Electronic and Optical Properties of van der Waals Heterostructures Based on Two-Dimensional Perovskite (PEA)(2)PbI(4) and Black Phosphorus

[Image: see text] Combining two-dimensional (2D) perovskites with other 2D materials to form a van der Waals (vdW) heterostructure has emerged as an intriguing way of designing electronic and optoelectronic devices. The structural, electronic, and optical properties of the 2D (PEA)(2)PbI(4)/black phosphorus (BP) [PEA:(C(4)H(9)NH(3))(+)] vdW heterostructure have been investigated using first-principles calculations. We found that the (PEA)(2)PbI(4)/BP heterostructure shows a high stability at room temperature. It is demonstrated that the (PEA)(2)PbI(4)/BP heterostructure exhibits a type-I band arrangement with high carrier mobility. Moreover, the band gap and band offset of (PEA)(2)PbI(4)/BP can be effectively modulated by an external electric field, and a transition from semiconductor to metal is observed. The band edges of (PEA)(2)PbI(4) and BP in the (PEA)(2)PbI(4)/BP heterostructure, which show significant changes with the external electric field, provide further support. Furthermore, the BP layers can enhance the light absorption of the (PEA)(2)PbI(4)/BP heterostructures. Our results indicate that the 2D perovskite and BP vdW heterostructures are competitive candidates for the application of low-dimensional photovoltaic and optoelectronic devices.