Diffusion Mechanism of Cations and Anions in Cation-Exchange Process for Fabrication of High-Tc Superconducting HgBa2CaCu2O6+δ Films


We have investigated the diffusion mechanism of Hg and Tl cations in cation-exchange process that has been used successfully for fabrication of Hg-based high-Tc superconducting films. Scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) was employed to map the distribution of Tl and Hg cations in films quenched at different stages of the cation exchange process. SEM/EDS mappings showed that the nonuniform distribution of Hg is visible in micrometer size on the surface of samples quenched after short-time (~10min) Hg-annealing, but this nonuniformity disappears for longer-time (~45 min) Hg-annealing samples. This change could be ascribed to different stages in Hg diffusion — the former is the early stage when Hg is concentrated in the channels and the latter Hg-cations have already diffuse to grains. Our experimental results hence suggest that Hg-cations channel through defects in the films then diffuse into grains along a-b planes and vise versa for Tl-cations. The diffusion mechanism of anions (oxygen) in post annealing has also been discussed. Fluorine-doped Hg-1212 films were post annealed in flowing oxygen at 300 °C for several hours. Magnetic measurement has shown these samples are comprised pure overdoped Hg-1212 phase with smooth and sharp transition below 120 K, but resistivity vs. temperature measurement shows a kink at ~123 K. This implies that the optimally doped Hg-1212 phase with higher Tc might be surrounded by overdoped Hg-1212 phase and their contribution to magnetization is minimized, thus the possible diffusion mechanism for anions is also through grain boundaries at a much larger time scale compared to the cations.

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Xie, Y.Y., Wu, J.Z., Aytug, T. et al. Diffusion Mechanism of Cations and Anions in Cation-Exchange Process for Fabrication of High-Tc Superconducting HgBa2CaCu2O6+δ Films. MRS Online Proceedings Library 689, 44 (2001). https://doi.org/10.1557/PROC-689-E4.4

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