Direct–Indirect Transition of Pressurized Two-Dimensional Halide Perovskite: Role of Benzene Ring Stack Ordering

Two-dimensional (2D) hybrid organic–inorganic metal halide perovskites (HOIPs) with considerably hydrophobic phenyl ethylammonium (PEA) organic cations have been used in highly efficient solar cells and LEDs, which are stable and enjoy a long lifetime, even when exposed to moisture. Different from other 2D HOIPs with alkyl amine cations, a benzene ring is present in the PEA cation. Until recently, an understanding of the effects of PEA on the structural, electronic, and optical properties of 2D HOIPs under pressure has remained limited. We find that there is a direct–indirect band gap transition at around 5.8 GPa and that the direct band gap recovers when the pressure is released. The stacking order of the benzene rings in the PEA cation plays a critical role in the mechanical and electronic properties. Our present work demonstrates that 2D HOIPs with organic cations containing benzene rings prove highly attractive for use in flexible optoelectronics.