A-site Ca2+ substitution induced polyvalent Cu cations and correlated polaron relaxations in colossal permittivity Li1-xCaxCuNb3O9

Abstract

LiCuNb3O9 has been reported newly a colossal permittivity (CP) perovskite, in which the B-site NbO6 octahedra play a bridging role in the polaron hopping. However, how the A-site modification affects the origin of the polarons and further the CP behaviours remains unexplored. To this end, A-site Ca2+ was incorporated to form Li1-xCaxCuNb3O9, and the local states, dielectric relaxations and conduction behaviours were comprehensively studied. The substitution induces the polyvalent Cu cations, i.e. Cu+/Cu2+/Cu3+. Bond valence sum calculations imply that Cu2+ and Cu3+ are underbonded, and Cu+ is overbonded, while B-site Nb5+ shows slightly different with theoretical pentavalence. All the compositions exhibit a similarly room-temperature CP response, but present two dielectric relaxations, i.e. TR1:170–300 K and TR2:260–400 K. Comprehensive investigations on universal dielectric response and bulk dc conductivity indicate that the TR1 follows the variable-range-hopping where the electron hopping between the mixed Cu+/Cu2+, while TR2 contributes from the Cu3+ nearest neighbor hopping.