Intrinsic point defects and the n- and p-type dopability in α- and β-Bi₂O₃ photocatalysts

In this work, all kinds of intrinsic point defects, unintentional N and H impurities and possible complex defects between impurities and native defects in α- and β-Bi₂O₃ with different growth conditions are systematically investigated using hybrid density functional calculations. And then, the n- or p-type doping mechanisms in α- and β-Bi₂O₃ are explored and discussed. It is found that α-Bi₂O₃ presents the n-type conductivity under O-poor conditions. The unintentional H interstitials as the shallow donors should be majorly responsible for the n-type conductivity character. While under O-rich conditions, α-Bi₂O₃ displays the p-type conductivity, and the unintentional complex defects V_Bi1 + 2H as the shallow acceptors should be the primary origins of the p-type conductivity. The hydrogenation of the Bi vacancy in α-Bi₂O₃ not only significantly lowers the formation energy of the Bi vacancy but also markedly decreases its acceptor transition level. This well explains the experimental observation that α-Bi₂O₃ changes from n-type to p-type conductivity with increasing O partial pressure. Compared to α-Bi₂O₃, β-Bi₂O₃ always presents the n-type conductivity behaviour regardless of the growth conditions. The native O1 vacancies (V_O1) and unintentional H interstitials in β-Bi₂O₃ are shallow and excellent donors. They are responsible for the n-type conductivity and further perfectly explain the observed unintentional n-type conductivity character in β-Bi₂O₃ experiments. Understanding the defect physics in α- and β-Bi₂O₃ could inspire more significant studies on developing Bi₂O₃-based photocatalysts.