LAUSR

The layered semiconductor Bi2O2Se is a promising new‐type 2D material that holds layered structure via electrostatic forces instead of van der Waals (vdW) attractions. Aside from the huge success in device performance, the non‐vdW nature in Bi2O2Se with a built‐in interlayer electric field has also provided an appealing platform for investigating unique photoexcited carrier dynamics. Here, experimental evidence for the observation of excimers in multilayer Bi2O2Se nanosheets via transient absorption spectroscopy is presented. It is found that the excimer formation is the primary decay pathway of photoexcited excitons and three‐stage excimer dynamics with corresponding time scales are established. Excitation‐fluence‐dependent excimer dynamics further suggest that the excimer is diffusive and its formation can be simply described as excitons relaxed to an excimer geometry. This work indicates the outstanding promise of unique excitonic processes in Bi2O2Se, which may motivate novel device designs.