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.