We report on the charge spill-out and work function of epitaxial few-layer graphene on 6H-SiC(0001). Experiments from high-resolution, energy-filtered X-ray photoelectron emission microscopy (XPEEM) are combined with ab initio Density Functional Theory calculations using a relaxed interface model. Work function values obtained from theory and experiments are in qualitative agreement, reproducing the previously observed trend of increasing work function with each additional graphene plane. Electrons transfer at the SiC/graphene interface through a buffer layer causes an interface dipole moment which is at the origin of the graphene work function modulation. The total charge transfer is independent of the number of graphene layers, and is consistent with the constant binding energy of the SiC component of the C 1s core-level measured by XPEEM. Charge leakage into vacuum depends on the number of graphene layers explaining why the experimental, layer-dependent C 1s-graphene core-level binding energy shift does not rigidly follow that of the work function. Thus, a combination of charge transfer at the SiC/graphene interface and charge spill-out into vacuum resolves the apparent discrepancy between the experimental work function and C1s binding energy.
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