Electrochemical Doping in Ordered and Disordered Domains of Organic Mixed Ionic–Electronic Conductors

Abstract Conjugated polymers are increasingly used as organic mixed ionic–electronic conductors in electrochemical applications for neuromorphic computing, bioelectronics, and energy harvesting. The design of efficient electrochemical devices relies on large modulations of the polymer conductivity, fast doping/dedoping kinetics, and high ionic uptake. In this work, structure–property relations are established and control of these parameters by the co‐existence of order and disorder in the phase morphology is demonstrated. Using in situ time‐resolved spectroelectrochemistry, resonant Raman, and terahertz (THz) conductivity measurements, the electrochemical doping in the different morphological domains of poly(3‐hexylthiophene) (P3HT) is investigated. The main finding is that bipolarons are found preferentially in disordered polymer regions, where they are formed faster and are thermodynamically more favored. On the other hand, polarons show a preference for ordered domains, leading to drastically different bipolaron/polaron ratios and doping/dedoping dynamics in the distinct regions. A significant enhancement of the electronic conductivity is evident when bipolarons start forming in the disordered regions, while the presence of bipolarons in the ordered regions is detrimental for transport. This study provides significant advances in the understanding of the impact of morphology on the electrochemical doping of conjugated polymers and the induced increase in conductivity.