Self-assembled molecular films of aminosilanes and their immobilization capacities

The assembly of two aminosilanes on silicon dioxide surfaces is investigated in this work. It is found that for 3-aminopropyltrimethoxysilane (APS), a smaller concentration of the silane and trace amounts of water in the deposition medium, an optimum time, and a postdeposition thermal curing are necessary to obtain a high primary-amine content. By optimization of deposition conditions, uniform APS films with a primary-amine content of 88.6% were obtained. The dependence of the primary-amine content on the experimental parameters is related to the extent to which amines are lost to hydrogen bonding with each other or with the substrate surface. When p-aminophenyltrimethoxysilane (APhS) was used, the primary-amine content in the film reached 100% and the surface morphology was more uniform than that of APS films under the same conditions. This is attributed to the rigid phenyl component in APhS that reduces opportunities for hydrogen bonding. In a comparison of the immobilization capacities of the different aminosilane substrates for pyromellitic dianhydride (PMDA), it is observed that higher primary-amine content favors higher uptake, and the APhS film yields 100% PMDA coverage. We infer that primary-amine content could be a measure of the film morphology and accessibility of the substrate amine groups.