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.Comment: To appear in Nature Photonic
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