Anode geometry can significantly affect the electrochemical synthesis of conductive polymers. Here, the effects of anode dimensions on the electropolymerization of pyrrole are investigated. Band microelectrodes were prepared with widths ranging from 2 to 500 μm. The anode dimension has a significant effect on the resulting thickness of polymer film. The electropolymerization process deviates significantly from that predicted by simple mass transfer considerations when electrode dimensions are less than ∼ 20 μm. Polymer film thickness is thinner than expected when electrode dimensions become less than ∼ 10 μm. A simple mathematical model was derived to explain the observed effects of anode dimensions on the polymerization process. Simulation results confirm that diffusive loss of reaction intermediates accounts for the observed experimental trends. The described simulation facilitates understanding of the electropolymerization processes and approaches to the controlled deposition of polypyrrole, particularly at the submicron scale, for microelectromechanical systems and biomedical applications.
Benjamin L. Fletcher, Jared T. Fern, Kevin Rhodes, Timothy E. McKnight, Jason D. Fowlkes, Scott T. Retterer, David J. Keffer, Michael L. Simpson, and Mitchel J. Doktycz, J. Appl. Phys. (2010). Effects of ultramicroelectrode dimensions on the electropolymerization of polypyrrole 105, 124312 DOI:10.1063/1.3152633