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Measurement of molecular motion in organic semiconductors by thermal diffuse electron scattering

Nature Materials volume 12, pages 1045–1049 (2013)Cite this article

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Abstract

Many of the remarkable electrical and optical properties of organic semiconductors are governed by the interaction of electronic excitations with intra- and intermolecular vibrational modes. However, in specific systems this interaction is not understood in detail at a molecular level and this has been due, at least in part, to the lack of easy-to-use and widely available experimental probes of the structural dynamics. Here we demonstrate that thermal diffuse scattering in electron diffraction patterns from organic semiconductors, such as 6,13-bistriisopropyl-silylethynyl pentacene, allows the dominant lattice vibrational modes to be probed directly. The amplitude and direction of the dominant molecular motions were determined by comparison of the diffuse scattering with simulations and molecular dynamics calculations. Our widely applicable approach enables a much deeper understanding of the structural dynamics in a broad range of organic semiconductors.

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Figure 1: Structure of TIPS-pentacene and its associated TDS observed in electron diffraction patterns.
Figure 2: Beam damage study of TIPS-pentacene.
Figure 3: Analysis of TDS in electron diffraction patterns and molecular dynamics simulations.

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Acknowledgements

Two of the authors, A.S.E. and P.A.M., acknowledge financial support through EPSRC grant EP/H017712 and from the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007-2013)/ERC grant agreement 291522-3DIMAGE and the Seventh Framework Programme of the European Commission: ESTEEM2, contract number 312483. H.S. would like to thank the EPSRC for financial support through EP/G060738/1 and A.T. would like to thank The Leverhulme Trust for support.

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Authors and Affiliations

  1. Department of Materials Science and Metallurgy, University of Cambridge, Pembroke Street, Cambridge CB2 3QZ, UK

    Alexander S. Eggeman & Paul A. Midgley

  2. Cavendish Laboratory, University of Cambridge, JJ Thompson Avenue, Cambridge CB3 0HE, UK

    Steffen Illig & Henning Sirringhaus

  3. Department of Chemistry and Centre for Scientific Computing, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, UK

    Alessandro Troisi

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  1. Alexander S. Eggeman
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  2. Steffen Illig
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  3. Alessandro Troisi
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  5. Paul A. Midgley
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Contributions

The experimental electron diffraction work was performed jointly by A.S.E. and S.I., with interpretation of the diffraction patterns by A.S.E., S.I. and P.A.M.. Electron diffraction simulations were conducted by A.S.E. and electron irradiation studies were performed by S.I. Molecular dynamics simulations were performed by A.T. The text was written primarily by A.S.E. and S.I. with significant input from A.T., H.S. and P.A.M.

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Correspondence to Alexander S. Eggeman or Steffen Illig.

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The authors declare no competing financial interests.

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Eggeman, A., Illig, S., Troisi, A. et al. Measurement of molecular motion in organic semiconductors by thermal diffuse electron scattering. Nature Mater 12, 1045–1049 (2013). https://doi.org/10.1038/nmat3710

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