High Conductivity and Electron-Transfer Validation in an n-Type Fluoride-Anion-Doped Polymer for Thermoelectrics in Air

Air-stable and soluble tetrabutylammonium fluoride (TBAF) is demonstrated as an efficient n-type dopant for the conjugated polymer ClBDPPV. Electron transfer from F⁻ anions to the π-electron-deficient ClBDPPV through anion–π electronic interactions is strongly corroborated by the combined results of electron spin resonance, UV–vis–NIR, and ultraviolet photoelectron spectroscopy. Doping of ClBDPPV with 25 mol% TBAF boosts electrical conductivity to up to 0.62 S cm⁻¹, among the highest conductivities that have been reported for solution-processed n-type conjugated polymers, with a thermoelectric power factor of 0.63 µW m⁻¹ K⁻² in air. Importantly, the Seebeck coefficient agrees with recently published correlations to conductivity. Moreover, the F⁻-doped ClBDPPV shows significant air stability, maintaining the conductivity of over 0.1 S cm⁻¹ in a thick film after exposure to air for one week, to the best of our knowledge the first report of an air-stable solution-processable n-doped conductive polymer with this level of conductivity. The result shows that using solution-processable small-anion salts such as TBAF as an n-dopant of organic conjugated polymers possessing lower LUMO (lowest unoccupied molecular orbital), less than −4.2 eV) can open new opportunities toward high-performance air-stable solution-processable n-type thermoelectric (TE) conjugated polymers.

Simple, air-stable, solution-processable tetrabutylammonium fluoride (TBAF) doping of an electron-deficient polymer can boost the electrical conductivity to 0.62 S cm⁻¹ and maintain it at >0.1 S cm⁻¹ in a thick film after exposure to air for one week, the first report of an air-stable solution-processable n-doped conductive polymer with this conductivity level. Electron transfer is verified using multiple techniques.

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