Interfacial water structure on a highly hydroxylated silica film

Evidence suggests that in order for a surface to support an extensive water structure, it must possess sufficient Lewis cites so that water-surface interactions are favored over water-water interactions. In this paper we use ATR-FTIR to comparatively study, as a function of relative humidity, the water structure that exists on three surfaces: silicon, PEG-modified silicon, and a highly hydroxylated silica film which is formed from the room temperature, vapor phase hydrolysis of tetrachlorosilane. Results indicate that the PEG-modified silicon surface supports a water structure nearly 2.5 times as extensive as that which exists on unmodified silicon surfaces, which is an expected result in light of previous molecular dynamics simulations that indicate extensive hydrogen bonding between PEG monolayers and water molecules. The silica layer supports a water structure that is nearly an order of magnitude more extensive than that which exists on clean silicon surfaces and approximately 3.5 times more extensive than is adsorbed on PEG-modified silicon surfaces at similar relative humidities. Furthermore, the water layer on the silica surface exists mostly in an "ice-like" structure which is also more strongly hydrogen bonded than that which exists on clean silicon and PEG-modified silicon surfaces.