Fractional coverage of defects in self-assembled thiol monolayers on gold

Au electrodes are alkylated by self-assembled organic monolayers of octadecanethiol from alcohol solution. The electron tunnelling resistance of a monolayer-coated gold electrode has been investigated by ac impedance. The relation between the fractional coverage of different defects and the corresponding film thickness at these 'collapsed' sites has been deduced from electron tunnelling theory. By using the concepts of average film thickness at defect (d_a) and average fractional coverage of defect (θ_a), we have obtained the θ_a approx. d_a plot. The influence of the apparent standard rate constant on the shape of the θ_a approx. d_a plot has been discussed. In our experiments, Fe(CN)₆^3-/4- is used as a redox probe to study the θ_a approx. d_a plot of an octadecanethiol monolayer. The θ_a versus d_a plot indicates that the defects with d_a < 6 methylene groups and θ_a < 0.1 can increase the apparent standard rate constant from 1.9 × 10^-10 cm s^-1, which is the theoretical value calculated from electron tunnelling theory, to 2.9 × 10^-7 cm s^-1. The average thickness of the whole monolayer (ATWM), which is obtained from the θ_a versus d_a plot and which can indicate the blocking property of the monolayer, is 11 methylene groups.