Fluoroalkylsilanes with Embedded Functional Groups as Building Blocks for Environmentally Safer Self-Assembled Monolayers

The fabrication of silane-based fluorinated self-assembled monolayers (FSAMs) on indium tin oxide (ITO, a transparent electrode) was carried out making use of the following fluoroalkylsilanes (FAS): 2,2,3,3,4,4,5,5,6,6,6-undecafluoro-N-[3-(trimethoxysilyl]propyl]hexanamide (1; R-F = C5F11) and 1,1,2,2,3,3,4,4,4-nonafluoro-N-[3-(trimethoxysilyl)-propyl]butane-1-sulfonamide (2; R-F = C4F9), containing an embedded amide and a sulfonamide group, respectively, between the short perfluoroalkyl chain (R-F with C < 6) and the syloxanic moiety. The obtained FSAM-modified/ITO systems were characterized by X-ray photoelectron spectroscopy (XPS), contact angle (CA), surface energy measurements, and electrochemical impedance spectroscopy (EIS) and compared to ITO modified with a 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluor-ooctyltriethoxysilane (3; R-F = C6F13), with the perfluoroalkyl group linked to the syloxanic moiety through a simple hydrocarbon chain. The results obtained show that the presence of the -NHCO- and -NHSO2- groups have a different mode of action and, with the former, despite the short perfluoroalkyl chain, the ITO-1 system presents a CA (Theta(water) = 113.5 degrees) and surface energy (gamma(1) = 14.0 mJ m(-2)) typical of amphiphobic materials. These properties can be exploited in a variety of applications, such as self-cleaning, anti-fouling, and anti-fingerprint coatings, and in advanced microelectronic components.