Dynamics of solution displacement in 1-adamantanethiolate self-assembled monolayers

We have investigated the dynamics of solution-phase displacement of preformed 1-adamantanethiolate self-assembled monolayers on Au{111} by n-dodecanethiol molecules on both the ensemble (millimeter) and molecular (nanometer) scales. Employing scanning tunneling microscopy, Fourier-transform infrared spectroscopy, and cyclic voltammetry, we have observed complete displacement of the preformed 1-adamantanethiolate self-assembled monolayers by n-dodecanethiol molecules via nucleation and growth. We have established and evaluated the experimental parameters that influence 1-adamantanethiolate self-assembled monolayer displacement. With established parameters, the resolution and reproducibility of chemically patterned surfaces, applicable in areas ranging from microelectronics to biocompatible systems, have been improved to fabricate and to control structures at the supramolecular 1-100 nm scale.