Local Energetic Analysis of the Interfacial and Surface Energies of Graphene from the Single Layer to Graphite

Recent advances in scanning probe methods that provide direct access to the surface free energy of inorganic layered materials in terms of the Hamaker constant, yield energetic values for monolayer graphene that differ substantially, by a factor of around 0.4, from bulk graphite. The onset of bulk deviating energy values was observed at a multilayer slab thickness of ~3 nm, corresponding to a layer number of 10. The findings, complemented with extractions from water contact angle measurements and calculated interlayer binding energies, find short-range ordinary Van der Waals interactions to be most prominently affected by dimensional constraints and many-body interactions.