Attenuated total reflection Fourier transform infrared (ATR-FTIR) investigations on the doping processes in substituted poly(isothianaphtene methine) (PIM), a new low band-gap conjugated polymer, are reported. The doping was studied in situ during chemical p-doping (oxidation) by iodine and during electrochemical p-doping (oxidation) and n-doping (reduction). During both signs of doping, infrared active vibrational (IRAV) bands due to strong coupling of the electrons to lattice vibrations are observed. The results are compared to FT-Raman spectra. Electrochemical p-doping shows two different doping regimes depending on the electrochemical potential. The narrow linewidth and low absorption intensities of the IRAV bands indicate a strong localization of the doping induced charge carriers, which is ascribed to a tilted geometry to the conjugated backbone due to steric repulsion effects.
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