We have demonstrated the use of a two-dimensional array of beads to direct the self-assembly of hexadecanethiol (HDT) molecules on gold from the vapour phase. The beads served as a guide to transport HDT molecules from the vapour phase to the gold, and their circular footprints defined the shape of the forming self-assembled monolayer. Depending on the deposition temperature and pressure, a monolayer in the form of either an array of rings or a membrane was generated, which were then transferred into the underlying gold by selective wet chemical etching. (c) 2005 Elsevier B.V. All rights reserved.