Oxygen vacancy $\left(V_{\mathrm{O}}\right)$ is a common native point defect that plays crucial roles in determining the physical and chemical properties of metal oxides such as ZnO. However, fundamental understanding of $V_{\mathrm{O}}$ is still very sparse. Specifically, whether $V_{\mathrm{O}}$ is mainly responsible for the $n$-type conductivity in ZnO has been still unsettled in the past 50 years. Here, we report on a study of oxygen self-diffusion by conceiving and growing oxygen-isotope ZnO heterostructures with delicately controlled chemical potential and Fermi level. The diffusion process is found to be predominantly mediated by $V_{\mathrm{O}}$. We further demonstrate that, in contrast to the general belief of their neutral attribute, the oxygen vacancies in ZnO are actually $+2$ charged and thus responsible for the unintentional $n$-type conductivity as well as the nonstoichiometry of ZnO. The methodology can be extended to study oxygen-related point defects and their energetics in other technologically important oxide materials.

Nitrogen doping is a promising method of engineering the electronic structure of a metal oxide to modify its optical and electrical properties; however, the doping effect strongly depends on the types of defects introduced. Herein, we report a comparative study of nitrogen-doping-induced defects in Cu2O. Even in the lightly doped samples, a considerable number of nitrogen interstitials (Ni) formed, accompanied by nitrogen substitutions (NO) and oxygen vacancies (VO). In the course of high-temperature annealing, these Ni atoms interacted with VO, resulting in an increase in NO and decreases in Ni and VO. The properties of the annealed sample were significantly modified as a result. Our results suggest that Ni is a significant defect type in nitrogen-doped Cu2O.