Sintering and Electrical Properties According to Sb/Bi Ratio(I) : ZnO-Bi2O3-Sb2O3-Mn3O4-Cr2O3 Varistor

Abstract

We aimed to examine the co-doping effects of 1/6 mol% <TEX>$Mn_3O_4$</TEX> and 1/4 mol% <TEX>$Cr_2O_3$</TEX> (Mn:Cr = 1:1) on the reaction, microstructure, and electrical properties, such as the bulk defects and grain boundary properties, of ZnO-<TEX>$Bi_2O_3-Sb_2O_3$</TEX> (ZBS; Sb/Bi = 0.5, 1.0, and 2.0) varistors. The sintering and electrical properties of Mn,Cr-doped ZBS, ZBS(MnCr) varistors were controlled using the Sb/Bi ratio. Pyrochlore (<TEX>$Zn_2Bi_3Sb_3O_{14}$</TEX>), <TEX>${\alpha}$</TEX>-spinel (<TEX>$Zn_7Sb_2O_{12}$</TEX>), and <TEX>${\delta}-Bi_2O_3$</TEX> (also <TEX>${\beta}-Bi_2O_3$</TEX> at Sb/Bi <TEX>${\leq}$</TEX> 1.0) were detected for all of the systems. Mn and Cr are involved in the development of each phase. Pyrochlore was decomposed and promoted densification at lower temperature on heating in Sb/Bi = 1.0 system by Mn rather than Cr doping. A more homogeneous microstructure was obtained in all systems affected by <TEX>${\alpha}$</TEX>-spinel. In ZBS(MnCr), the varistor characteristics were improved dramatically (non-linear coefficient, <TEX>${\alpha}$</TEX> = 40~78), and seemed to form <TEX>${V_o}^{\cdot}$</TEX>(0.33 eV) as a dominant defect. From impedance and modulus spectroscopy, the grain boundaries can be seen to have divided into two types, i.e. one is tentatively assigned to ZnO/<TEX>$Bi_2O_3$</TEX> (Mn,Cr)/ZnO (0.64~1.1 eV) and the other is assigned to the ZnO/ZnO (1.0~1.3 eV) homojunction.