Interfacial Structure in Thin Water Layers Formed by Forced Dewetting on Self-Assembled Monolayers of ω-Terminated Alkanethiols on Ag

A method for the spectroscopic characterization of interfacial fluid molecular structure near solid substrates is reported. The thickness and interfacial molecular structure of residual ultrathin D2O films remaining after forced dewetting on alkanethiolate self-assembled monolayers (SAMs) of 11-mercaptoundecanoic acid (11-MUA), 11-mercaptoundecanol (I I-MUD), and undecanethiol (UDT) on Ag are investigated using ellipsometry and surface Raman spectroscopy. The residual film thickness left after withdrawal is greater on hydrophilic SAMs than on hydrophobic SAMs. This behavior is rationalized on the basis of differing degrees of fluid slip within the interfacial region due to different interfacial molecular structure. The v(O-D) regions of surface Raman spectra clearly indicate unique interfacial molecular properties within these films that differ from bulk D2O. Although the residual films are created by shear forces and Marangoni flow at the three-phase line during the forced dewetting process, the nature of the films sampled optically must also be considered from the standpoint of thin film stability after dewetting. Thus, the resulting D2O films exist in vastly different morphologies depending on the nature of the water-SAM interactions. Residual D2O is proposed to exist as small nanodroplets on UDT surfaces due to spontaneous rupture of the film after dewetting. In contrast, on 11-MUD and 11-MUA surfaces, these films exist in a metastable state that retains their conformal nature on the underlying modified surface. Analysis of the peak intensity ratios of the so-called ice-like to liquid-like v(O-D) modes suggests more ice-like D2O character near 11-MUD surfaces, but more liquid-like character near 11-MUA and UDT surfaces. The creation of residual ultrathin films by forced dewetting is thus demonstrated to be a powerful method for characterizing interfacial molecular structure of fluids near a solid substrate under ambient conditions of temperature and pressure.