Atomic-Scale Model and Electronic Structure of Cu₂O/CH₃NH₃PbI₃ Interfaces in Perovskite Solar Cells

Cuprous oxide has been conceived as a potential alternative to traditional organic hole-transport layers in hybrid halide perovskite-based solar cells. Device simulations predict record efficiencies using this semiconductor, but experimental results do not yet show this trend. More detailed knowledge about the Cu₂O/perovskite interface is mandatory to improve the photoconversion efficiency. Using density functional theory calculations, here, we study the interfaces of CH₃NH₃PbI₃ with Cu₂O to assess their influence on device performance. Several atomistic models of these interfaces are provided for the first time, considering different compositions of the interface atomic planes. The interface electronic properties are discussed on the basis of the optimal theoretical situation, but in connection with the experimental realizations and device simulations. It is shown that the formation of vacancies in the Cu₂O terminating planes is essential to eliminate dangling bonds and trap states. The four interface models that fulfill this condition present a band alignment favorable for photovoltaic conversion. Energy of adhesion and charge transfer across the interfaces are also studied. The termination of CH₃NH₃PbI₃ in PbI₂ atomic planes seems optimal to maximize the photoconversion efficiency.