Spin signatures of photogenerated radical anions in polymer-[70]fullerene bulk heterojunctions: high frequency pulsed EPR spectroscopy.

Charged polarons in thin films of polymer-fullerene composites are investigated by light-induced electron paramagnetic resonance (EPR) at 9.5 GHz (X-band) and 130 GHz (D-band). The materials studied were poly(3-hexylthiophene) (PHT), [6,6]-phenyl-C61-butyric acid methyl ester (C(60)-PCBM), and two different soluble C(70)-derivates: C(70)-PCBM and diphenylmethano[70]fullerene oligoether (C(70)-DPM-OE). The first experimental identification of the negative polaron localized on the C(70)-cage in polymer-fullerene bulk heterojunctions has been obtained. When recorded at conventional X-band EPR, this signal is overlapping with the signal of the positive polaron, which does not allow for its direct experimental identification. Owing to the superior spectral resolution of the high frequency D-band EPR, we were able to separate light-induced signals from P(+) and P(-) in PHT-C(70) bulk heterojunctions. Comparing signals from C(70)-derivatives with different side-chains, we have obtained experimental proof that the polaron is localized on the cage of the C(70) molecule.