Constructing Caesium-Based Lead-Free Perovskite Photodetector Enabling Self-Powered Operation with Extended Spectral Response

Since the discovery of the state-of-the-art hybrid halide perovskites, their application in optoelectronic systems has drawn considerable attention. However, the toxicity from lead (Pb) and the volatility induced by organic constituents hinder their future large-scale market development. Herein, a fully inorganic Pb-free halide perovskite based on robust Cs₃Bi₂I₉ is synthesized and realized its potential in photodetector application. The material property investigation suggests the good crystalline quality with strong absorption coefficient suitable for photodetection. An interesting feature based on the extended absorption is obtained, which is the characteristic of a weak phonon-assisted transition. Additionally, the morphological features display the beautifully grown micrometer-sized crystals of Cs₃Bi₂I₉. The fabricated photodetector demonstrated the self-powered operation (zero-bias state) with a very low dark current of 0.46 pA. Profiting from this, an improved photosensitivity of 1.4 × 10⁴ is achieved. Moreover, along with self-powered photodetection, the photodetector exhibits a broad spectral response (450–950 nm), high detectivity (1.2 × 10¹⁰/1.6 × 10¹² Jones), high responsivity (0.59 μA W–¹/3.8 mA W–¹), and fast response speed (ms) under a weak optical signal of 0.1 mW cm–² with a larger active area of 0.25 cm². The photodetector shows high photostability which was well retained for almost 2000 repetitive cycles without degradation. More strikingly, based on the core stability of the perovskite film, an excellent long-term stability of 3 months (90 days) is achieved for the photodetector even after exposure to moist air (75% relative humidity). This study thus highlights one of the few Pb-free all-inorganic perovskite photodetectors employing a simple device architecture with a larger active area that outshines by showing efficient and comparable performance under the self-powered mode under low light conditions.