Complementary Hydrogen─Bonded Functionalized Mixed Conducting Terpolymers for High‐Performance n‐type Organic Electrochemical Transistors and Healable Inverters

Abstract

Abstract High‐performing n‐type organic electrochemical transistors (OECTs), crucial for integrated circuits in wearable bioelectronics, demand organic mixed ion‐electron conductors (OMIECs) that exhibit efficient mixed conduction and biological functionality for practical applications. However, the development of self‐healing OMIECs has not yet been achieved due to the lack of suitable synthetic strategies. Here, we present a design concept through incorporating dynamic cross‐linked hydrogen‐bonded in the polymer backbone for the first demonstration of self‐healing polymeric mixed conductors, enabling high‐performing OECTs and high gain, self‐healing inverters. These devices exhibit a mixed conducting figure of merit µ C* of 118 F cm −1 V −1 s −1 , three times higher than the copolymer without hydrogen bond, along with simultaneously improved volumetric capacitance and electron mobility. These improvements are attributed to the unique microstructure created by hydrogen bond, which results in a closer π‐π stacking distance within smaller crystalline domain sizes. Additionally, a cost‐effective post‐processing side chain removal method is proposed, which retains high performance in n‐type OECTs. Remarkably, inverters based on the hydrogen‐bonded terpolymer demonstrate high gain and self‐healing capabilities through solvent vapor exposure and annealing treatment. Insights from these terpolymers emphasize the use of dynamic hydrogen bonds in the conjugated backbone to enhance performance and enable self‐healing high‐gain inverters, advancing wearable bioelectronics for practical applications.