Characterisation, coverage, and orientation of functionalised graphene using sum-frequency generation spectroscopy

We report the unambiguous detection of phenyl groups covalently attached to functionalised graphene using non-linear spectroscopy. Sum-frequency generation was employed to probe graphene on a gold surface after chemical functionalisation using a benzene diazonium salt. We observe a distinct resonance at 3064 cm1 which can clearly be assigned to an aromatic C–H stretch by comparison with a self-assembled monolayer on a gold substrate formed from benzenethiol. Not only does sum-frequency generation spectroscopy allow one to characterise functionalised graphene with higher sensitivity and much better specificity than many other spectroscopic techniques, but it also opens up the possibility to assess the coverage of graphene with functional groups, and to determine their orientation relative to the graphene surface