Direct and indirect excitons in boron nitride polymorphs: a story of atomic configuration and electronic correlation

Abstract

We compute and discuss the electronic band structure and excitonic dispersion of hexagonal boron nitride (hBN) in the single layer configuration and in three bulk polymorphs (usual AA' stacking, Bernal AB, and rhombohedral ABC). We focus on the changes in the electronic band structure and the exciton dispersion induced by the atomic configuration and the electron-hole interaction. Calculations are carried out on the level of \textit{ab initio} many-body perturbation theory (GW and Bethe Salpeter equation) and by means of an appropriate tight-binding model. We confirm the change from direct to indirect electronic gap when going from single layer to bulk systems and we give a detailed account of its origin by comparing the effect of different stacking sequences. We emphasize that the inclusion of the electron-hole interaction is crucial for the correct description of the momentum-dependent dispersion of the excitations. It flattens the exciton dispersion with respect to the one obtained from the dispersion of excitations in the independent-particle picture. In the AB stacking this effect is particularly important as the lowest-lying exciton is predicted to be direct despite the indirect electronic band gap.