Autocatalytic effect of amine-terminated precursors in mixed self-assembled monolayers

We investigated the formation of mixed self-assembled monolayers (SAMs), comprising two silanes terminated with an amine and a non-reactive functional group, to demonstrate the autocatalysis of the mixed SAMs by the amine-terminated precursors. Measurements of surface energy and angle-resolved X-ray photoelectron spectroscopy on the mixed SAMs revealed that the final composition and the surface coverage of the mixed SAMs after deposition strongly depended on the presence and the concentration of the aminesilane precursor in solution. To explain the observed dependence, we further suggested a mechanism based on the autocatalytic effect of the aminesilane precursor on the mixed SAM. These results highlight the complex role of the aminesilane, which behaves simultaneously as a component of the mixed SAM and a catalyst. An important implication of this is that the compositions of mixed SAMs can be significantly influenced by the autocatalytic effect of the component carrying a reactive functional group such as amine.