Abstract
Hexagonal boron nitride is a large band-gap insulating material which complements the electronic and optical properties of graphene and the transition metal dichalcogenides. However, the intrinsic optical properties of monolayer boron nitride remain largely unex- plored. In particular, the theoretically expected crossover to a direct-gap in the limit of the single monolayer is presently not confirmed experimentally. Here, in contrast to the tech- nique of exfoliating few-layer 2D hexagonal boron nitride, we exploit the scalable approach of high-temperature molecular beam epitaxy to grow high-quality monolayer boron nitride on graphite substrates. We combine deep-ultraviolet photoluminescence and reflectance spectroscopy with atomic force microscopy to reveal the presence of a direct gap of energy 6.1eV in the single atomic layers, thus confirming a crossover to direct gap in the monolayer limit.