POSS-ProDOT Crosslinking of PEDOT

Alkoxy-functionalized polythiophenes such as poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-propylenedioxythiophene) (PProDOT) have become promising materials for a variety of applications including bioelectronic devices due to their high conductivity, relatively soft mechanical response, good chemical stability and excellent biocompatibility. However the long-term applications of PEDOT and PProDOT coatings are still limited by their relatively poor electrochemical stability on various inorganic substrates. Here, we report the synthesis of an octa-ProDOT-functionalized polyhedral oligomeric silsesquioxane (POSS) derivative (POSS-ProDOT) and its copolymerization with EDOT to improve the stability of PEDOT coatings. The POSS-ProDOT crosslinker was synthesized via thiol-ene "click" chemistry, and its structure was confirmed by both Nuclear Magnetic Resonance and Fourier Transform Infrared spectroscopies. PEDOT copolymer films were then electrochemically deposited with various concentrations of the crosslinker. The resulting PEDOT-co-POSS-ProDOT copolymer films were characterized by Cyclic Voltammetry, Electrochemical Impedance Spectroscopy, Ultraviolet-Visible spectroscopy and Scanning Electron Microscopy. The optical, morphological and electrochemical properties of the copolymer films could be systematically tuned with the incorporation of POSS-ProDOT. Significantly enhanced electrochemical stability of the copolymers was observed at intermediate levels of POSS-ProDOT content (3.1 wt%). It is expected that these highly stable PEDOT-co-POSS-ProDOT materials will be excellent candidates for use in bioelectronics devices such as neural electrodes.