Excitonic ground states in phosphorene nanoflakes

Abstract

By using a configuration–interaction approach beyond the framework of independent multiexcitons, we predict that an excitonic ground state may exist in phosphorene nanoflakes when an in-plain electric field is applied. The ground state of the system is shown to undergo a transition from purely electronic to almost fully biexcitonic with the increasing strength of the electric field. As the field exceeds 0.25 V nm⁻¹, a biexcitonic ground state is revealed to be energetically more favorable by a few hundred meV than the system without excitons. A similar transformation of the ground state is also found as the screening effect varies from strong to weak. The enhanced electron–hole correlation, mostly caused by the applied electric field as well as the lack of strong screening in low-dimensional nanostructures, is believed to account for such an extraordinary transition. Furthermore, the system with a biexcitonic ground state is found to exhibit an absorption spectrum where many transitions are polarized along the zigzag direction, which breaks the optical anisotropy well-known for bulk phosphorene.