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Morphology evolution via self-organization and lateral and vertical diffusion in polymer:fullerene solar cell blends


Control of blend morphology at the microscopic scale is critical for optimizing the power conversion efficiency of plastic solar cells based on blends of conjugated polymer with fullerene derivatives. In the case of bulk heterojunctions of regioregular poly(3-hexylthiophene) (P3HT) and a soluble fullerene derivative ([6,6]-phenyl C61-butyric acid methyl ester, PCBM), both blend morphology and photovoltaic device performance are influenced by various treatments, including choice of solvent, rate of drying, thermal annealing and vapour annealing. Although the protocols differ significantly, the maximum power conversion efficiency values reported for the various techniques are comparable (4–5%). In this paper, we demonstrate that these techniques all lead to a common arrangement of the components, which consists of a vertically and laterally phase-separated blend of crystalline P3HT and PCBM. We propose a morphology evolution that consists of an initial crystallization of P3HT chains, followed by diffusion of PCBM molecules to nucleation sites, at which aggregates of PCBM then grow.

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Figure 1: Absorption spectra for P3HT:PCBM films and EQE spectra for P3HT:PCBM devices.
Figure 2: Lateral segregation in P3HT:PCBM films as observed by optical microscopy, Raman spectroscopy and atomic force microscopy.
Figure 3: Vertical composition profiles in P3HT:PCBM films as deduced using ellipsometry.
Figure 4: Real-time evolution of P3HT:PCBM blend morphology.


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The authors thank the UK Engineering and Physical Sciences Research Council (project no. EP4/C5403361) and BP Solar (OSCER project) for financial support. We also thank I. McCulloch, M. Heeney and M. Giles, from Merck Chemicals, for supplying the P3HT polymer. M.C.-Q. thanks S. Choulis, S. Sidat and S. Sohel for useful discussions at the early stages of these investigations, J. Dane for help with the evaporation mask designs and Rod Bottom and Phil Williams (Mettler Toledo Ltd) for their help with the real-time microscopy measurements.

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Correspondence to Mariano Campoy-Quiles, Donal D. C. Bradley or Jenny Nelson.

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Supplementary figures S1-S4 and supplementary table S1 (PDF 341 kb)

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Campoy-Quiles, M., Ferenczi, T., Agostinelli, T. et al. Morphology evolution via self-organization and lateral and vertical diffusion in polymer:fullerene solar cell blends. Nature Mater 7, 158–164 (2008).

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