Structural and electronic properties of c-BN (111) surface with hydrogen/fluorine functionalization and nitrogen-based small-molecule adsorption

Using first-principles density functional theory calculations, we systematically investigate the structural and electrical properties of pure, hydrogen (H) and fluorine (F) functionalized polar (111) cubic boron nitride (c-BN) surface. In the absence of surface functionalization, the reconstructed B-terminated surface is energetically preferable. The hydrogenation is favorable for stabilizing N- and B-terminated surfaces, while the fluorination leads to the stable unreconstructed B-terminated structure due to strong site preference of F atoms. The reconstructed c-BN surface has magnetic characteristic, and the spin density distributions are mainly localized around the interlayer weak B–B bonds. The unreconstructed structures are nonmagnetic. Meantime, the adsorption behavior of nitric oxide (NO) and ammonia (NH₃) molecules are investigated on the reconstructed c-BN surface. It is found that the adsorption of NO has a considerable effect on the energy levels near the Fermi level, while the energy levels of NH₃ are located at the deep energy level below the Fermi level. Our theoretical results are helpful for understanding experimental phenomenon in practical applications and designing novel c-BN based molecule sensors. (paper)