We have examined the co-doping effects of 1/2mol% NiO and 1/4mol% Cr2O3 (Ni:Cr=1:1) on the reaction,microstructure, and electrical properties, such as the bulk defects and the grain boundary properties, of ZnO-Bi2O3-Sb2O3 (ZBS;Sb/Bi=0.5, 1.0, and 2.0) varistors. The sintering and electrical properties of Ni,Cr-doped ZBS, ZBS(NiCr) varistors werecontrolled using the Sb/Bi ratio. Pyrochlore (Zn2Bi3Sb3O14), α-spinel (Zn7Sb2O12), and δ-Bi2O3 were detected for all ofcompositions. For the sample with Sb/Bi=1.0, the Pyrochlore was decomposed and promoted densification at lowertemperature by Ni rather than by Cr. A homogeneous microstructure was obtained for all of the samples affected by α-spinel.The varistor characteristics were not dramatically improved (non-linear coefficient, α=5~24), and seemed to formZni..(0.17eV) and Vo.(0.33eV) as dominant defects. From impedance and modulus spectroscopy, the grain boundaries werefound to have been divided into two types, i.e., one is tentatively assigned to ZnO/Bi2O3 (Ni,Cr)/ZnO (0.98eV) and the otheris assigned to a ZnO/ZnO (~1.5eV) homojunction.

In this study we aimed to examine the co-doping effects of 1/6mol% Co3O4 and 1/4mol% Cr2O3 (Co:Cr=1:1)on the reaction, microstructure, and electrical properties, such as the bulk defects and the grain boundary properties, of ZnO-Bi2O3-Sb2O3 (ZBS; Sb/Bi=0.5, 1.0, and 2.0) varistors. The sintering and electrical properties of Co,Cr-doped ZBS, ZBS(CoCr)varistors were controlled using the Sb/Bi ratio. Pyrochlore (Zn2Bi3Sb3O14), α-spinel (Zn7Sb2O12), and δ-Bi2O3 were formed inall systems. Pyrochlore was decomposed and promoted densification at lower temperature on heating in Sb/Bi=1.0 by Cr ratherthan Co. A more homogeneous microstructure was obtained in all systems affected by α-spinel. In ZBS(CoCr), the varistorcharacteristics were improved (non-linear coefficient, α=20~63), and seemed to form Zni..(0.20eV) and Vo.(0.33eV) asdominant defects. From impedance and modulus spectroscopy, the grain boundaries were found to be composed of anelectrically single barrier (0.94~1.1eV) that is, however, somewhat sensitive to ambient oxygen with temperature. The phasedevelopment, densification, and microstructure were controlled by Cr rather than by Co but the electrical and grain boundaryproperties were controlled by Co rather than by Cr.

We aimed to examine the co-doping effects of 1/6mol% Mn3O4 and 1/4mol% Cr2O3 (Mn:Cr=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,Cr-doped ZBS, ZBS(MnCr) varistors werecontrolled using the Sb/Bi ratio. Pyrochlore (Zn2Bi3Sb3O14), α-spinel (Zn7Sb2O12), and δ-Bi2O3 (also β-Bi2O3 at Sb/Bi≤1.0)were detected for all of the systems. Mn and Cr are involved in the development of each phase. Pyrochlore was decomposedand promoted densification at lower temperature on heating in Sb/Bi=1.0 system by Mn rather than Cr doping. A morehomogeneous microstructure was obtained in all systems affected by α-spinel. In ZBS(MnCr), the varistor characteristics wereimproved dramatically (non-linear coefficient, α=40~78), and seemed to form Vo.(0.33eV) as a dominant defect. Fromimpedance and modulus spectroscopy, the grain boundaries can be seen to have divided into two types, i.e. one is tentativelyassigned to ZnO/Bi2O3 (Mn,Cr)/ZnO (0.64~1.1eV) and the other is assigned to the ZnO/ZnO (1.0~1.3eV) homojunction.