Environment-Controlled Tethering by Aggregation and Growth of Phosphonic Acid Monolayers on Silicon Oxide

Phosphonic acid monolayers are being considered as versatile surface modification agents due to their unique ability to attach to surfaces in different configurations, including mono-, bi-, or even tridentate arrangements. Tethering by aggregation and growth (T-BAG) of octadecylphosphonic acid (ODPA) on silicon oxide surfaces has proven to be a robust method to establish a strong chemical bond. However, it requires a long processing time (> 48 h) that is a substantial drawback for industrial applications. We demonstrate here that the humidity level during processing is the most important parameter controlling the reaction. Using in situ Fourier Transform Infrared Spectroscopy (FTIR), we first show that the initially physisorbed layer obtained upon immersion in ODPA is composed of well-ordered bilayers and only reacts with the SiO2 surface at 140 °C. Importantly, we show that the presence of water at the interface (determined by the humidity level) greatly influences the reaction time and completion. In hu...