Investigation of the role of the interplay between water and temperature on the growth of alkylsiloxane submonolayers on silicon

We have investigated the influence of the interplay of the temperature and the water concentration in the adsorption solution on the growth of self-assembled monolayers on silicon using octadecyltrichlorosilane as the precursor. Toluene has been used as the solvent. The morphology of the submonolayer films has been investigated by atomic force microscopy (AFM). The surface coverages have been determined both with ellipsometry and through quantitative evaluation of AFM images. The size distribution of species in the precursor solution has been studied with dynamic light scattering. The influence of water concentrations between 8 and 18 mmol/L has been investigated in the temperature range from 2 to 35 degreesC. Dynamic light scattering revealed a unimodal size distribution of ordered aggregates in solution with a hydrodynamic radius of 200 nm regardless of the temperature and water concentration. However, formation of these features was faster at higher water contents and lower temperatures. Moreover, a characteristic temperature, which was higher for higher water concentrations, was found, above which such aggregates could not be detected anymore. Below this temperature an increase of the aggregate concentration has been observed until a plateau had been reached within a temperature range of approximately 5 degreesC. AFM measurements and ellipsometry on the corresponding submonolayer films showed that this temperature range is also associated with a transition from fast growth via characteristic fractally shaped islands to comparatively slow homogeneous growth via adsorption of individual molecules. The results are discussed in terms of diffusion and adsorption limitations.