Defect energetics in ZnO: A hybrid Hartree-Fock density functional study

TLDR

Hybrid Hartree‑Fock density functional calculations reveal that in ZnO, oxygen vacancies and hydrogen impurities are the dominant donor‑like defects, whereas zinc interstitials and antisites are energetically less favorable. Under oxygen‑poor conditions, the study finds that oxygen vacancies and hydrogen impurities are strongly favored over zinc vacancies, implying they drive nonstoichiometry and donor behavior without significant compensation, in agreement with experimental data.

Abstract

First-principles calculations based on hybrid Hartree-Fock density functionals provide a clear picture of the defect energetics and electronic structure in ZnO. Among the donorlike defects, the oxygen vacancy and hydrogen impurity, which are deep and shallow donors, respectively, are likely to form with a substantial concentration in $n$-type ZnO. The zinc interstitial and zinc antisite, which are both shallow donors, are energetically much less favorable. A strong preference for the oxygen vacancy and hydrogen impurity over the acceptorlike zinc vacancy is found under oxygen-poor conditions, suggesting that the oxygen vacancy contributes to nonstoichiometry and that hydrogen acts as a donor, both of which are without significant compensation by the zinc vacancy. The present results show consistency with the relevant experimental observations.