The interface structure of n-alkylthiolate self-assembled monolayers on coinage metal surfaces

The current state of understanding of the structure of the metal/thiolate interface of n-alkylthiolate 'self-assembled monolayers' (SAMs) on Cu(111), Ag(111) and Au(111) is reviewed. On Cu(111) and Ag(111) there is now clear evidence that adsorbate-induced reconstruction of the outermost metal layer occurs to a less atomically-dense structure, with the S head-group atom bonded to four-fold and three-fold coordinated hollow sites, respectively, and that intermolecular interaction plays some role in the periodicity of the resulting SAMs. On the far more heavily-studied Au(111) surface, the detailed interface structure remains controversial, but there is growing evidence for the role of Au-adatom-thiolate moieties in the layer ordering.