Non-monotonically changes in double Schottky barrier of MnCO₃–doped ZnO varistors during DC aging

Abstract ZnO varistors play a crucial role as core component in metal oxide arresters due to their excellent nonlinear current density-electrical field ( J–E ) characteristics. After long-term operation under DC stress (DC aging), the J–E curves of ZnO varistors invented in the last decade cross with the original curve. Unexpectedly, the ‘crossover’ phenomenon cannot be explained by the vastly-accepted ion migration mechanism by which the barrier height monotonically declines after DC aging. In the present study, aging and recovery experiments were carried out on MnCO 3 -doped ZnO varistors. The symmetry of J–E characteristics in the same direction as and the opposite direction to the DC stress was compared, parameters of double Schottky barrier were analyzed, and evolution of point defects was deduced using dielectric spectra. It was found that, in addition to ion migrations, there are electrons ionized by zinc interstitials filling the interface states in the early stage of aging. Because these processes are dominant in different stages, the barrier height changes non-monotonically. MnCO 3 can suppress the formation of zinc interstitials, so it simultaneously inhibits ion migrations and filling of the interface states by electrons. When 0.38 mol% MnCO 3 is doped, J–E characteristics and the Schottky barrier of ZnO varistors show the smallest deviations during aging and recovery. The findings are helpful in updating criteria for the long-term stability of ZnO varistors and suggest that modifications to their formulae targeting the suppression of the filling the interface states by electrons are also expected to bolster the stability.