The electrochemical characteristics of an Au(111) electrode were investigated in 0.1 M KOH ethanol solutions containing various concentrations of decanethiol. Anodic and cathodic peaks corresponding to the oxidative adsorption and reductive desorption, respectively, of a self-assembled monolayer (SAM) of decanethiol were observed. Both peaks negatively shifted with the increase in the thiol concentration by ca. 57 mV/decade, showing that the redox process is a one-electron process. The adsorbed amount determined from the charge corresponding to the reductive desorption increased with an increase in the decanethiol concentration but never reached the saturated amount as long as the cyclic voltammograms were continuously recorded with the sweep rate of 10 -200 mV s-1. It increased with the holding time at +0.1 V, which was much more positive than the anodic peak potential, and reached the saturated amount in ca. 10 min in the 10 μM thiol solution. The reductive peak potential also negatively shifted with the holding time but for a longer period. It kept shifting for ca. 60 min in the 10 μM thiol solution, which is much longer than the time when the adsorbed amount reached the saturated value. These results suggest that the formation of a highly ordered SAM requires a much longer time than the adsorption of the thiol.2

Electrochemical oxidative formation and reductive desorption processes of a self-assembled monolayer (SAM) of hexanethiol on a Au(111) surface in KOH ethanol solutions containing various concentrations of hexanethiol were investigated by in situ scanning tunneling microscopy in real time. The generation and disappearance of vacancy islands (VIs), corresponding to the formation and desorption of the SAM, respectively, were observed as anodic and cathodic current, respectively, flowed when the thiol concentration was higher than ca. 1 microM. When the VIs disappeared after the reductive desorption of the SAMs, the herringbone structure corresponding to the (radical3 x 23) structure of Au(111), was observed on the surface, indicating that a clean reconstructed surface was exposed even in the hexanethiol ethanol solution. During both oxidative adsorption and reductive desorption of the SAMs, the shape of the steps of the gold substrate changed drastically and the step lines became parallel to the 121 direction of the Au(111) surface, suggesting that gold atoms on the surface were extremely mobile during these processes. The coalescence of adjacent vacancy islands and growth of larger islands triangular in shape accompanied with the disappearance of nearby smaller islands were observed, confirming that the VIs grew according to the Ostward ripening model.