Pressure‐Tuning Localized Excitons Toward Enhanced Emission, Photocurrent Enhancement and Piezochromism in Unconventional ACI‐Type 2D Hybrid Perovskites

Simultaneous enhancement of free excitons (FEs) emission and self‐trapped excitons (STEs) emission remains greatly challenging because of the radiative pathway competition. Here, a significant fluorescence improvement, associated with the radiative recombination of both FEs and STEs is firstly achieved in an unconventional ACI‐type hybrid perovskite, (ACA)(MA)PbI4 (ACA=acetamidinium) crystals with {PbI6} octahedron units, through hydrostatic pressure processing. Note that (ACA)(MA)PbI4 exhibits a 91.5‐fold emission enhancement and considerable piezochromism from green to red in a mild pressure interval of 1 atm to 2.5 GPa. The substantial distortion of both individual halide octahedron and the Pb‐I‐Pb angles between two halide octahedra under high pressure indeed determines the pressure‐tuning localized excitons behavior. Upon higher pressure, photocurrent enhancement is also observed, which is attributed to the promoted electronic connectivity in (ACA)(MA)PbI4. The anisotropic compaction reduces the distance between neighboring organic molecules and {PbI6} octahedra, leading to the enhancement of hydrogen bonding interactions. This work not only offers a deep understanding of the structure‐optical relationships of ACI‐type perovskites, but also presents insights into breaking the limits of luminescent efficiency by pressure‐suppressed nonradiative recombination.