Bias‐Switchable Dual‐Mode Organic Photodetector with High Operational Stability Using Self‐Trapped Cs3Cu2I5 Interfacial Layer

Abstract Conventional photovoltaic (PV)‐photodetectors are hard to detect fainted signals, while photomultiplication (PM)‐capable devices indispensable for detecting weak light and are prone to degrade under strong light illumination and large bias, and it is urgent to realize highly efficient integrated detecting system with both PM and PV operation modes. In this work, one lead‐free Cs 3 Cu 2 I 5 nanocrystals with self‐trapping exciton nature was introduced as interfacial layer adjacent to bulk and layer‐by‐layer heterojunction structure, and corresponding organic photodetectors with bias‐switchable dual modes are demonstrated. The fabricated device exhibits low operating bias (0 V for PV mode and 0.8 V for PM mode), high specific detectivity (~10 13 Jones), fast response speed as low as 1.59 μs, large bandwidth over 0.2 MHz and long‐term operational stability last for 4 months in ambient condition. This synergy strategy also validated in different materials and device architectures, providing a convenient and scalable production process to develop highly efficient bias‐switchable multi‐functional organic optoelectrical applications.