Hexagonal boron nitride is an indirect bandgap semiconductor

TL;DR

This paper establishes that hexagonal boron nitride is an indirect bandgap semiconductor with a bandgap of 5.955 eV, providing key insights into its optical properties and exciton binding energy, relevant for deep ultraviolet applications.

Contribution

The study conclusively determines the indirect nature of the bandgap in hexagonal boron nitride using optical spectroscopy, resolving previous controversies.

Findings

Hexagonal boron nitride has an indirect bandgap of 5.955 eV.

Phonon-assisted optical transitions are observed.

Exciton binding energy is approximately 130 meV.

Abstract

Hexagonal boron nitride is a wide bandgap semiconductor with a very high thermal and chemical stability often used in devices operating under extreme conditions. The growth of high-purity crystals has recently revealed the potential of this material for deep ultraviolet emission, with an intense emission around 215 nm. In the last few years, hexagonal boron nitride has been raising even more attention with the emergence of two-dimensional atomic crystals and Van der Waals heterostructures, initiated with the discovery of graphene. Despite this growing interest and a seemingly simple structure, the basic questions of the bandgap nature and value are still controversial. Here, we resolve this long-debated issue by bringing the evidence for an indirect bandgap at 5.955 eV by means of optical spectroscopy. We demonstrate the existence of phonon-assisted optical transitions, and we measure an exciton binding energy of about 130 meV by two-photon spectroscopy.