Highly Deformable and Durable PEDOT:PSS Printed Electrodes via Tailored Chemistry and Fabrication Synergy for Scalable Wearable Electronics

ABSTRACT Next‐generation wearable electronics demand electrodes that combine flexibility, durability, and consistent performance under mechanical deformations. Poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is a leading candidate, offering good conductivity, flexibility, and solution‐processability. However, maintaining electrical performance under mechanical deformations remains a key challenge. Moreover, conventional fabrication strategies are often cumbersome, multistep, and not amenable to large‐scale manufacturing. Herein, we report fabrication of highly deformable and durable PEDOT:PSS printed electrodes (HDDPPEs) via facile, single‐step spray pyrolysis deposition method. By tailoring PEDOT:PSS material chemistry through incorporating polyvinyl alcohol and dimethyl sulfoxide, and optimizing deposition parameters, we successfully fabricated HDDPPEs on various polymer substrates in both large‐area and micro‐patterned formats. HDDPPE S exhibited an exceptionally low sheet resistance (18.5 ± 2.6 Ω sq −1 ) (among the lowest via such a simple process), outstanding mechanical deformability (bending radius ≈2 mm), and long‐term stability exceeding 2 months, outperforming commercial ITO‐PET electrodes. Mechanistic investigations revealed that polyvinyl alcohol enhances adhesion via dual hydrogen‐bonding, while dimethyl sulfoxide induces PEDOT chain ordering through enhanced π–π stacking and phase separation, thereby enhancing conductivity. With excellent conductivity, transparency, and mechanical robustness, HDDPPEs are successfully applied in various wearable electronic devices, including wearable sensors, robotic skins, flexible triboelectric and electrochromic devices, offering scalable pathway for next‐generation wearable electronics.