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Spin Signatures of Photogenerated Radical Anions in Polymer−[70]Fullerene Bulk Heterojunctions: High Frequency Pulsed EPR Spectroscopy†

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Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 Cass Avenue, Argonne, Illinois 60439, Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040, Madrid, Spain, IMDEA-Nanociencia, Campus Universidad Autónoma de Madrid, Spain, and Julius-Maximilians University of Würzburg and Bavarian Centre for Applied Energy Research e. V. (ZAE Bayern), D-97074 Würzburg, Germany
†Part of the “Michael R. Wasielewski Festschrift”.
* Corresponding authors. E-mail: [email protected] (O.G.P.); [email protected] (V.D.).
‡Argonne National Laboratory.
§Universidad Complutense de Madrid and IMDEA-Nanociencia.
∥Julius-Maximilians University of Würzburg and Bavarian Centre for Applied Energy Research e. V.
Cite this: J. Phys. Chem. B 2010, 114, 45, 14426–14429
Publication Date (Web):April 14, 2010
https://doi.org/10.1021/jp1012347
Copyright © 2010 American Chemical Society
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Abstract

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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 (C60-PCBM), and two different soluble C70-derivates: C70-PCBM and diphenylmethano[70]fullerene oligoether (C70-DPM-OE). The first experimental identification of the negative polaron localized on the C70-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−C70 bulk heterojunctions. Comparing signals from C70-derivatives with different side-chains, we have obtained experimental proof that the polaron is localized on the cage of the C70 molecule.

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