Dynamic self-assembly and electropolymerization processes of 3,4-ethylenedioxythiophene on Au(1 0 0) single crystal electrode as probed by in situ scanning tunneling microscopy

Abstract

Electrochemical scanning tunneling microscopy (EC-STM) was employed to examine the molecular assembly and electropolymerization processes of 3,4-ethylenedioxythiophene (EDOT) onto reconstructed and unreconstructed Au(100) single crystal electrodes in a 0.1M HClO4 electrolyte solution. The EDOT adsorption onto the Au(100)-hex surface induced lifting of the reconstruction at potentials as low as E=0.150V (vs. reversible hydrogen electrode (RHE)), which is clear evidence of the strong EDOT–Au interaction that was also observed by cyclic voltammetry (CV). EC-STM was also able to reveal, for the first time, the dynamic process of EDOT molecular self-assembly onto the Au(100)-(1×1) surface. The EDOT adlayer was found to fit into a 42×32 unit cell. High-resolution STM imaging revealed a vertically tilted geometry for the EDOT molecules. Electropolymerization was also performed, revealing the solution-process formation of polymer bundles.