Controlling n‑Type Molecular Doping via Regiochemistry and Polarity of Pendant Groups on Low Band Gap Donor–Acceptor Copolymers

We demonstrate the impact of the type and position of pendant groups on the n-doping of low-band gap donor–acceptor (D–A) copolymers. Polar glycol ether groups simultaneously increase the electron affinities of D–A copolymers and improve the host/dopant miscibility compared to nonpolar alkyl groups, improving the doping efficiency by a factor of over 40. The bulk mobility of the doped films increases with the fraction of polar groups, leading to a best conductivity of 0.08 S cm^–1 and power factor (PF) of 0.24 μW m^–1 K^–2 in the doped copolymer with the polar pendant groups on both the D and A moieties. We used spatially resolved absorption spectroscopy to relate commensurate morphological changes to the dispersion of dopants and to the relative local doping efficiency, demonstrating a direct relationship between the morphology of the polymer phase, the solvation of the molecular dopant, and the electrical properties of doped films. Our work offers fundamental new insights into the influence of the physical properties of pendant chains on the molecular doping process, which should be generalizable to any molecularly doped polymer films.