The surface structure of Few-Layer Graphene (FLG) epitaxially grown on the C-face of SiC has been investigated by TM-AFM in ambient air and upon interaction with diluted aqueous solutions of bio-organic molecules (dimethyl sulfoxide, DMSO, and L-Methionine). On pristine FLG we observe nicely ordered, three-fold oriented rippled domains, with a 4.7+/-0.2 nm periodicity (small periodicity, SP) and a peak-to-valley distance in the range 0.1-0.2 nm. Upon mild interaction of the FLG surface with the molecular solution, the ripple periodicity relaxes to 6.2+/-0.2 nm (large periodicity, LP), while the peak-to-valley height increases to 0.2-0.3 nm. When additional energy is transferred to the system through sonication in solution, graphene planes are peeled off from FLG, as shown by quantitative analysis of XPS and Raman spectroscopy data which indicate a neat reduction of thickness. Upon sonication rippled domains are no longer observed. Regarding HOPG, we could not observe ripples on cleaved samples in ambient air, while LP ripples develop upon interaction with the molecular solutions. Recent literature on similar systems is not univocal regarding the interpretation of rippling. The complex of our comparative observations on FLG and HOPG can be hardly rationalized solely on the base of surface assembly of molecules, either organic molecules coming from the solution or adventitious species. We propose to consider the ripples as the manifestation of the free-energy minimization of quasi-2D layers, eventually affected by factors such as the interplane stacking, the interaction with molecules and/or with the AFM tip.
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