Thermal history dependence of superconducting properties in La 2CuO 4+δ

Abstract

We studied the thermal history dependence of the superconducting properties below/above room temperature (RT) in the ceramic La 2CuO 4+δ with excess oxygen. The phase separation (O-rich phase: superconducting and O-poor phase: antiferromagnetic) was concluded to occur above 373 K, in contrast with the usual report of the phase separation around 320 K. As for the superconducting phases, the well-known T c onset of 32 or 36 K, dependent on thermal history around 200 K, in the samples annealed in high-pressure oxygen gas, was not changed by thermal history between RT and 373 K. The samples electrochemically oxidized at RT included the phase with the high T c of 45 K, which was not changed by thermal history below RT, and the phase with the low T c of 32 or 36 K. The 45 K phase was changed into the low-T c phase by annealing at 373 K. The samples electrochemically oxidized at 333 K, which was accompanied with the diffusion of excess oxygen, showed gradual change of superconducting behavior: the single low-T c (32 or 36 K) phase (oxidation time = 24 h), coexistence of the low-T c phase and the high- T c (45 K) phase (36 h), and the single high T c phase (48 and 72 h). Thus, the single superconducting phase with the high T c of 45 K has been obtained, which showed a metallic behavior in normal resistivity and apparent changes of lattice constant in comparison with that of stoichiometric La 2CuO 4.