The effect of point defects and interactions with the substrate are shown by density functional theory calculations to be of significant importance for the structure and functional properties of hexagonal boron nitride (h-BN) films on highly ordered pyrolytic graphite (HOPG) and Ni(111) substrates. The structure, surface chemistry, and electronic properties are calculated for h-BN systems with selected intrinsic, oxygen, and carbon defects and with graphene hybrid structures. The electronic structure of a pristine monolayer of h-BN is dependent on the type of substrate, as h-BN is decoupled electronically from the HOPG surface and acts as bulk-like h-BN, whereas on a Ni(111) substrate, metallic-like behavior is predicted. These different film/substrate systems therefore show different reactivities and defect chemistries. The formation energies for substitutional defects are significantly lower than for intrinsic defects regardless of the substrate, and vacancies formed during film deposition are expected to be filled by either ambient oxygen or carbon from impurities. Significantly lower formation energies for intrinsic and oxygen and carbon substitutional defects were predicted for h-BN on Ni(111). In-plane h-BCN hybrid structures were predicted to be terminated by N-C bonding. Substitutional carbon on the boron site imposes n-type semiconductivity in h-BN, and the n-type character increases significantly for h-BN on HOPG. The h-BN film surface becomes electronically decoupled from the substrate when exceeding monolayer thickness, showing that the surface electronic properties and point defect chemistry for multilayer h-BN films should be comparable to those of a freestanding h-BN layer.
© 2023 The Authors. Published by American Chemical Society.