In Situ Observations of Nanofibril Nucleation and Growth during the Electrochemical Polymerization of Poly(3,4-ethylenedioxythiophene) Using Liquid-Phase Transmission Electron Microscopy

Abstract

The electrochemical deposition of poly(3,4-ethylenedioxythiophene) (PEDOT) has been carried out previously in the presence of a variety of counterions. Previous studies have shown that elongated nanofibrillar structures of PEDOT would form reproducibly when certain counterions such as poly(acrylic acid) (PAA) were added to the reaction mixture. However, details of the nanofibril nucleation and growth stages were not yet clear. Here, we describe the structural evolution of PEDOT nanofibrils using liquid-phase transmission electron microscopy (LPTEM). We measured the growth velocities of nanofibrils in different directions at various stages of the process and their intensity profiles, and we have estimated the number of EDOT monomers involved. We observed that fibrils initially grew anisotropically in a direction nominally perpendicular to the local edge of the electrodes, with rates that were faster along their lengths as compared those along to their widths and thicknesses. These real-time observations have helped us elucidate the nucleation and growth of PEDOT nanofibrils during electrochemical deposition.