Designing Light‐Sensitive Organic Semiconductors with Azobenzenes for Photoelectrochemical Transistors as Neuromorphic Platforms

Organic neuromorphic electronics aim to emulate the adaptive behavior of biological synapses using soft, biocompatible materials capable of analog and stimulus-responsive modulation. While azobenzene-based semiconductors provide reversible light-induced switching, their application in mixed ionic-electronic conductors for neuromorphic systems remains largely unexplored. In this study, photoresponsive organic photoelectrochemical transistors (OPECTs) are engineered by functionalizing PEDOT:PSS with azobenzene derivatives bearing nitro or fluorine substituents. These modifications alter the electronic structure and surface properties of the gate, enabling systematic tuning of interfacial capacitance, a critical parameter governing photogating and neuromorphic response. Optical and electrochemical measurements, supported by DFT calculations reveal that substituent-dependent modulation of bulk and interfacial capacitance directly impacts gating efficiency. Devices exhibit reversible, analog conductance changes under optical and electrical co-stimulation, emulating both short- and long-term synaptic plasticity. These results establish a structure–capacitance–function relationship and provide a chemically tunable platform for the development of light-responsive neuromorphic interfaces in adaptive bioelectronics.