Impact of A-Site Cation Deficiency on Charge Transport in La0.5−xSr0.5FeO3−δ

Abstract

The electrical conductivity of La_0.5-<i>x</i>Sr_0.5FeO_3-<i>δ</i>, investigated as a function of the nominal cation deficiency in the A-sublattice, <i>x</i>, varying from 0 to 0.02, has demonstrated a nonlinear dependence. An increase in the <i>x</i> value from 0 to 0.01 resulted in a considerable increase in electrical conductivity, which was shown to be attributed mainly to an increase in the mobility of the charge carriers. A combined analysis of the defect equilibrium and the charge transport in La_0.5-<i>x</i>Sr_0.5FeO_3-<i>δ</i> revealed the increase in the mobility of oxygen ions, electrons, and holes by factors of ~1.5, 1.3, and 1.7, respectively. The observed effect is assumed to be conditioned by a variation in the oxide structure under the action of the cationic vacancy formation. It was found that the cation deficiency limit in La_0.5-<i>x</i>Sr_0.5FeO_3-<i>δ</i> did not exceed 0.01. A small overstep of this limit was shown to result in the formation of (Sr,La)Fe₁₂O₁₉ impurity, which even in undetectable amounts reduced the conductivity of the material. The presence of (Sr,La)Fe₁₂O₁₉ impurity was revealed by X-ray diffraction on the ceramic surface after heat treatment at 1300 °C. It is most likely that the formation of traces of the liquid phase under these conditions is responsible for the impurity migration to the ceramic surface. The introduction of a cation deficiency of 0.01 into the A-sublattice of La_0.5-<i>x</i>Sr_0.5FeO_3-<i>δ</i> can be recommended as an effective means to enhance both the oxygen ion and the electron conductivity and improve ceramic sinterability.