Physical origin and control of exciton spatial localization in high-κMOene monolayers under external perturbations

Two-dimensional (2D) materials hold great promise for the next-generation optoelectronics applications, many of which, including solar cell, rely on the efficient dissociation of exciton into free charge carriers. However, photoexcitation in atomically thin 2D semiconductors typically produces exciton with a binding energy of ∼500 meV, an order of magnitude larger than thermal energy at room temperature. This inefficient exciton dissociation can limit the efficiency of photovoltaics. In this study, employing the first principles approach-DFT, GW + BSE, and analytical model, we demonstrate the role of asymmetric halogenation, dielectric environment, and magnetic field in 2D Ti₂O MOene as an efficient strategy for regulating exciton binding energy (EBE) towards spontaneous exciton dissociation. Our study goes beyond the exciton ground state and quantifies the degree of spatial delocalization of exciton in excited states as well. We determine the quantitative impact of varying dielectric screening and magnetic field strength on EBE for different excited states (1 s, 2 s, 3 s, 4 s, and so on). Importantly, we reveal the significant role of orbital orientation (whether in-plane or out-of-plane) and symmetry (related to the angular momentum quantum number) in understanding the spatial localization of excitons and their binding energy. Additionally, a high dielectric constant in 2D MOene enables easier exciton dissociation, similar to that observed in 3D bulk semiconductors, while also harnessing the advantages of 2D materials. This makes it an effective material that combines the best of both 3D bulk and 2D structures. The study offers a promising strategy for designing next-generation optoelectronic devices.