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

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 Li_1-xCa_xCuNb₃O₉, 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. T_R1:170–300 K and T_R2:260–400 K. Comprehensive investigations on universal dielectric response and bulk dc conductivity indicate that the T_R1 follows the variable-range-hopping where the electron hopping between the mixed Cu⁺/Cu²⁺, while T_R2 contributes from the Cu³⁺ nearest neighbor hopping.