Electrical conductivity and defect chemistry of Ba x Sr 1 x Co y Fe 1 y O 3 d perovskites

Bulk BaxSr1 xCoyFe1 yO3 d compositions (BSCF) were synthesized by the solid-state reaction method. The electrical conductivity of ceramic bars was measured using a dc four-probe method as a function of temperature in air up to 970 °C. All compositions showed thermally activated p-type semi-conductivity up to ~450 °C and then a transition to metal-like conductivity. The smallpolaron hopping p-type semi-conductivity depends on the oxygen nonstoichiometry, which increases with increasing temperature. Metal-like conductivity is attributed to the overlap of the transition metal d-electron orbitals with the oxygen p-orbitals. Strontium-rich compositions show higher conductivity. The Co/Fe ratio does not influence much the p-type semi-conduction. Iron-rich compositions revealed more metal-like conduction behavior. The degree of overlap between transition metal d-orbitals and oxygen p-orbitals depends on the Ba/Sr as well as on the Co/Fe ratios.