Correlation between electrical properties and thermodynamic stability of ACoO3-δ perovskites (A= La, Pr, Nd, Sm, Gd)

For perovskites with the general formula ACoO3-δ (A = La, Pr, Nd, Sm, and Gd) the influence of the A-site cation on the electrical conductivity, electronic structure, thermodynamic stability, and oxygen stoichiometry was studied. The perovskite oxide powders were produced by a combined citric acid and ethylenediaminetetraacetic acid complexing method. Ceramic specimens sintered at 1100 deg. C in air were single-phase perovskites. With increasing temperature, the electrical conductivity shows three discrete regimes. All compositions show semiconductivity up to a transition temperature of ∼300 deg. C-450 deg. C and then behave like metallic conductors. The activation energies for the semiconductivity, as well as the transition temperatures to the metallic-like conduction, decrease monotonically with increasing pseudocubic lattice parameters, i.e., with increasing ionic radii of the A cation. This behavior correlates with decreasing oxygen nonstoichiometry and increased thermodynamic stability. The highest conductivity and the lowest activation energy of 0.66 eV were found for LaCoO3-δ, which also had the lowest semiconductor-metal transition temperature at 269 deg. C, the lowest oxygen nonstoichiometry of δ= 0.008, and the highest Gibbs free energy change for the decomposition reaction of 42.37 kJ/mol at 850 deg. C. GdCoO3-δ had the highest oxygen nonstoichiometry with δ0.032, a high activation energy of 1.19 eV for the semiconductivity with a high transition temperature at 452 deg. C, and the lowest Gibbs free energy change of 26.54 kJ/mol at 850 deg. C. X-ray absorption spectroscopy data imply an increasing Co low-spin character with decreasing cation radius from La to Gd, while an increase in temperature increases the number of holes or Co 3d bandwidth. This correlates well with the electrical conductivity data.