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Singlet exciton fission in solution

Nature Chemistry volume 5, pages 1019–1024 (2013)Cite this article

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An Erratum to this article was published on 17 December 2013

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Abstract

Singlet exciton fission, the spin-conserving process that produces two triplet excited states from one photoexcited singlet state, is a means to circumvent the Shockley–Queisser limit in single-junction solar cells. Although the process through which singlet fission occurs is not well characterized, some local order is thought to be necessary for intermolecular coupling. Here, we report a triplet yield of 200% and triplet formation rates approaching the diffusion limit in solutions of bis(triisopropylsilylethynyl (TIPS)) pentacene. We observe a transient bound excimer intermediate, formed by the collision of one photoexcited and one ground-state TIPS-pentacene molecule. The intermediate breaks up when the two triplets separate to each TIPS-pentacene molecule. This efficient system is a model for future singlet-fission materials and for disordered device components that produce cascades of excited states from sunlight.

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Figure 1: Overview of TIPS-pentacene.
Figure 2: Transient absorption spectra of TIPS-pentacene.
Figure 3: Triplet yield in TIPS-pentacene solutions.
Figure 4: Ultrafast transient absorption spectra of TIPS-pentacene with a time resolution of 0.28 ps.
Figure 5: Photoluminescence of TIPS-pentacene solutions.
Figure 6: TDDFT analysis of TIPS-pentacene excimer structures.

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Change history

  • 21 November 2013

    In the version of this Article originally published, the colour scales on Figs 2 and 4 were incorrect. These have now been corrected in the online versions of the Article.

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Acknowledgements

B.J.W. was supported by a Herchel Smith Research Fellowship. A.J.M. received funding from a Marie Curie Scholarship. D.B. is a FNRS Research Director. Both A.J.M and D.B. acknowledge support from the European Community's Initial Training Network SUPERIOR (PITN-GA-2009-238177). Further funding for this project came from the Engineering and Physical Sciences Research Council and a pump-prime grant from the Winton Programme for the Physics of Sustainability. We thank A. Rao, K. Johnson and S. Gélinas for general discussion, and D. Howe for assistance with diffusion-ordered NMR spectroscopy.

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  1. Cavendish Laboratory, University of Cambridge, J. J. Thomson Avenue, Cambridge, UK

    Brian J. Walker, Andrew J. Musser & Richard H. Friend

  2. Laboratory for Chemistry of Novel Materials, Université de Mons, Place du Parc 20, Mons, 7000, Belgium

    David Beljonne

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Contributions

B.J.W. conceived the project, B.J.W. and A.J.M. planned and carried out the experiments, A.J.M. performed the calculations, B.J.W., A.J.M., D.B. and R.H.F. discussed the experiments and results, and B.J.W., A.J.M. and R.H.F. wrote the manuscript.

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Correspondence to Richard H. Friend.

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Walker, B., Musser, A., Beljonne, D. et al. Singlet exciton fission in solution. Nature Chem 5, 1019–1024 (2013). https://doi.org/10.1038/nchem.1801

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