Variable-range-hopping conduction and polaron dielectric relaxation in Cu and Nb co-doped BaTiO3

Abstract

BaTi0.7(Cu0.1Nb0.2)O3 ceramic was prepared using a solid-state method and its structure, valence states, conduction mechanism and dielectric properties were investigated in detail. A fine-grained microstructure and a distorted pseudo-cubic perovskite structure were confirmed by scanning electron microscopy, X-ray diffraction analysis and Raman spectroscopy. X-ray photoelectron spectroscopy analysis suggested that Cu in BaTi0.7(Cu0.1Nb0.2)O3 was polyvalent but the valence states of Ti and Nb were invariable. Mott's variable-range-hopping (VRH) conduction was observed. The two colossal dielectric constant plateaus in low- and high-temperature ranges were ascribed to the electrode and grain boundary responses, respectively. The VRH model described the low-temperature relaxation well, indicating that the dielectric relaxation was a polaron relaxation rather than Maxwell–Wagner type. Both grain and grain boundary resistances were well fitted by the VRH model, suggesting that the VRH mechanism was tenable in both grain and grain boundaries. The electron paramagnetic resonance signal was ascribed to Cu ions, and the linewidth showed a linear relationship with T−1/4, corresponding to the charge transfer between different valence via Cu+-O-Cu2+ and Cu2+-O-Cu3+ paths. The hopping of carriers was also responsible for the conduction and polaron dielectric relaxations.