Atomic-resolution structural and spectroscopic characterization techniques (scanning transmission electron microscopy and electron energy loss spectroscopy) are combined with nanoscale electrical measurements (conductive atomic force microscopy) to study at the atomic scale the properties of graphene grown epitaxially through the controlled graphitisation of Si-face and C-face hexagonal SiC (0001) substrates by high temperature annealing. A scanning transmission electron microscopy analysis, carried out at 60KeV of beam energy, below the knock-on threshold for carbon to ensure no damage is imparted to the film by the electron beam, demonstrates that the buffer layer present on the planar SiC (0001) Si-face delaminates from it on the (11-2n) facets of SiC surface steps, In addition, electron energy loss spectroscopy reveals that the delaminated layer has a similar electronic configuration to purely sp2 …