Modern varistors are made of polycrystalline ZnO, doped to create Schottky-like barriers at the grain boundaries. To allow the study of tailored single barrier junctions, we have implanted ZnO crystals with Bi, Sb and transition metals. The electrical properties and the distribution of Bi and Sb were measured in the implanted crystals as a function of annealing temperature. After implantation and before heating, no barriers can be observed. After heating to 600–800°C, a high voltage (insulating) barrier is created. Heating to above 1000°C produces a 2-1/2 Volt barrier with high nonlinearity. The temperatures at which these barriers appear correspond, respectively, to temperatures at which motion of Sb and Bi first can be observed by ion backscattering techniques, and at which these elements diffuse freely.