STM Studies of Self-Assembled Tetrathiafulvalene (TTF) Derivatives on Graphene: Influence of the Mode of Deposition

The conformations and the self-assembly process of tetrathiafulvalene (TTF) derivatives functionalized by lateral alkylthio chains deposited on graphene/SiC(0001) in ultrahigh vacuum (UHV) and at the solid–liquid interface are studied by scanning tunneling microscopy (STM). The study in UHV evidences a “molecular fastener” effect induced by the increase of van der Waals interactions between the alkylthio side chains which forces the major part of the molecules to self-organize in π–π stacked edge-on conformation. The study at the solid–liquid interface reveals a drastically different behavior with molecules lying flat on the surface as the solvent is involved in the stabilization of the molecular layer. This work raises a burning issue concerning the choice of the deposition method for graphene functionalization with such molecules