Revealing photochromic function and its physical mechanism in electrochromic material PEDOT:PSS

Abstract Integrating electrochromic (EC) and photochromic (PC) functions within a single material system holds great significance for the development of next-generation intelligent responsive materials. Traditional organic photochromic materials are all small molecules and oligomers, which require the photochemical response of specific photosensitive groups. However, PEDOT:PSS, a classic electrochromic polymer, has never been reported to exhibit photochromic properties due to the absence of photosensitive groups. Herein, we report for the first time the photochromic properties of PEDOT:PSS films, demonstrating their simultaneous capability of multi-field coupling response in the aspects of light, electricity and chemistry. The composite film undergoes a rapid color change from light blue to dark blue under ultraviolet light irradiation. This is attributed to the transformation process from the bipolarons state to the polarons state in the PEDOT:PSS, induced by photogenerated electrons as confirmed by EPR and Raman analyses. Furthermore, the developed hydrogel system enhances charge separation, yielding a 30.1% relative transmittance change and month-long stability. This work fills the long-standing gap in the understanding of the photochromic and electrochromic mechanisms of PEDOT:PSS, providing fundamental insights into carrier dynamics at organic−inorganic interfaces and laying the foundation for the development of multi-mode stimuli-responsive devices.