Ethanol vs. water: influence of the terminal functional group of the alkyl chain and environment of the self-assembly process on electron transport through the thiol layer

Self-assembly of alkanethiol chains on metallic surfaces is a spontaneous process which leads to the formation of highly ordered layers. However, the organization of the thiol chains on the surface strongly depends on the intermolecular interactions between the terminal groups in the chain. The solution environment also plays an important role. In this paper we present the effect of solution solvent (water and ethanol) and the presence of various hydrophilic terminal groups (–OH, –NH(2) and –COOH) on the quality and electrochemical properties of the formed alkanethiol layers. In the studies we applied voltammetry, atomic force microscopy and quartz crystal microbalance to characterize the morphology, packing density and ability to electron exchange through the thiol layer. The blocking properties of the formed SAMs expressed as the electron-transfer rate constant as well as their organization have been examined using a model electrochemical probe, Fe(CN)(6)(3−). With the increase in the polarity of the terminal functional group the regularity of the thiol layer decreased.