Designing Donor–Acceptor Copolymers for Stable and High-Performance Organic Electrochemical Transistors

Organic electrochemical transistors (OECTs) are oft-used for bioelectronic applications, and a variety of OECT channel materials have been developed in recent years. However, the majority of these materials are still limited by long-term performance and stability challenges. To resolve these issues, we implemented a next-generation design of polymers for OECTs. Specifically, diketopyrrolopyrrole (DPP) building blocks were copolymerized with propylene dioxythiophene-based (Pro-based) monomers to create a donor–acceptor-type conjugated polymer (PProDOT-DPP). These PProDOT-DPP macromolecules were synthesized using a straightforward direct arylation polymerization synthetic route. The PProDOT-DPP polymer thin film exhibited excellent electrochemical response, low oxidation potential, and high crystallinity, as evidenced by spectroelectrochemical measurements and grazing incidence wide-angle X-ray scattering measurements. Thus, the resultant polymer thin films had high charge mobility and volumetric capacitance values (i.e., μC* as high as 310 F cm–1 V–1 s–1) when they were used as the active layer materials in OECT devices, which places PProDOT-DPP among the highest performing accumulation-mode OECT polymers reported to date. The performance of the PProDOT-DPP thin films was also retained for 100 cycles and over 2000 s of ON–OFF cycling, indicating the robust stability of the materials. Therefore, this effort provides a clear roadmap for the design of electrochemically active macromolecules for accumulation-mode OECTs, where crystalline acceptor cores are incorporated into an all-donor polymer. We anticipate that this will ultimately inspire future polymer designs to enable OECTs with both high electrical performance and operational stability.