Visible‐Light‐Driven Aqueous Polymerization Enables in Situ Formation of Biocompatible, High‐Performance Organic Mixed Conductors for Bioelectronics

Abstract Polymer‐based organic mixed ion‐electron conductors (OMIECs) are a class of materials offering unique coupled dual charge transport characteristics along with appealing properties including mechanical softness, biocompatibility, tunability, volumetric capacitance, and stability. These features have been exploited in devices including organic electrochemical transistors (OECTs), neuromorphic computing, energy storage, sensors, neural electrodes, and actuators. Conventionally, OMIEC polymers are prepared through chemical, vapor‐phase, electrochemical, or enzymatic polymerization, typically relying on oxidants, metal catalysts, and/or organic solvents, significantly limiting their scalability, sustainability, and biocompatibility. Here, we introduce an initiator‐free, visible‐light‐induced polymerization of water‐soluble conducting polymer precursors, enabling facile formation of high‐performance and inherently biocompatible OMIECs. This novel approach allows direct photopatterning and seamless film deposition and manufacturing of OECTs across rigid, flexible, and biological substrates, exemplified by glass, textiles, and mouse skin (in vivo). Through careful optimization of the photopolymerization process, resulting OMIECs possess state‐of‐the‐art electrical, electrochemical, and device properties along with exceptional compatibility and conformability with various flexible and biological surfaces. Finally, we demonstrate the utility of these photopatterned electrodes, manufactured directly on mouse skin in vivo, where they significantly enhance the recording efficacy and signal‐to‐noise ratio of low‐frequency brain activity in anesthetized mice.