Revisiting the effects of Co₂O₃ on multiscale defect structures and relevant electrical properties in ZnO varistors

Element doping is an effective method to improve the performance of ZnO varistors. Previous studies mainly focused on the variation of microstructures and Schottky barriers. In this study, the effects of Co dopant on electrical properties are investigated from the aspect of multiscale defect structures, including intrinsic point defects, the heterogeneous interface of depletion/intergranular layers, and interface states at grain boundaries. Combining with analysis of phase composition and energy dispersive spectroscopy, it is found that Co tends to dissolve into ZnO grains when slightly doped. It substitutes Zn²⁺ with the same valence and affects little on densities of donors. Segregation of Co at grain boundaries would result in the formation of spinel phase Co(Co_4/3Sb_2/3)O₄ and transformation of the intergranular phase from α-Bi₂O₃ to δ-Bi₂O₃. Meanwhile, densities of point defects are indirectly affected by oxygen ambient during sintering, resulting in abnormal variation of grain resistivity. And interface states are enhanced, leading to improved barriers at grain boundaries. Therefore, reduced leakage current, enhanced grain resistivity, and improved non-linear coefficient in Co-doped ZnO varistor blocks are understood from the underlying multiple defect structures. This presents a potential approach to explore short-term performance and long-term stability of ZnO varistors from the aspect of defect responses.