Evidence of Self-Assembled Monolayers Preorganization Prior to Surface Contact: a First Principles Study

We explore the main gas and liquid phase chemistry that governs the typical self assembled monolayers (SAMs) deposition processes before precursors interaction with the surface. A number of pathways are determined (enthalpies and associated activation barriers). These include gas phase hydrolysis, effect of low polar solvent, effect of an excess of water molecules, and gas and liquid phase self-condensation of silane precursors. We demonstrate that partial to full hydrolysis is easily performed in the presence of water molecules. Subsequently, condensation is also shown to occur indicating that preorganization of SAMs is to be expected in practice in the gas and liquid phase, leading to the actual deposition of SAMs aggregates.