Self-Assembly of Alkanethiols on an Oxide-Free Surface of a Copper Electrode from Alkaline Solutions under Electrochemical Control

Using voltammetry and chronoamperometry, the formation process and properties of insulating nanofilms of alkanethiols with different chain lengths (butane-, octane-, dodecanethiol) obtained on an oxide-free copper surface were studied. The electrochemical method for modifying the copper surface includes the removal of the oxide layer by its cathodic reduction, the adsorption of a thiol under electrochemical control, followed by studying the properties of the resulting nanofilm by voltammetry in one solution. It is shown that, with this approach, a dense thiol film is formed, with its blocking properties depending on the adsorption potential, the time of contact of the electrode with the thiol-containing solution, the thiol concentration, and the presence of dissolved oxygen in the solution. The introduction of ethanol into an aqueous alkali solution leads to a significant acceleration of the process of self-assembly of dodecanethiol, but greatly inhibits the process of self-assembly of butanethiol. The approach proposed in this work makes it possible to use aerated low-concentration thiol-containing solutions to obtain alkanethiol films on the Cu surface with good blocking properties.