Surface studies of pristine and surface‐modified polypyrrole films

Abstract

Polypyrrole (PPY) films having high conductivity were synthesized electrochemically in acetonitrile at low temperature and low current density. Pristine, deprotonated, and ozone-pretreated PPY films were subjected to either thermally induced or near-UV-light-induced graft copolymerization with acrylic acid (AAc), or sodium salt of 4-styrenesulfonic acid (NaSS). Surface structures and redox states of the pristine, deprotonated, reprotonated, and surface-modified polypyrrole films were studied by angle-dependent X-ray photoelectron spectroscopy (XPS). The morphology of the PPY surface after modification by graft co-polymerization was revealed by atomic force microscopy (AFM). The results showed that the density of surface grafting decreased with ozone pretreatment. Surface grafting of the two polymeric acids also gave rise to a self-protonated surface structure. A substantial proportion of the grafted protonic acid groups at the surface remained free for further surface functionalization. The surface characteristics, in particular the charge-transfer interactions and the changes in the intrinsic redox states of the substrate films, associated with the external protonation and surface self-protonation processes were also discussed. © 1996 John Wiley & Sons, Inc.