Balancing Charge Storage and Mobility in an Oligo(Ether) Functionalized Dioxythiophene Copolymer for Organic‐ and Aqueous‐ Based Electrochemical Devices and Transistors

Abstract

This work presents a soluble oligo(ether)-functionalized propylenedioxythiophene (ProDOT)-based copolymer as a versatile platform for a range of high-performance electrochemical devices, including organic electrochemical transistors (OECTs), electrochromic displays, and energy-storage devices. This polymer exhibits dual electroactivity in both aqueous and organic electrolyte systems, redox stability for thousands of redox cycles, and charge-storage capacity exceeding 80 F g −1 . As an electrochrome, this material undergoes full colored-to-colorless optical transitions on rapid time scales (<2 s) and impressive electrochromic contrast (Δ%T > 70%). Incorporation of the polymer into OECTs yields accumulation-mode devices with an I ON/OFF current ratio of 10 5 , high transconductance without post-treatments, as well as competitive hole mobility and volumetric capacitance, making it an attractive candidate for biosensing applications. In addition to being the first ProDOT-based OECT active material reported to date, this is also the first reported OECT material synthesized via direct(hetero)arylation polymerization, which is a highly favorable polymerization method when compared to commonly used Stille cross-coupling. This work provides a demonstration of how a single ProDOTbased polymer, prepared using benign polymerization chemistry and functionalized with highly polar side chains, can be used to access a range of highly desirable properties and performance metrics relevant to electro chemical, optical, and bioelectronic applications. Electroactive Polymers[+] Present address:

Energetic Control of Redox‐Active Polymers toward Safe Organic Bioelectronic Materials

“…[ 34 ] The volumetric capacitance of p(gPyDPP‐MeOT2) is 60 F cm −3 at an offset potential of 0.7 V versus Ag/AgCl (Figure S24, Supporting Information), which is on par with values reported for other donor‐acceptor copolymers with glycol side‐chains. [ 18 ] g m,norm of p(gPyDPP‐MeOT2) OECTs is comparable to other p‐type OECTs based on benzodithiophene (BDT) copolymers [ 2 ] or propylenedioxythiophene (ProDOT) copolymers [ 6 ] but is lower in performance compared to state‐of‐the‐art polymers such as p(g2T‐TT) [ 3 ] or PEDOT:PSS, [ 16 ] due to lower values for both μ h and C *. [ 15 ]…”

“…These materials, also called organic mixed ionic/electronic conductors (OMIECs), can exchange ions with aqueous electrolytes when electronic charge carriers are injected, transported, and stored in the bulk of the material. [ 1 ] Recent developments of OMIECs based on redox‐active conjugated polymers [ 2–8 ] and novel device concepts [ 9,10 ] have opened up new pathways for bioelectronic devices including integrated circuits for electroencephalogram (EEG) monitoring [ 9 ] or low‐power voltage amplifiers based on organic electrochemical transistors (OECTs). [ 11 ] Specifically, the OECT has drawn significant attention in the field of organic bioelectronics.…”

The Effect of Oligo(Ethylene Oxide) Side Chains: A Strategy to Improve Contrast and Switching Speed in Electrochromic Polymers

“…Moreover, polyether‐based electrolytes show high ionic conductivities . The introduction of highly polar chains in conjugated polythiophene derivatives can effectively enhance the ionic sensitivity . Many attempts have been paid on polythiophene, and 3,4‐alkylenedioxythiophene (XDOT)‐based ECPs .…”

“…Reynolds et al . functionalized 3,4‐propylenedioxythiophenes) (ProDOT) with two oligo(ether) chains to achieve high redox activity of polymer in aqueous electrolytes . Besides, other highly polar chains e. g .…”

Conducting Polymer‐Based Biocomposites Using Deoxyribonucleic Acid (DNA) as Counterion

“…[54] Today significant work is still being dedicated toward chemical modifications and further improvements of PEDOT:PSS [55,56] and meanwhile substantial effort is devoted to develop alternative conjugated polymer structures. [57][58][59][60][61][62][63] Therefore, the search of new conducting polymer biocomposites is clearly essential to the field of bioelectronics.…”