Nonaggregating Doped Polymers Based on Poly(3,4-Propylenedioxythiophene)

TitleNonaggregating Doped Polymers Based on Poly(3,4-Propylenedioxythiophene)
Publication TypeJournal Article
Year of Publication2019
AuthorsMazaheripour, Amir, Elayne M. Thomas, Rachel A. Segalman, and Michael L. Chabinyc

Electrical doping of organic semiconductors is critical for their use in electrical devices. However, many high-performance semiconductors exhibit drastically reduced solubilities when doped in solution, making it difficult to deconvolute the roles of doping and morphological changes on their electrical properties. Here, we report the synthesis of a semiconducting polymer based on poly(3,4-propylenedioxythiophene) (ProDOT) substituted with oligo(ethylene glycol) (EG) side chains that is designed to solvate dopant molecules. When doped with F4TCNQ in solution, the polymer P(ProDOT-EG) undergoes efficient charge transfer while remaining soluble with no indication of aggregation. The electrical conductivity of thin films cast from heavily doped solutions is ∼1 S/cm; optical spectroscopy reveals that the doping efficiency is reduced upon formation of the solid film. Diffusion of F4TCNQ from the vapor phase into films of neutral P(ProDOT-EG) yields comparable conductivities to films cast from doped solutions. Absorption spectroscopy and X-ray diffraction of doped films reveal that the doping efficiency and nature of charge carriers (polaron or bipolaron) are strongly affected by the processing route. The lack of the localized polaron signature for films doped by infiltration of the dopant from the vapor phase indicates that morphology has a large role in determining the nature of the charge carriers in semiconducting polymers.