Correlation between charge transport and lattice dynamics in La- and Y-doped Ca2MnO4 perovskites

Abstract

Transition metal oxides exhibit fascinating physical phenomena and hold potential for next-generation electronic devices; therefore, fundamental understanding of their conduction mechanisms is of prime technological importance. We investigate charge transport kinetics and elastic behavior of bulk polycrystalline Ca2-xRxMnO4 oxides, where R = Y or La and 0.01 ≤ x ≤ 0.20. Analysis of temperature dependent electronic transport properties considering the nearest neighbor small polaron hopping model in combination with first-principles calculations of elastic properties indicates tight correlation between charge transport and lattice elasticity. We find that the polaron hopping energies of Y-doped compounds are lower than their La-doped counterparts, and attain minimum values of 60 and 73 meV, respectively. This is associated to softening of interatomic bonds, which is more pronounced for Y-doping compared to La-doping. This is corroborated by a fundamental model for elastically isotropic materials, indicating that the elastic energy induced by small polarons corresponds with the measured polaron hopping energies. Accordingly, the lattice shear and Young moduli, sound velocities and Debye temperatures calculated for Y-doped cells are smaller than for La-doped ones. The non-monotonous dependence of hopping energies on dopant concentration is explained in terms of polaron-polaron separation and mutual electrostatic interactions across the Mn+3-O-Mn+4 conduction path. Our study shows how charge carrier dynamics are strongly coupled with elastic properties, implying that the latter can be used to predict charge carrier mobility in oxide semiconductors.