In this study we aims to examine the co-doping effects of 1/3 mol% Mn3O4+Co3O4 (1:1) on the reaction, microstructure, and electrical properties such as the bulk defects and grain boundary properties of ZnO-Bi2O3-Sb2O3 (ZBS; Sb/Bi=0.5, 1.0, and 2.0) varistors. The sintering and electrical properties of Mn,Co-doped ZBS, ZBS(MCo) varistors were controlled by Sb/Bi ratio. Pyrochlore (Zn2Bi3Sb3O14) was decomposed and promoted densification at lower temperature on heating in Sb/Bi=1.0 by Mn rather than Co. Pyrochlore on cooling was reproduced in all systems however, spinel (α- or β-polymorph) did not formed in Sb/Bi=0.5. More homogeneous microstructure was obtained in Sb/Bi≥1.0. In ZBS(MCo), the varistor characteristics were improved drastically (non-linear coefficient, α=30∼49), and seemed to form (0.17 eV) and (0.33 eV) as dominant defects. From impedance and modulus spectroscopy (IS & MS), the grain boundaries have divided into two types, i.e. the one is tentatively assign to ZnO/Bi2O3(Mn,Co)/ZnO (0.47 eV) and the other ZnO/ZnO (0.80∼0.89 eV) homojunctions.

In this study, we investigated the effects of Mn dopant (0.1∼3.0 at% Mn3O4 sintered at 100 0℃ for 1 h in air) on the bulk trap (i.e. defect) and grain boundary properties of ZnO, ZM(0.1∼3.0) using admittance spectroscopy (AS), and impedance-modulus spectroscopy (IS & MS). As a result, three kinds of defect were found below the conduction band edge of ZnO as 0.09∼0.14 eV (attractive coulombic center), 0.22∼25 eV (Zn¨(i)), and 0.32∼0.33 eV (V`o). The oxygen vacancy increased with Mn doping. In ZM, an electrically single grain boundary as double Schottky barrier was formed with 0.82∼1.0 eV of activation energies by IS & MS. We also find out that the barriers of grain boundary of Mn-doped ZnO (α-factor=0.13) were more stabilized and homogenized with temperature compared to pure ZnO.

In this study, we have investigated the effects of Mn dopant on the bulk trap levels and grain boundary characteristics of Bi2O3-based ZnO (ZB) varistor using admittance spectroscopy and dielectric functions (such as Z*, Y*, M*, ε*, and tanδ). Admittance spectra and dielectric functions show two bulk traps of Zn(i) (0.20 eV) and Vo (0.29~0.33 eV) in ZnO-Bi2O3-Mn3O4 (ZBM). The barrier of grain boundaries in ZBM could be electrochemically single type. However, its thermal stability was slightly disturbed by ambient oxygen because the apparent activation energy of grain boundaries was changed from 0.79 eV at lower temperature to 1.08 eV at higher temperature. The grain boundary capacitance Cgb was decreased slightly with temperature as 1.3~1.8 nF but resistance Rgb decreased exponentially. The relaxation time distribution can result from the heterogeneity of the barriers constituting the varistor. It is revealed that Mn dopant in ZB reduced the heterogeneity of the barrier in grain boundaries and stabilized the barrier against the ambient temperature.