Spontaneous graphitization of ultrathin cubic structures: a computational study

Results based on ab initio density functional calculations indicate that cubic diamond, boron nitride, and many other cubic structures including rocksalt share a general graphitization tendency in ultrathin films terminated by close-packed (111) surfaces. Whereas such compounds often show an energy preference for cubic rather than layered atomic arrangements in the bulk, the surface energy of layered systems is commonly lower than that of their cubic counterparts. We determine the critical slab thickness for a range of systems, below which a spontaneous conversion from a cubic to a layered graphitic structure occurs, driven by surface energy reduction in surface-dominated structures.