Design Strategy for Improving Detection Sensitivity in a Bromoplumbate Photochromic Semiconductor

Reducing the dark current of photodetectors is an important strategy for enhancing the detection sensitivity, but hampered by the manufacturing cost due to the need for controlling the complex material composition and processing intricate interface. This study reports a new single‐component photochromic semiconductor, [(HDMA)4(Pb3Br10)(PhSQ)2]n (1, HDMA = dimethylamine cation, PhSQ = 1‐(4‐sulfophenyl)−4,4’‐bipyridinium), by introducing a redox‐active monosubstituted viologen zwitterion into inorganic semiconducting skeleton. It features yellow to green coloration after UV irradiation with the sharply dropping intrinsic conductivity of 14.6‐fold, and the photodetection detection sensitivity gain successfully doubles. The reason of decreasing conductivity originates from the increasing the band gap of the inorganic semiconducting component and formation of Frenkel excitons with strong Coulomb interactions, thereby decreasing the concentration of thermally excited intrinsic carriers. This study reports a new photochromic semiconductor with conductivity dropping sharply by 14.6‐fold after photochromism, and succeeds in realizing photodetection detection sensitivity gain by photoinduced electron transfer strategy for the first time.