Substrate effects on the formation of alkylsiloxane monolayers

Submonolayers of octadecylsiloxane (ODS) were prepared by adsorption from dilute solutions of octadecyltrichlorosilane (OTS) onto a series of different substrates: mica, native silicon (Si/SiO2), and mica coated with a defined number n(SiO) of SiO2 monolayers (n(SiO) = 1, 2, 4, 6). Atomic force microscopy (AFM) was used to investigate the adsorption rate and the submonolayer island morphology as a function of the substrate composition. Two types of substrate effects were observed-first, an abrupt change of the shape, size, and height distribution of the submonolayer islands between mica and SiO2-coated mica or silicon substrates, and second, an exponential decrease of the adsorption rate with n(SiO) up to a thickness of about 6 SiO2 monolayers. The first effect is independent of the SiO2 film thickness and the nature of the underlying substrate (mica or Si) and is therefore believed to arise from the different surface concentrations of OH groups on mica and SiO2 surfaces. The adsorption rate decrease with n(SiO), in contrast, appears to be a long-range, bulk effect of mica and might reflect an electrostatic interaction between the negatively charged mica surface and the polar head groups of the film molecules, which accelerates the adsorption in comparison to that of an uncharged substrate such as silicon.