Self-assembled monolayers (SAMs) of alkanethiols and dialkanethiols on gold are key elements for building many systems and devices with applications in the wide field of nanotechnology. Despite the progress made in the knowledge of these fascinating two-dimensional molecular systems, there are still several “hot topics” that deserve special attention in order to understand and to control their physical and chemistry properties at the molecular level. This critical review focuses on some of these topics, including the nature of the molecule–gold interface, whose chemistry and structure remain elusive, the self-assembly process on planar and irregular surfaces, and on nanometre-sized objects, and the chemical reactivity and thermal stability of these systems in ambient and aqueous solutions, an issue which seriously limits their technological applications (375 references).

A review article on fundamental aspects of thiolate self-assembled monolayers (SAMs) on the (111) and (100) surfaces of the Cu and Ni groups is presented.

The electrodeposition of gold on highly oriented pyrolytic graphite (HOPG) from acid aqueous solutions was studied by using electrochemical techniques complemented with ex-situ scanning tunneling microscopy (STM). The kinetics of gold electrodeposition is consistent with a nucleation and three-dimensional growth process under diffusion control from the solution side. As the applied potential moves in the negative direction, the gold crystal density increases, and the crystal shape changes from a Euclidean to a dendritic fractal morphology. This transition can be assigned to the anisotropic surface diffusion of gold adatoms induced by the applied electric potential. A model including a potential-dependent energy barrier at step edges accounts for the morphology transition for gold electrodeposition on HOPG.