Formation energy of oxygen vacancies in ZnO determined by investigating thermal behavior of Al and In impurities

Abstract

Thermal behavior and interacting nature of 100-ppm Al and ∼100-ppt In impurities doped in zinc oxide (ZnO) were investigated by means of the time-differential perturbed angular correlation method with the 111In(→111Cd) probe. Contrasting interactions between Al and In impurities were observed depending on different atmospheric conditions: (1) in air, Al and In impurities irreversibly associate with each other in the process of their thermal diffusion, but (2) in vacuum, their bound state formed in air dissociates by heat treatment at temperatures higher than 873 K, and this process is enhanced with increasing temperature. Detailed investigation of the thermal behavior of the impurities has revealed that the dissociation reaction is triggered by the formation of oxygen vacancies in the vicinity of the locally associated In-Al structure. A unique method to determine the activation energy of the oxygen-vacancy formation is presented with the estimated experimental value of Ea = 0.72(6) eV.