Light-Induced ESR Studies of Quadrimolecular Recombination Kinetics of Photogenerated Charge Carriers in Regioregular Poly(3-alkylthiophene)/C60 Composites: Alkyl Chain Dependence

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Light-induced ESR (LESR) measurements have been performed on the composites of regioregular poly(3-alkylthiophene) (RR-P3AT) and C60 by using polymers having different alkyl chains (CmH2m+1 with $m=6$, 8, 10, 12). The quadrimolecular recombination (QR) kinetics of photogenerated charge carriers, previously reported, have been confirmed for all the composites from the excitation power ($I_{\text{ex}}$) dependence of the LESR intensity showing an ${\sim}I_{\text{ex}}^{0.25}$ dependence. The time decay of LESR intensity is also consistent with the QR model. Considering that only bimolecular recombination is observed in regiorandom polymer composites, the occurrence of QR strongly suggests the formation of doubly charged states, either bipolarons or polaron pairs on the regioregular polymer chains. On the other hand, the QR rate constant $\gamma$ has been found to exhibit weak alkyl chain dependence, contrary to the case of the field-effect mobility of pure regioregular polymers with systematic alkyl chain dependence. This implies the significant contribution of the polymer and fullerene interface in determining $\gamma$.
2007-08-15