometrical and chemical factors at the interfaces, resulting in making the lowest interfacial free energies.

NdBa2Cu3O7-x (NdBCO) superconducting films were successfully grown on MgO substrates by liquid-phase epitaxy (LPE) using YBa2Cu3O7-x (YBCO) seed films which have lower peritectic temperatures. Microstructural characterizations using optical and electron microscopes revealed that most of the seed grains decomposed at the high processing temperature and dissolved when they touched the solution. The NdBCO grains were formed first by the quasi-homoepitaxial growth of NdBCO units on the few surviving YBCO seed grains and then grew pendently to cover the large bare surface areas of the MgO substrates quickly by lateral overgrowth. A micrometer-thick melt layer was entrapped between the film and the substrate. Through the few links provided by the surviving seed grains, a stable film/substrate orientation relationship could still be maintained. A semiquantitative analysis was done for the lateral overgrowth process, and two different lateral overgrowth stages were observed with about 50 times difference in the lateral overgrowth rate. Then, a semiquantitative understanding for the entire YBCO-seeded NdBCO LPE growth process was finally reached.

Non-steady-state solidification of YBa2Cu3O6+δ (Y-123) superconducting oxides was observed by the isothermal undercooling experiment. A sudden decrease in crystal growth rate was found for all the Y-123 samples processed at the different temperatures and from the different Y2BaCuO5 (Y-211) contents in the initial composition. Quantitative analysis revealed that the Y-211 particles are pushed by the Y-123 crystal and accumulate in the liquid during solidification. It is also found that the particle volume fraction increased and reached a constant value of about 0.6, when the growth rate decreased abruptly, regardless of a variety of growth conditions. A simple solidification model is developed to interpret the experimental observation. This model shows that particle accumulation, as a result of the particle-pushing behavior, causes less connectivity of the liquid and thereby decreases the liquid diffusion flux, which is responsible for the non-steady-state solidification of Y-123.

Growth of YBa2Cu3Oy (YBCO) crystals both on the MgO and the YBCO substrates has been investigated in order to clarify the growth mechanism of the liquid phase epitaxy (LPE) process for the coated conductor. It was found that the slope angle of the growth grain varied with growing in the initial stage of the LPE growth. In the case of the MgO substrate, the slope angle increased with laterally growing the crystal. On the other hand, the slope angle decreased with growing the crystal in the case of the YBCO substrate. This phenomenon with the opposite tendency could be explained by considering the difference in the step-advancing rates between on the MgO and the YBCO surfaces. It was found that the deep and steep valley of the LPE grains due to the slow step-advancing rate on the MgO is the origin of the flux trapping inclusions. It is necessary that the seed films should cover the entire MgO surface without undesired orientation grains and impurity particles in order to obtain the high quality LPE layer.

The microstructures and the solidification behavior in unidirectionally solidified Y–Ba–Cu–O/Ag (YBCO/Ag) superconducting current leads were investigated. The solidification model of this system was discussed by the Y2Ba1Cu1O5–Ba3Cu5Ox–Ag quasiternary phase diagrams constructed by analysis of the solute compositions in the melt. The diffusion fields and the spacing between silver particles in the YBCO/Ag system were discussed. The relationship between the shapes of entrapped silver particulates, the miscibility gap in the phase diagram, and the wetting behavior at the growth interface in two-dimensional monotectic reactions were also discussed.

Microstructure control of SmBCO superconductor was carried out using the floating zone partial melting and solidification method under 0.01 atm oxygen partial pressure which is a preferable atmosphere to obtain a crystal with stoichiometric SmBCO. The growth rate, initial composition, and addition of small amount of platinum dependences on the microstructure formations of the (Sm211 + L) mixture during melting and the Sm123 or Sm123/211 during solidification were investigated. Furthermore, superconductive properties of the solidified Sm123/211 were measured by SQUID after appropriate oxygen annealing. Estimated critical current density of the single crystalline Sm123/211 was 3.6 × 104 A/cm at 77 K, 1 T.

Microstructure in melt-textured bulk RE1Ba2Cu3O6+d crystals (RE123; RE = Sm, Nd) was investigated, changing the initial composition from the tie-line composition of RE123–Sm2Ba1Cu1O5 (Sm211)/Nd4Ba2Cu2O10 (Nd422) to the Ba-enriched side. It was found that the Sm211/Nd422 particle size decreased in the liquid with increasing the Ba/Cu ratio of the initial composition, and this tendency was also found in the grown Sm123 crystals. Composition of the Sm123 grown crystal could be controlled by selecting the Ba-enriched initial composition to obtain an almost stoichiometric compound, which resulted in higher Tc values. Furthermore, the Jc values also increased under low magnetic fields due to the significant decrease of Sm211 particle size. Therefore, changing the initial composition toward the Ba-enriched side was found to be a new process to enhance both Jc and Tc values simultaneously.

Nd1+xBa2−xCu3O6+d (Nd123) single crystals have been successfully grown by the top-seeded solution-growth method. Compositions of Nd123 could be controlled by applying two different methods: control of the oxygen partial pressure of the atmosphere and control of the liquid composition in air. The critical temperatures of Nd123 obtained by these two methods were 96 K (oxygen control) and 95 K (liquid composition control), respectively. The relationship between the peak effect in the Jc-H curve and heat treatment was investigated. The peak effect was found not to be an intrinsic property of Nd123; consequently it could be controlled by heat treatment.

Microstructure control of the SmBCO superconductor was carried out using the floating zone partial melting and solidification method. It is generally recognized that finely and uniformly dispersed nonsuperconductive high temperature stable phase (Sm211) particles included in the superconductive Sm123 matrix act as effective pinning centers. Microstructure formation of the partial molten mixture (Sm211 particles and BaO–CuO liquid) by decomposition of the precursor Sm123 on melting and solidification of Sm123 from the mixture have to be controlled concurrently to fabricate the 123/211 composite fiber with the optimum microstructure. During unidirectional solidification, planar crystal growth which provides the single crystal growth of Sm123 becomes unstable with increased growth rate. During unidirectional melting, the mean diameter of aligned Sm211 particles behind the melting interface decreases with increased growth rate and with decreased temperature gradient at the melting interface. Initial composition of the precursor significantly affects the formation behavior of Sm211 particles. The contribution of process parameters to the microstructure formation is also briefly discussed.

A simple model is proposed to analyze the interface stability of the RE123 superconductor in accordance with the constitutional supercooling criterion. As the single crystal growth of the 123 phase is largely dependent on the growth interface stability, a quantitative analysis has been required. From the numerical analysis for the case of peritectically solidified Sm123, it was clarified that the constitutional supercooling must exist in the liquid when the 123 growth interface comes close to a 211 particle. It could also predict that larger 211 particle radius, smaller volume fraction of the 211 particles, larger growth rate, or smaller imposed temperature gradient cause easy occurrence of the constitutional supercooling. The growth rate and a 211 particle radius are determining parameters. Further consideration of the nucleation at the L/211 interface just ahead of the 123 growth front could describe the 123 growth morphological transition from with the planar interface to the equiaxed blocky.

This study investigates the influences of Y–Ba–Cu–O compounds solidification under different oxygen partial pressures by a zone melting method. In the Y–Ba–Cu–O system, P(O2) ranged from 0.02 to 1 atm, and the following reaction occurred during heating: YBa2Cu3O6−δ (Y123) → Y2BaCuO5 (Y211) + L. With an increase of oxygen partial pressure or decrease of pulling rate, the morphology of the solidified interface changed from mushy to equiaxed, cellular, and planar. The continuous Y123 grains were readily obtained under high oxygen partial pressure. Based on the constitutional supercooling theory and combining the result of the yttrium solubility limit for different oxygen partial pressures, the influences of oxygen partial pressure on Y123 morphological evolution were clarified.

Bulk single crystals of Y123 are required to clarify the superconductivity phenomena and develop electronic devices using unique superconductive properties. Only the Solute-Rich Liquid–Crystal Pulling (SRL-CP) method has succeeded in continuous growth of the Y123 single crystal. In this paper, we investigated the growth of Y123 single crystals under different temperature gradients in the solution in order to understand the growth mechanism of Y123. It was revealed that Y123 single crystals grow with a spiral growth mode, which is in good agreement with the BCF theory.

A peritectic solidification growth model considering both solute diffusion in the liquid and interface kinetics is developed for the growth of YBa2Cu3O61x (123) superconductive oxide. The effect of interface kinetics on the growth rate and the rate control process is discussed using this model. The growth rate of the 123 crystal is evaluated as a function of the undercooling using the proper kinetic equation. The evaluated results by this model show good agreement with the experimental results. As a result of this evaluation, the growth of the 123 crystal is predicted to be limited by a mixed control process in general.

To clarify the effect of undercooling on the crystal growth of Y-123, the growth rate was measured with different undercoolings. The growth rate of the {100} face shows a quadratic dependence of undercooling, while that of the {001} face shows a linear dependence in the sample with nominal 123 composition. In the case with 211-rich composition, the growth rate of each face was larger than that compared with nominal 123 composition since the mass flux from 211 particle for peritectic reaction becomes large. Addition of excess 211 alters the undercooling dependence of Ra from quadratic to linear. It is considered that the entrapment of 211 particles into 123 crystals supplies step sources beside screw dislocations. The growth rate of the {001} face is larger than that of the {100} face up to 26° of undercooling.

Zn-doped YBa2Cu3O6+δ (YBCO) single crystals were fabricated by the solute-rich liquid-crystal pulling (SRL-CP) method. The Zn content of x ranged from 0.0035–0.029 and almost uniformly distributed in YBa2(Cu1−xZnx)3O6+δ. There is a nearly linear relationship between the added Zn content in the liquid and the analyzed Zn content in the liquid/in the crystal. When the added Zn content Cl was 1.086 at. %, decreasing of growth temperature led to increasing growth rate. However, growth temperature had no obvious effect on the doped Zn content in the crystal Cs, the Zn content in the flux Cl, and the effective distribution ratio of k′. In addition, growth spirals on the grown crystal surface were observed by atomic force microscopy (AFM). X-ray Laue pattern and RBS measurements are indicative of good crystallinity of YBa2(Cu1−xZnx)3O6+δ. Critical temperatures of Tc changed from 89 to 57 K when the Zn content x ranged 0.0035 to 0.029 after appropriate oxygenation.

Y1Ba2Cu307−x (Y123) crystals were grown by two different methods, the constant undercooling solidification and the continual cooling method, with top seeding by Sm123 seed crystals in order to investigate a relationship between undercooling (ΔT) and a growth rate (R). The crystals of Y123 with a sharp faceted interface, which consisted of {100} and {001} faces, grew epitaxially from the seed. It was found that the growth rates of {100} face (Ra) and that of {001} face (Rc) showed an increasing trend with increasing ΔT, and Rc was faster than Ra within these experimental conditions, ΔT < 20 K. The relation between R and ΔT follows the parabolic equation, viz. Ra ∝ ΔT1.9 and Rc ∝ ΔT1.3 for {100} and {001} faces, respectively. The simulated crystal size using the R and ΔT relations obtained from the constant undercooling method showed good agreement with experimental data by the continual cooling.

Large YBa2Cu3O7−x (Y123) single crystals (larger than 13 mm cubed) have been grown along the c-axis reproducibly by the modified pulling method. The crystallinity of Y123 single crystal was investigated by x-ray diffraction and x-ray topography. Crystals grown from an MgO single crystal seed had some low angle subgrain boundaries which tilted 0.1–0.8° from each other. These grain boundaries originated from the seed crystal, and the subgrains were extended along the growth direction from the seed crystal. Y123 single crystals with no marked subgrains in the whole area were obtained by using Y123 single subgrain crystal seeds. FWHM of the x-ray rocking curve for the crystal so produced was about 0.14°, which was much better than the spectrum consisting of several separated peaks obtained from the previous crystals. Tc onset of the annealed sample was about 93.6 K, and the transition width was about 0.9 K. The low angle subgrain boundaries did not seem to be effective pinning centers for the magnetic flux.