Gate-Tunable Bound Exciton Manifolds in Monolayer MoSe₂

Two-dimensional (2D) semiconductors with point defects are predicted to host a variety of bound exciton complexes analogous to trions and biexcitons due to strong many-body effects. However, despite the common observation of defect-mediated subgap emission, the existence of such complexes remains elusive. Here, we report the observation of bound exciton (BX) complex manifolds in monolayer MoSe₂ with intentionally created monoselenium vacancies (V_Se) using proton beam irradiation. The emission intensity of different BX peaks is found to exhibit contrasting dependence on electrostatic doping near the onset of free electron injection. The observed trend is consistent with the model in which free excitons exist in equilibrium with excitons bound to neutral and charged V_Se defects, which act as deep acceptors. These complexes are more strongly bound than trions and biexcitons, surviving up to around 180 K, and exhibit moderate valley polarization memory, indicating partial free exciton character.