Manipulation of Band Alignment in Two-Dimensional Vertical WSe 2 /BA 2 PbI 4 Ruddlesden-Popper Perovskite Heterojunctions via Defect Engineering.

Transition metal dichalcogenides (TMDs), two-dimensional (2D) layered Ruddlesden-Popper perovskite material, and their heterojunctions have attracted a great deal of interest in optoelectronic applications. Although various approaches for modulating their properties and applications have been demonstrated, knowledge of the interface band alignment and defect engineering on the TMD/2D perovskite heterojunction is still lacking. Herein, the optoelectronic properties and defect engineering of the WSe 2 /BA 2 PbI 4 heterojunction have been investigated with density functional theory simulations. We find that the WSe 2 /BA 2 PbI 4 van der Waals heterojunction maintains an indirect bandgap and S-scheme alignment, facilitating the efficient splitting of light excited carriers across the interface. Importantly, we find that defect engineering could manipulate the band alignment. The introduction of the BA vacancies could switch the interface from the S-scheme to the typical type II interface, whereas Se vacancies would facilitate recombination at the S-scheme interface. Our work proves that the interfacial properties of heterojunctions can be regulated by defect modulation to address different optoelectronic applications.