The Superconducting Bismuth-Based Mixed Oxides

The present paper describes the synthesis, characterization of mixedvalence bismuthates with 3- or 2-dimensional perovskite-like structures and structural criteria that influence superconductivity in these compounds. Single phase samples of Sr1−xKxBiO3 were prepared for the broad range of K-content: 0.25≤x≤0.65. For these bismuthates the symmetry of the structure changes from monoclinic to orthorhombic and finally to tetragonal upon increasing the K-content thus resulting in the decrease of the Bi-O distances and reduction of the network distortions. Superconductivity with maximum Tc=12K exists in the narrow range (x≈0.5–0.6) within the stability field of the tetragonal phase (0.33≤x≤0.65), when the 3-dimensional octahedral framework has close to the ideal perovskite structure arrangement. At the same time compositions with close to optimal Bi-valence (x=0.33 and 0.43) do not show any sign of superconductivity, probably, due to structural distortions. The layered type (Ba, K)3Bi2O7 and (Ba, K)2BiO4 bismuthates belonging to the An+1BnO3n+1 homologous series were investigated. Buckling of the (BiO2) layers in the structure of the n=2 member was revealed. The formation of the n=1 bismuthate was found by Electron Microscopy and X-ray powder diffraction studies. Both types of compounds are considered to be possible candidates for new superconducting materials among bismuthates.