Role of covalent and metallic intercalation on the electronic properties of epitaxial graphene on SiC(0001)

We present an orbital-resolved density functional theory study on the electronic properties of hydrogen and lithium intercalated graphene grown on the Si face of SiC. Starting from the $(6\sqrt{3}\times 6\sqrt{3})R{30}^{\circ }$ surface reconstruction of the graphene/SiC heterosystem, we find that both H and Li can restore the ideal structural characteristics of the two nonequivalent junction parts (i.e. graphene and the SiC substrate) when inserted at the interface. However, the chemical/electrostatic interactions remain different for the two cases. Hence, H-intercalated epitaxial graphene is subject to a sublattice symmetry-breaking electronic interference that perturbs the Dirac point, whereas Li intercalation gives rise to a highly $n$-doped system due to a nonuniform delocalization of Li charges. Results bring to discussion the role of substrate engineering in epitaxial graphene on SiC.