Excitons in few-layer hexagonal boron nitride: Davydov splitting and surface localization

TL;DR

This paper theoretically investigates how the number of layers in hexagonal boron nitride influences excitonic properties, including Davydov splitting and surface localization, revealing layer-dependent optical and electronic behaviors.

Contribution

It introduces a combined ab initio and tight-binding approach to analyze excitonic states and surface localization effects in few-layer hBN, highlighting the impact of layer number on excitonic splitting.

Findings

Surface excitons are lower in energy than inner excitons for N > 2.

Layer number affects the absorption spectrum shape.

Distinct symmetry and selection rules for excitonic states depending on layer configuration.

Abstract

Hexagonal boron nitride (hBN) has been attracting great attention because of its strong excitonic effects. Taking into account few-layer systems, we investigate theoretically the effects of the number of layers on quasiparticle energies, absorption spectra, and excitonic states, placing particular focus on the Davydov splitting of the lowest bound excitons. We describe how the inter-layer interaction as well as the variation in electronic screening as a function of layer number $N$ affects the electronic and optical properties. Using both \textit{ab initio} simulations and a tight-binding model for an effective Hamiltonian describing the excitons, we characterize in detail the symmetry of the excitonic wavefunctions and the selection rules for their coupling to incoming light. We show that for $N > 2$, one can distinguish between surface excitons that are mostly localized on the outer layers and inner excitons, leading to an asymmetry in the energy separation between split excitonic states. In particular, the bound surface excitons lie lower in energy than their inner counterparts. Additionally, this enables us to show how the layer thickness affects the shape of the absorption spectrum.