Enhanced UV Light Responsivity in <110>‐Oriented 2D Perovskites Realized by Pressure‐induced Ultrafast Exciton Transport

Two‐dimensional (2D) <100>‐oriented perovskites exhibit superior optoelectronic properties, offering significant potential in photovoltaic, light‐emitting, and photodetection applications. Nevertheless, their enlarged interlayer spacing restricts longitudinal carrier transport, thereby limiting its potential applications. While <110>‐oriented 2D perovskites provide a prospective solution with their compact interlayer spacing, their inherent structure, characterized by octahedra tilting, indirectly hinders carrier transport due to the generation of self‐trapped excitons (STEs) caused by strong electron‐phonon coupling. Here, we adeptly regulate the photoluminescence (PL) from STEs to free excitons (FEs) emission within the 2D <110>‐oriented (API)PbBr4 single crystal through structure optimization under pressure treatment. Besides, we observed anisotropic FE transport with an anisotropy ratio of 4.97. The exciton mobility reaches a peak of 93.6 cm2 V‐1s‐1 at 2.7 GPa, a value comparable to those of their three‐dimensional (3D) counterparts, which is attributed to a reduction in electron‐phonon coupling and exciton reduced mass. Additionally, this ultrafast exciton transport significantly enhances UV light responsivity, exhibiting an increase of approximately 5000 times at 2.7 GPa in comparison to ambient conditions. These findings highlight the prospective application of 2D <110>‐oriented perovskites in high‐performance optoelectronic devices through intrinsic structural modulation.