Abstract
This article reviews recent progress in the spectroscopic characterization ofaliphatic and aromatic thiol-derived self-assembled monolayers (SAMs) on noblemetal substrates. Several complementary techniques such as nearedge x-rayabsorption fine structure spectroscopy, x-ray photoelectron spectroscopy, andinfrared reflection absorption spectroscopy were applied to study the balancebetween intermolecular and adsorbate-substrate interactions, chemicalidentity of the headgroup, and absorption site homogeneity at thesulphur-metal interface. Whereas in the thioaliphatic SAMs the headgroup-substrate interaction was found to be a decisive factor for thestructure and packing in these films, these parameters are mainly determinedby the intermolecular interactions in the thioaromatic films. Only one sulphurspecies could be detected in the S 2p HRXPS spectra of both aliphatic andaromatic SAMs suggesting binding of individual molecules as thiolates.Conclusions on the heterogeneity of the adsorption sites are derived andevidence that the investigated films represent highly correlated molecularassemblies are presented.
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