Origins of the p-type nature and cation deficiency in Cu2O and related materials

While most of crystalline wide gap oxides are both stoichiometric and insulating, a handful of them including ZnO and In2O3 are naturally anion-deficient and electron conductors. Even fewer of the oxides are naturally cation-deficient and hole conductors, the arch-type of which is Cu2O. Based on first principles calculation of equilibrium nonstoichiometry and defect stability, we explain why the Cu I d10 oxide-based materials are both p-type and naturally cation-deficient, and why cation vacancies lead to delocalized, conductive states, whereas in other oxides e.g., ZnO and MgO , they lead to localized, nonconductive states.