Electrochemically polymerized conjugated polymer films: stability improvement and surface functionalization

Martin, David C.Conjugated polymers have been widely used in various applications including organic solar cells, electrochromic devices, chemical sensors, and biomedical devices. Poly(3,4-ethylenedioxythiophene) (PEDOT) and its derivatives have received considerable interest because of their low oxidation potential, relatively high chemical stability, and high conductivity. Electrochemical deposition is a convenient method for precisely fabricating conjugated polymer thin films. Here, we report the stability improvement and surface functionalization of electrochemically polymerized PEDOT films. The long-term performance of PEDOT coatings is limited by their relatively poor stability on various inorganic substrates. Two different methods were used to improve the stability of PEDOT coatings, one involved using carboxylic acid functionalized EDOT (EDOT-acid) as adhesion promoter. EDOT-acid molecules were chemically bonded onto activated metal oxide substrates via chemisorption. PEDOT was then polymerized onto the EDOT-acid modified substrates, forming covalently bonded coatings. An aggressive ultrasonication test confirmed the significantly improved adhesion of the PEDOT films on electrodes with EDOT-acid treatment over those without treatment. The other method was to use an octa-ProDOT-functionalized POSS derivative (POSSProDOT) as cross-linker. PEDOT copolymer films were electrochemically deposited with various concentrations of POSS-ProDOT. The optical, morphological and electrochemical properties of the copolymer films could be systematically tuned with the incorporation of POSS-ProDOT. Significantly enhanced electrochemical and mechanical stability of the copolymers were observed at intermediate levels of POSS-ProDOT content (3.1 wt%) via chronic stimulation tests. Surface functionalization of conducting polymer films provides a potential means for systematically tailoring their chemical and physical properties. We have synthesized, polymerized and characterized a dialkene-functionalized variant of the ProDOT monomer. With the alkene side groups, highly efficient post-polymerization functionalization of the conducting film was successfully achieved via a radical-based thiol-ene “click” reaction with various terminal thiols, including alkanes, ethylene glycols, and ferrocenes. These surface modification led to dramatic changes in the charge transport and wetting behavior of the chemically functionalized films.University of Delaware, Department of Materials Science and EngineeringPh.D