Efficient n-type doping in epitaxial graphene through strong lateral orbital hybridization of Ti adsorbate

In recent years, various doping methods for epitaxial graphene have been demonstrated through atom substitution and adsorption. Here we observe by angle-resolved photoemission spectroscopy (ARPES) a coupling-induced Dirac cone renormalization when depositing small amounts of Ti onto epitaxial graphene on SiC. We obtain a remarkably high doping efficiency and a readily tunable carrier velocity simply by changing the amount of deposited Ti. First-principles theoretical calculations show that a strong lateral (non-vertical) orbital coupling leads to an efficient doping of graphene by hybridizing the 2p_z orbital of graphene and the 3d orbitals of the Ti adsorbate, which attached on graphene without creating any trap/scattering states. This Ti-induced hybridization is adsorbate-specific and has major consequences for efficient doping as well as applications towards adsorbate-induced modification of carrier transport in graphene.