Interfacial Interactions in Monolayer and Few‐Layer SnS/CH3NH3PbI3 Perovskite van der Waals Heterostructures and Their Effects on Electronic and Optical Properties

Abstract A high light‐absorption coefficient and long‐range hot‐carrier transport of hybrid organic–inorganic perovskites give huge potential to their composites in solar energy conversion and environmental protection. Understanding interfacial interactions and their effects are paramount for designing perovskite‐based heterostructures with desirable properties. Herein, we systematically investigated the interfacial interactions in monolayer and few‐layer SnS/CH3NH3PbI3 heterostructures and their effects on the electronic and optical properties of these structures by density functional theory. It was found that the interfacial interactions in SnS/CH3NH3PbI3 heterostructures were van der Waals (vdW) interactions, and they were found to be insensitive to the layer number of 2D SnS sheets. Interestingly, although their band gap decreased upon increasing the layer number of SnS, the near‐gap electronic states and optical absorption spectra of these heterostructures were found to be strikingly similar. This feature was determined to be critical for the design of 2D layered SnS‐based heterostructures. Strong absorption in the ultraviolet and visible‐light regions, type II staggered band alignment at the interface, and few‐layer SnS as an active co‐catalyst make 2D SnS/CH3NH3PbI3 heterostructures promising candidates for photocatalysis, photodetectors, and solar energy harvesting and conversion. These results provide first insight into the nature of interfacial interactions and are useful for designing hybrid organic–inorganic perovskite‐based devices with novel properties.