Construction of artificial monolayer assemblies on Si(111) surface using silicon monofluoride as a chemisorption site

Adsorption of molecules from a solution onto a fluorine-terminated Si(111) surface has been examined using X-ray photoelectron spectroscopy. The decrease in the F1s peak intensity assigned to the surface Si–F bond is accompanied by a quantitative increase in the core electron peaks ascribed to the molecule, while some Si–F remain intact. The adsorption of molecules with larger dimensions results in a decrease in the proportion of surface fluorine that is replaced. These results show that the substitution reaction proceeds until the steric hindrance of adsorbed molecules limits further adsorption. Fourier transform infrared attenuated total reflection reveals the molecule to be covalently bonded to the silicon surface giving monomolecular coverage. Dicarboxylic acids are shown to adsorb through only one of the two carboxyl groups, the other end being exposed at the monolayer–air or monolayer–liquid interface. Free carboxyl groups on the adlayer, after being converted to chloroformyl groups by chlorination reagents, act as chemisorption sites for other molecules.