Post-Fabrication Deprotection of Semiconducting Polymers for High-Performance Organic Electrochemical Transistors

Abstract Conventionally, the development of high-performance organic electrochemical transistor (OECT) devices heavily depends on side-chain optimization of glycolated and alkylated organic mixed ionic-electronic conducting polymers (OMIECs), which typically leads to a compromise between solubility and performance. In this study, we present a versatile design strategy employing silyl-protected side chains which can be acid-cleaved in a post-fabrication process to reveal short chains with alcohol termini, which would otherwise be unprocessable by conventional coating methods due to their insolubility. This approach decouples solubility from final device functionality, enabling solution processability during fabrication while ultimately optimizing hydrophilicity and charge transport in devices. Using PgBTTT and P100 as model polymer backbones, we demonstrate that their alcohol-functionalized analogues exhibit high μC*, excellent solvent resistance, and good electrochemical stability compared to their glycolated counterparts. Spectroelectrochemical and GIWAXS analyses reveal enhanced doping efficiency and reduced onset potentials, arising from favorable morphological reorganization upon cleavage. Overall, this work establishes alcohol functionalization as an attractive alternative to glycolation, expanding the chemical space for OMIEC device optimization and providing a platform for next-generation high-performance OECT materials.