Single and binary self-assembled monolayers of phenyl- and pentafluorophenyl-based silane species, and their phase separation with octadecyltrichlorosilane

In this paper, we first present the study of the formation of phenyltrichlorosilane film and self-assembled monolayers of phenylalkyltrichlorosilane (PATCl), pentafluoro-phenylalkyltrichlorosilane (PFATCl), and a mixture of the two, on silicon covered by its native oxide. These monolayers are shown to grow in two steps with characteristic time constants. The first step is characterized by a similar time constant of growth for all the studied trichlorosilane molecules and attributed to chemisorption. The second step corresponds to the arrangement between molecules, accelerated by the presence of the short alkyl chain (3-4 carbon atoms), and by mixing phenyl and pentafluoro-phenyl terminal moieties, which is accounted for by hydrogen bonding CH···FC and/or attractive quadrupolar interactions within a face-to-face phenyl/pentafluoro-phenyl alternating stack arrangement. Such results should allow improvement of intermolecular stacking within conjugated molecular domains, which is particularly important for molecular electronic devices. In the second part, we studied how PATCl, PFATCl, and their mixture phase separate with octadecyltrichlorosilane (OTS) molecules in various ratios. The way to improve phase separation was studied modifying aromatic ring to ring as well as aromatic-aliphatic interactions. OTS island size and coverage are shown to be smaller with the aromatic phase that involves stronger ring to ring interactions, i.e., attractive interactions between the phenyl species by mixing phenyl and pentafluoro-phenyl rings. The best phase separation is obtained with PFATCl as the aromatic molecule. If nanoislands of aromatic molecules could not be observed in these experiments, we show that they are attainable by mixing OTS and aromatic small organotriethoxysilanes whose grafting kinetics is slower. These results pave the way to the control improvement of the composition and nanostructuration of SAMs, essential for their further use within molecular devices.