context: We are able to clarify that the electrochemical doping of the polymer is still predominantly caused by the formation of ion pairs between charged polymer and PF6− anions, as DBSA itself causes irreversible doping of the polymer (Fig. 4). Fig. 4a shows the behaviour of DBSA in an electrochemical cell with no other salts present by exposing a P3HT thin film to 0.1 M DBSA in ACN electrolyte and measuring in situ ERRS. We observe the typical hole polaron signature in P3HT even at 0 V, indicating the ability of DBSA to chemically dope the polymer film when no other salts are present. We monitor the CC peak position as a function of oxidising potential and find the doping level has a minor dependence on applied bias indicated by the CC peak downshifting from 1425 cm−1 to 1417 cm−1 (Fig. 4b); the electric field causes more DBSA anions (dissociated from protons) to drift and penetrate into the P3HT film causing further doping. After discharge (0 V) the film is irreversibly doped and the CC peak position remains at 1417 cm−1 (green triangle Fig. 4a). Further evidence for irreversible p-type doping caused by DBSA is provided by changes in the UV-Vis absorbance spectra, HOMO level, and work function (see Fig. S2, ESI†). Thus, we elucidate that the mixed ionic electrolyte (with DBSA and TBA:PF6) causes reversible electrochemical doping of the polymer caused by the formation of ion pairs between charged polymer and PF6− anions. This suggests that the effect of DBSA in the mixed electrolyte is to modify the interaction between the polymer and the electrolyte allowing electrochemical doping at a lower voltage. DBSA has previously been used as a surfactant added to PEDOT:PSS formulations to improve wettability. We believe that DBSA could be having a similar effect on P3HT, interacting with the polymer and acting as a surfactant to enhance the strength of the interactions between the polymer and the electrolyte. In other words, DBSA may modulate the RED between the polymer and the solvent. We demonstrated the effect of RED between the solvent and the polymer on oxidation onset during cyclic voltammetry measurements: there is a lower RED between DCM and P3HT compared to ACN and P3HT, which results in a reduction in the oxidation onset of 0.28 V (Fig. 2). Thus, the RED between the polymer and the electrolyte solvent appears to influence the injection barrier into the film. By adding DBSA to the electrolyte, it may reduce the RED, thus causing a higher mass in the polymer film (solvent and ions), ultimately decreasing the injection barrier into the film.
answer: 0.1 M DBSA in ACN 