Origins of the p -type nature and cation deficiency in Cu 2 O and related materials

TLDR: In this article, a first-principle calculation of equilibrium nonstoichiometry and defect stability is proposed to explain why oxides are both $p$-type and naturally cation-deficient, whereas in other oxides (e.g., ZnO and MgO), they lead to localized, nonconductive states.

Abstract: While most of crystalline wide gap oxides are both stoichiometric and insulating, a handful of them including ZnO and ${\mathrm{In}}_{2}{\mathrm{O}}_{3}$ 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 ${\mathrm{Cu}}_{2}\mathrm{O}$. Based on first principles calculation of equilibrium nonstoichiometry and defect stability, we explain why the ${\mathrm{Cu}}^{(I)}({d}^{10})$ 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.