Electrostatic Tailoring of Freestanding Polymeric Films for Multifunctional Thermoelectrics, Hydrogels, and Actuators

Organic conducting polymer poly­(3,4-ethylene­dioxythiophene):poly­(4-styrene­sulfonate) (PEDOT:PSS) has garnered enormous attention in organic electronics due to its low-cost solution processability, highly tunable conductivity, superior mechanical flexibility, and good biocompatibility together with excellent atmospheric stability. Nevertheless, limited electrical properties and unfavorable water instability of pristine PEDOT:PSS film impede its further implementation in a broad spectrum of practical applications. In this work, the successful tailoring of the intrinsic electrostatic interaction within PEDOT:PSS and consequent optimized electrical properties are enabled by a simple yet effective ionic salt post-treatment strategy. The choice of zinc di­[bis­(trifluoro­methylsulfonyl)­imide] (Zn­(TFSI)2) not only endows the post-treated PEDOT:PSS film with high electrical properties but also other compelling characteristics, including superior water stability, excellent mechanical flexibility, and fast humidity responsiveness. Multidimensional characterizations are conducted to gain in-depth insights into the mechanisms underlying such improved performance, ranging from intermolecular interactions, polymer conformations, and doping levels to microstructural characteristics. Benefiting from these versatile properties, the as-prepared freestanding Zn­(TFSI)2-post-treated PEDOT:PSS films can serve as promising candidates for high-performance polymeric materials integrated into multifunctional flexible electronics, including thermoelectric power generators, conductive hydrogels, and humidity-responsive actuators. This study demonstrates a facile methodology for the exploration of multifunctional conducting polymers, whose implications can extend across a wide range of next-generation wearable devices, bioelectronics, and soft robotics.