Surface Dipoles: A Growing Body of Evidence Supports Their Impact and Importance.

Surface dipoles arise from differences in the distribution of electron density of interfacial molecular structures as expressed by charge separation. The direction and magnitude of the associated dipole moments directly impact a variety of interfacial phenomena. For example, the wettability of thin film-coated solid surfaces toward polar contacting liquids can be systematically adjusted by reorienting the direction of an array of interfacial dipoles, while the vector sum total of all of the dipole moments associated with such thin films can be used to tune the work function of a metal. One method of producing such dipole arrays is by coating a surface with a self-assembled monolayer (SAM), which is a thin organic film of amphiphilic adsorbates that spontaneously assemble on a surface. The interfacial properties of SAMs can be menu-selected by choice of adsorbate structure using ω-terminated thiols on gold surfaces as a convenient system for studying and utilizing these properties. In this Account, we describe the impact of an array of oriented surface dipoles upon the interfacial energy of the thin film bearing such an array. Our analysis of these films divides the subject of surface dipole arrays into three types: (1) those directing a well-defined electronegative pole toward the interface, (2) those incorporating an invertable polar group, and (3) those directing a well-defined electropositive pole toward the interface. With regard to the first category, we analyze the impact of permanent dipoles on the wettability of alkanethiolate SAMs generated from adsorbates possessing well-defined transitions between terminal fluorocarbon and underlying hydrocarbon chain segments. The second category covers recent reports of light-responsive SAMs formed from azobenzene-based adsorbates. Finally, the third category explores a unique example of a dipole array that exposes the positive ends of the interfacial dipoles formed from CH3-terminated fluorocarbon tailgroups. Our analysis of the SAMs formed from these carefully crafted adsorbates encompassing several series of fluorocarbon-containing thiols provides support for a conclusion that oriented surface dipoles exert a significant influence on interfacial energetics and wettability. In contrast to the limited distance from the interface that a surface dipole array will have upon contacting liquids, the work function of a thin film reflects the influence of all the polar groups within the film. Therefore, we also explore the change in the substrate work function for n-alkanethiol-modified gold surfaces as a function of molecular length and for other adsorbates as a function of their chemical composition.