Well-defined carboxyl-terminated alkyl monolayers grafted onto H-Si(111): Packing density from a combined AFM and quantitative IR study

This work demonstrates that well-defined mixed carboxyl-terminated/methyl-terminated alkyl monolayers can be prepared in one step on H-terminated Si(111) via direct photochemical hydrosilylation of undecylenic acid and 1-decene mixtures. As evidenced by AFM imaging and IR spectroscopy, a final rinse in hot acetic acid leaves the functionalized surface atomically smooth and perfectly free of physisorbed contaminants while unwanted material remains atop the monolayer with most other common solvents. The compositional surface chemistry was determined from a truly quantitative IR (ATR geometry) study in the range of 900-4000 cm(-1). Results prove that neither surface oxidation nor grafting through the carboxyl end groups occurs. Monolayers are fairly dense for such bulky end groups, with a total molecular surface density of similar to 2.7 10(14) cm(-2) corresponding to a surface coverage of 0.35 (maximum theoretical value similar to 0.5). Careful analysis of the CH- and COOH-related IR bands reveals that the composition of the Grafted layers is richer in acid chains than the starting grafting mixture. A simple model is presented that shows that the grafting kinetics is about twice as fast for undecylenic acid as for 1-decene. Complementary electrochemical impedance measurements indicate the excellent electronic properties of the interface with a very low density of gap states. They also show that the acid terminal groups promote the penetration of water in the outer part of the organic film.