F4-TCNQ on Epitaxial Bi-Layer Graphene: Concentration- and Orientation-Dependent Charge Transfer at the Interface.

Bi-layer epitaxial graphene (BLG) on 6H-SiC(0001) (EG/SiC) was grown and modified by thermal deposition of the molecular electron acceptor tetrafluoro-tetra cyano quinodimethane (F4-TCNQ). The surface-modified system, F4-TCNQ/EG/SiC, was studied by X-ray photoelectron spectroscopy (XPS) and angle-resolved polarized Raman spectroscopy (ARPRS). XPS results indicate that bonding of deposited F4-TCNQ molecules depends on their concentration. Although bonding through the cyano groups is present at all concentrations, charge transfer from graphene to fluorine is evident only at sub-monolayer concentrations. The corresponding change in bond character is coupled with a change in molecular orientation. Raman spectroscopy not only provides results consistent with the findings from the XPS study but also reveals a significant degree of molecular stacking above the monolayer concentration. Thus, both the variation of the acceptor concentration and the number of graphene layers provide further handles to manipulate charge and doping that may be useful in device applications.