Thermal Behaviour of PrCo_{1-x}Fe_xO₃ Probed by X-ray Synchrotron Powder Diffraction and Impedance Spectroscopy Measurements

Crystal structure and transport properties of the mixed praseodymium cobaltites-ferrites PrCo_{1-x}Fe_xO₃ have been studied in the temperature range of 298-1173 K by a combination of in situ X-ray synchrotron powder diffraction and temperature dependent impedance spectroscopy measurements. In situ high temperature powder diffraction examination of PrCo_{1-x}Fe_xO₃ series revealed considerable anomalies in the lattice expansion which are especially pronounced for the cobalt-rich specimens. These anomalies, which are reflected in a sigmoidal dependence of the unit cell dimensions and in the considerable increase of the thermal expansion coefficients, are obviously associated with transitions of Co^{3+} ions from low spin to the higher spin states and the coupled metal-insulator transitions, occurring in in rare earth cobaltites at the elevated temperatures. Indeed, the temperature-dependent impedance measurements clearly prove the change of conductivity type from dielectric to the metallic behaviour in the mixed cobaltite-ferrites PrCo_{1-x}Fe_xO₃ at the elevated temperatures.