Electrodeposition of bilayers of dithiols

We report an electrochemical method to form a bilayer of dithiol. The cyclic voltammogram of the oxidative deposition of an aromatic dithiol on gold from an alkaline aqueous solution reveals two current peaks separated by more than 400 mV. The integrated charge of the oxidative current peak (B) at the most positive potential is twice that of the other oxidative current peak (A). These two oxidative current peaks were characterized by differential capacitance and electrochemical quartz crystal microbalance (EQCM) measurements. A decrease of the capacity by a factor of two, and an increase of the EQCM frequency change by a factor of two were observed when the potential was scanned from a value where only the first oxidative peak (A) is obtained, to a potential where both oxidative current peaks (A and B) are obtained. Infrared spectra show that the aromatic dithiols adsorb vertically at potentials corresponding to the current peak A and they become tilted for potentials corresponding to the current peak B. The simple relationships between the properties of the two oxidative current peaks are found to be compatible with a step-wise oxidative deposition of a bilayer of dithiol.