We have studied submonolayer coverages of N,N-1H,1H-perfluorobutyl dicyanoperylenecarboxydiimide (PDIF-CN2) on mechanically exfoliated graphene transferred onto SiO2 substrates. Our atomic force microscopy (AFM) data show that PDIF-CN2 forms irregularly-shaped 1.4 nm-high islands. From the selected area diffraction performed with transmission electron microscope (TEM) we conclude that this height corresponds to π−π
stacks of molecules, which are inclined for 43° relative to the graphene surface. AFM also showed complete absence of PDIF-CN2 on single-layer graphene (SLG). Electric force microscopy revealed a marked difference in surface charge density between a single-layer graphene and bilayer graphene, with a higher surface charge on SLG than on the bilayer graphene. We associate this behavior with p−
type doping of graphene due to the electrostatic dipole induced by the molecular water layer present at the graphene/SiO2 interface. The crucial role of the graphene/SiO2 interface in determining growth of PDIF-CN2 was further confirmed by TEM examination of PDIF-CN2 deposited onto unsupported SLG
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