Cation Size and Disorder Effects in Conducting Perovskite Oxides

Abstract

AbstractThe electronic and magnetic properties of ATO3 and related perovskites (A is a mixture of lanthanide Ln3+ and alkaline earth M2+ cations; T is a transition metal) are very sensitive to the A site composition. The importance of doping effects controlled by the Ln3+/M2+ ratio is well-known, but the other lattice effects controlled by the sizes of these cations are less well understood. A simple approach making use of the mean (first moment) and the variance (second moment) in the A cation distribution has been applied to the metal-insulator transition temperature in colossal magnetoresistance AMnO3 perovskites and to the critical temperature in A2CuO4 and LnBa2Cu3O7-δ superconductors. Series of compositions prepared with a constant doping level and mean A cation radius show a linear decrease of the transition temperature Tt with the A cation size variance σ2. The rate of decrease -dTt/dσ2 is found to lie in the range 1,000-30,000 KÅ-2. The orthorhombic-tetra onal structural transition in the A2CuO4 materials is found to show a linear increase with σ2. A pair of quadratic relationships for the mean size and size variance effects are proposed to be the result of changing strain energies that give rise to these effects.