Low Breakdown Voltage Varistors by Grain Boundary Diffusion of Molten Bi2O3 in ZnO

Diffusion of molten Bi2O3 into the grain boundaries of sintered, alumina‐doped (0.23 and 0.7 mol%) ZnO pellets resulted in varistors with breakdown voltages in the 3–5 V range and nonlinearity coefficients of 10–24. The varistors were fabricated by spreading a thin layer of Bi2O3 powder on the surface of ZnO pellets and heating the combination to various temperatures (860–1155°C) and different times. The highest nonlinearity coefficients (20–24) and lowest breakdown voltages (3–5 V) were recorded in samples annealed at 860°C for 35 min. Longer annealing times and/or higher temperatures resulted in progressively higher breakdown voltages. Eventually the devices became insulating, which was attributed to the formation of an insulating Bi2O3 layer between the grains. Separate wetting experiments have shown that the penetration of Bi2O3 into ZnO grain boundaries was a strong function of alumina doping —the penetration rate was decreased by a factor of 5–7 as the ZnO was doped with as little as 0.2 mol% alumina. It is this slowing down of the penetration of the ZnO grain boundaries that is believed to be critical in the development of the low breakdown voltages observed.