Activated singlet exciton fission in a semiconducting polymer

Andrew J. Musser, Mohammed Al-Hashimi, Margherita Maiuri, Daniele Brida, Martin Heeney, Giulio Cerullo, Richard H. Friend, Jenny Clark

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Abstract

Singlet exciton fission is a spin-allowed process to generate two triplet excitons from a single absorbed photon. This phenomenon offers great potential in organic photovoltaics, but the mechanism remains poorly understood. Most reports to date have addressed intermolecular fission within small-molecular crystals. However, through appropriate chemical design chromophores capable of intramolecular fission can also be produced. Here we directly observe sub-100 fs activated singlet fission in a semiconducting poly(thienylenevinylene). We demonstrate that fission proceeds directly from the initial 1Bu exciton, contrary to current models that involve the lower-lying 2Ag exciton. In solution, the generated triplet pairs rapidly recombine and decay through the 2Ag state. In films, exciton diffusion breaks this symmetry and we observe long-lived triplets which form charge-transfer states in photovoltaic blends.

Original languageEnglish
Pages (from-to)12747-12754
Number of pages8
JournalJournal of the American Chemical Society
Volume135
Issue number34
DOIs
Publication statusPublished - 28 Aug 2013

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Musser, A. J., Al-Hashimi, M., Maiuri, M., Brida, D., Heeney, M., Cerullo, G., Friend, R. H., & Clark, J. (2013). Activated singlet exciton fission in a semiconducting polymer. Journal of the American Chemical Society, 135(34), 12747-12754. https://doi.org/10.1021/ja405427j