Chemical doping is a vital tool for tuning electronic properties of conjugated polymers. Most single electron acceptors used for p-doping necessitate high dopant concentrations to achieve good electrical conductivity. However, high-molar doping ratios hamper doping efficiency. Here a new concept of using multielectron acceptor (MEA) salts as dopants for conjugated polymers is presented. Two novel MEA salts are synthesized and their doping efficiency towards two polymers differing in their dielectric properties are compared with two single electron acceptors such as NOPF6 and magic blue. Cutting-edge methods such as ultraviolet photoelectron spectroscopy/X-ray photoelectron spectroscopy (XPS), impedance spectroscopy, and density of states analysis in addition to UV-vis-NIR absorption, spectroelectrochemistry, and Raman spectroscopy methods are used to characterize the doped systems. The tetracation salt improves the conductivity by two orders of magnitude and quadruples the charge carrier concentration compared to single electron acceptors for the same molar ratio. The differences in charge carrier density and activation energy on doping are delineated. Further, a strong dependency of the carrier release on the polymer polarity is observed. High carrier densities at reduced dopant loadings and improved doping efficacies using MEA dopants offer a highly efficient doping strategy for conjugated polymers.
Keywords: doping; electron transfer; polymers; radical ions; semiconductors.
© 2021 The Authors. Macromolecular Rapid Communications published by Wiley-VCH GmbH.