Self-Trapped Excitons in 3R ZnIn2S4 with Broken Inversion Symmetry for High-Performance Photodetection.

Abstract

Exploring novel materials with intrinsic self-trapped excitons (STEs) is crucial for advancing optoelectronic technologies. In this study, 2D 3R-phase ZnIn2S4, featuring broken inversion symmetry, is introduced to investigate intrinsic STEs. This material exhibits a broadband photoluminescence (PL) emission with a full width at half maximum of 164nm and a large Stokes shift of ≈0.6eV, which arises from the distortion of [ZnS4]6- tetrahedral unit induced by the symmetry breaking and strong electron-phonon coupling. The photophysical properties of the STEs exhibit a high Huang-Rhys factor (15.0), rapid STEs formation time (166fs), and extended STEs lifetime (1039ps), as demonstrated by experimental evidence from temperature-dependent PL, Raman spectroscopy, and ultrafast absorption spectroscopy. Additionally, STE-induced photoconductiveeffect is elucidated, indicating that intrinsic STEs in 3R-ZnIn2S4 can provide a synergistic effect that enhances absorption capacity, localization, and lifetime by capturing the self-trapped hole state. Consequently, the 2D 3R-ZnIn2S4 photodetector exhibits remarkable broad-spectrum photosensitivity, including a photo-switching ratio of 11286, response times of less than 0.6ms, responsivity of 15.2AW-1, detectivity of 1.02×10¹¹ Jones, and external quantum efficiency of 5032% under 375nm light. These findings provide new ideas for exploring materials with intrinsic STEs to achieve novel high-performance photodetector applications.