  The non-covalent functionalisation of graphene is an attractive strategy to
alter the surface chemistry of graphene without damaging its superior
electrical and mechanical properties. Using the facile method of aqueous-phase
functionalisation on large-scale CVD-grown graphene, we investigated the
formation of different packing densities in self-assembled monolayers (SAMs) of
perylene bisimide derivatives and related this to the amount of substrate
contamination. We were able to directly observe wet-chemically deposited SAMs
in scanning tunnelling microscopy (STM) on transferred CVD graphene and
revealed that the densely packed perylene ad-layers adsorb with the conjugated
{\pi}-system of the core perpendicular to the graphene substrate. This
elucidation of the non-covalent functionalisation of graphene has major
implications on controlling its surface chemistry and opens new pathways for
adaptable functionalisation in ambient conditions and on the large scale.
