When the first paper describing the formation of self-assembled monolayers (SAMs) of octadecyltrichlorosilane [CH3(CH2)17SCl3, or OTS] by adsorption on SiO2 was published, it could not have been predicted that this area of research would become so important in only one decade. Although Zisman was the first to discover that monolayers can be prepared by adsorption of a surfactant onto a clean metal surface, the real revolution in the field occurred when Nuzzo and Allara showed that SAMs of alkanethiolates on gold can be prepared by adsorption of di-n-alkyl disulfides from dilute solutions. A decrease in the use of moisture-sensitive alkyl trichlorosilanes and the increased use of crystalline gold surfaces were two important reasons for the success of these SAMs. Indeed, monolayers of alkanethiolates on gold are the most studied SAMs to date and thus deserve the most detailed discussion.
SAMs have been intensively studied in the past few years because of their relevance to science and technology. Due to their dense and stable structure, SAMs have potential applications in corrosion prevention, wear protection, and biosensing, for example. The ability to tailor both head and tail groups of the constituent molecules makes them ideal for gaining a more fundamental understanding of phenomena affected by competing intermolecular, molecular-substrate, and molecule-solvent interactions like ordering and growth, wetting adhesion, lubrication, and corrosion.