A Universal, Highly Stable Dopant System for Organic Semiconductors Based on Lewis-Paired Dopant Complexes

Chemical doping of organic semiconductors is an essential enabler for applications in electronic and energy-conversion devices such as thermoelectrics. Here, Lewis-paired complexes are advanced as high-performance dopants that address all the principal drawbacks of conventional dopants in terms of limited electrical conductivity, thermal stability, and generality. The study focuses on the Lewis acid B(C₆F₅)₃ (BCF) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F₄TCNQ) bearing Lewis-basic −CN groups. Due to its high electron affinity, BCF:F₄TCNQ dopes an exceptionally wide range of organic semiconductors, over 20 of which are investigated. Complex activation and microstructure control lead to conductivities for poly(3-hexylthiophene) (P3HT) exceeding 300 and 900 S cm^–1 for isotropic and chain-oriented films, respectively, resulting in a 10 to 50 times larger thermoelectric power factor compared to those obtained with neat dopants. Moreover, BCF:F₄TCNQ-doped P3HT exhibits a 3-fold higher thermal dedoping activation energy compared to that obtained with neat dopants and at least a factor of 10 better operational stability.