Organic Mixed Ionic-Electronic Conductors Based on Tunable and Functional Poly(3,4-ethylenedioxythiophene) Copolymers

Organic mixed ionic-electronic conductors (OMIECs) are being explored in applications such as bioelectronics, biosensors, energy conversion and storage, and optoelectronics. OMIECs are largely composed of conjugated polymers that couple ionic and electronic transport in their structure as well as synthetic flexibility. Despite extensive research, previous studies have mainly focused on either enhancing ion conduction or enabling synthetic modification. This limited the number of OMIECs that excel in both domains. Here, a series of OMIECs based on functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) copolymers that combine efficient ion/electron transport with the versatility of post-functionalization were developed. EDOT monomers bearing sulfonic (EDOTS) and carboxylic acid (EDOTCOOH) groups were electrochemically copolymerized in different ratios on oxygen plasma-treated conductive substrates. The plasma treatment enabled the synthesis of copolymers containing high ratios of EDOTS (up to 68%), otherwise not possible with untreated substrates. This flexibility in synthesis resulted in the fabrication of copolymers with tunable properties in terms of conductivity (2-0.0019 S/cm) and ion/electron transport, for example, as revealed by their volumetric capacitances (122-11 F/cm³). The importance of the organic nature of the OMIECs that are amenable to synthetic modification was also demonstrated. EDOTCOOH was successfully post-functionalized without influencing the ionic and electronic transport of the copolymers. This opens a new way to tailor the properties of the OMIECs to specific applications, especially in the field of bioelectronics.