Abstract

Abstract 2D Ruddlesden─Popper (RP) halide perovskites are attracting increasing research interest due to their enhanced stability compared to 3D perovskites. However, the quantum confinement effect of bulk organic spacers hinders the separation and transport of photo‐generated carriers. Here, a multiple aromatic ring spacer, 3‐benzothiophene methylammonium (BTMA), is developed for a new 2D RP perovskite. The BTMA spacer is demonstrated, with a significant dipole moment, can impair the influence of the quantum confinement effect, and the presence of S atoms or thiophene is favorable for enhancing the interaction between organic spacers and inorganic sheets, improving the stability of perovskites. The perovskite photodetector with BTMA as spacers displays higher device performance than the control sample with 1‐naphthalene methylammonium (NMA) as spacers. Importantly, the outstanding stability of BTMA‐based perovskite films and devices is also confirmed under moisture, heat, and illumination conditions. Combining the asymmetric coplanar nanogap electrode architecture, the photodetectors' enhanced responsivity, detectivity, and external quantum efficiency of 314 A W −1 , 3.4 × 10 13 Jones, and 865%, respectively, are demonstrated. Importantly, the nanogap photodetectors display promising self‐power characteristics, which makes them attractive for numerous energy‐efficient applications. The work highlights a new route toward developing high‐performance 2D RP perovskite‐based photodetectors with excellent long‐term stability.