Potential-Induced Defects in <i>n</i>-Alkanethiol Self-Assembled Monolayers Monitored by Impedance Spectroscopy

Abstract

The ionic permeability of alkanethiol self-assembled monolayers (SAMs) chemisorbed on gold is studied using ac impedance spectroscopy in the absence of redox active species. CH3(CH2)nS/Au (n = 7−15) SAMs behave as ionic insulators until a critical potential, Vc, is reached or exceeded. At potentials more cathodic than Vc, SAMs are no longer ionic insulators and a significant change in the phase angle is associated with ion penetration in the low-frequency region. Vc is chain length dependent and is observed at potentials (−0.15 to −0.35 V vs Ag/AgCl) that are considerably more anodic than the alkanethiol electrodesorption potential. The relaxation frequency of trans-SAM ion migration (4−100 Hz) can be calculated from fitting of the impedance data to an appropriate equivalent circuit or from Bode phase plots.