This review summarises high performing n-type polymers for use in organic thin film transistors, organic electrochemical transistors and organic thermoelectric devices with a focus on stability issues arising in these electron transporting materials.

Conjugated polymers achieve redox activity in electrochemical devices by combining redox-active, electronically conducting backbones with ion-transporting side chains that can be tuned for different electrolytes. In aqueous electrolytes, redox activity can be accomplished by attaching hydrophilic side chains to the polymer backbone, which enables ionic transport and allows volumetric charging of polymer electrodes. While this approach has been beneficial for achieving fast electrochemical charging in aqueous solutions, little is known about the relationship between water uptake by the polymers during electrochemical charging and the stability and redox potentials of the electrodes, particularly for electron-transporting conjugated polymers. We find that excessive water uptake during the electrochemical charging of polymer electrodes harms the reversibility of electrochemical processes and results in irreversible swelling of the polymer. We show that small changes of the side chain composition can significantly increase the reversibility of the redox behavior of the materials in aqueous electrolytes, improving the capacity of the polymer by more than one order of magnitude. Finally, we show that tuning the local environment of the redox-active polymer by attaching hydrophilic side chains can help to reach high fractions of the theoretical capacity for single-phase electrodes in aqueous electrolytes. Our work shows the importance of chemical design strategies for achieving high electrochemical stability for conjugated polymers in aqueous electrolytes.

Recent research demonstrates the viability of organic electrochemical transistors (OECTs) as an emergent technology for biosensor applications. Herein, a comprehensive summary is provided, highlighting the significant progress and most notable advances within the field of OECT‐based biosensors. The working principles of an OECT are detailed, with specific attention given to the current library of organic mixed ionic‐electronic conductor (OMIEC) channel materials utilized in OECT biosensors. The application of OECTs for metabolite, ion, neuromorphic, electrophysiological, and virus sensing as well as immunosensing is reported, detailing the breadth and scope of OECT‐based biosensors. Furthermore, an outlook and perspective on synthetic molecular design of future channel materials, specifically designed for OECT biosensors, is provided. The development of optimized channel materials, creative device architectures, and operational nuances will set the stage for OECT‐based biosensors to thrive and accelerate their clinical prevalence in the near future.