Understanding the presence of vacancy clusters in ZnO from a kinetic perspective

Abstract

Vacancy clusters have been observed in ZnO by positron-annihilation spectroscopy (PAS), but detailed mechanisms are unclear. This is because the clustering happens in non-equilibrium conditions, for which theoretical method has not been well established. Combining first-principles calculation and kinetic Monte Carlo simulation, we determine the roles of non-equilibrium kinetics on the vacancies clustering. We find that clustering starts with the formation of Zn and O vacancy pairs (VZn - Vo)f which further grow by attracting additional mono-vacancies. At this stage, vacancy diffusivity becomes crucial: due to the larger diffusivity of Vzn compared to Vf), more VZn-abundant clusters are formed than VQ-abundant clusters. The large dissociation energy barriers, e.g., over 2.5 eV for (Vzn - Vo), suggest that, once formed, it is difficult for the clusters to dissociate. By promoting mono-vacancy diffusion, thermal annealing will increase the size of the clusters. As the PAS is insensitive to VQ donor defects, our results suggest an interpretation of the experimental data that could not have been made without the in-depth calculations.