A model bismuth oxide intergranular thin film in a ZnO twist grain boundary.

The electronic properties of a model bismuth oxide intergranular film in ZnO were investigated using density functional plane wave calculations. It was found that oxygen excess plays a fundamental role in the appearance of electrical activity. The introduction by oxygen interstitials or zinc vacancies results in depletion of the charge in deep gap states introduced by the bismuth impurities. This makes the boundary less metallic and promotes the formation of acceptor states localized to the boundary core, resulting in Schottky barrier enhancement. The results indicate that the origin of electrical activity in thin intergranular bismuth oxide films is probably not distinct from that in decorated ZnO boundaries.