Electron-Ion Coupling Breaks Energy Symmetry in Organic Electrochemical Transistors

Abstract: Organic electrochemical transistors are extensively studied for applications ranging from bioelectronics to analog and neuromorphic computing. Despite significant advances, the fundamental interactions between the polymer semiconductor channel and the electrolyte, which critically determine the device performance, remain underexplored. Here, we examine the coupling between the benchmark semiconductor PEDOT:PSS and ionic liquids to explain the bistable and non-volatile behavior observed in OECTs. Using X-ray scattering and spectroscopy techniques, we demonstrate how the electrolyte modifies the channel composition, enhances molecular order, and reshapes the electronic and energetic landscape. Notably, the observed bistability arises from asymmetric and path-dependent energetics during doping and dedoping, resulting in two distinct, stable states, driven by a direct interaction between the electronic and ionic charge carriers. These findings highlight a compelling method to control charge carrier dynamics via the electrolyte, positioning it as a powerful yet underutilized tool for enabling novel device functionalities.