Crystal structure, thermal expansion and electrical conductivity of Nd_0.7Sr_0.3Fe_1−xCo_xO₃ (0≤x≤0.8)

Abstract

The crystal structure, thermal expansion and electrical conductivity of the solid solution Nd_0.7Sr_0.3Fe_1−xCo_xO₃ for 0≤x≤0.8 were investigated. All compositions had the GdFeO₃-type orthorhombic perovskite structure. The lattice parameters were determined at room temperature by X-ray powder diffraction (XRPD). The pseudo-cubic lattice constant decreased continuously with x. The average linear thermal expansion coefficient (TEC) in the temperature range from 573 to 973 K was found to increase with x. The thermal expansion curves for all values of x displayed rapid increase in slope at high temperatures. The electrical conductivity increased with x for the entire temperature range of measurement. The calculated activation energy values indicate that electrical conduction takes place primarily by the small polaron hopping mechanism. The charge compensation for the divalent ion on the A-site is provided by the formation of Fe⁴⁺ ions on the B-site (in preference to Co⁴⁺ ions) and vacancies on the oxygen sublattice for low values of x. The large increase in the conductivity with x in the range from 0.6 to 0.8 is attributed to the substitution of Fe⁴⁺ ions by Co⁴⁺ ions. The Fe site has a lower small polaron site energy than Co and hence behaves like a carrier trap, thereby drastically reducing the conductivity. The non-linear behaviour in the dependence of log σT with reciprocal temperature can be attributed to the generation of additional charge carriers with increasing temperature by the charge disproportionation of Co³⁺ ions.