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Self-assembled polymeric solid films with temperature-induced large and reversible photonic-bandgap switching

Nature Materials volume 3, pages 872–876 (2004)Cite this article

Abstract

In aqueous solutions the response of polymers and biological matter to external conditions, such as temperature and pH, is typically based on the hydrophobic/hydrophilic balance and its effects on the polymer conformation1,2. In the solid state, related concepts using competing interactions could allow novel functions. In this work we demonstrate that polymeric self-assembly, reversibility of hydrogen bonding, and polymer–additive phase behaviour allow temperature response in the solid state with large and reversible switching of an optical bandgap. A complex of polystyrene-block-poly(4-vinylpyridinium methanesulphonate) and 3-n-pentadecylphenol leads to the supramolecular comb-shaped architecture with a particularly long lamellar period. The sample is green at room temperature, as an incomplete photonic bandgap due to a dielectric reflector is formed. On heating, hydrogen bonds are broken and 3-n-pentadecylphenol additionally becomes soluble in polystyrene, leading to a sharp and reversible transition at ∼125 °C to uncoloured material due to collapse of the long period. This encourages further developments, for example, for functional coatings or sensors in the solid state.

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Figure 1: PS-block-P4VP(MSA)1.0(PDP)1.5 at room temperature and at T ≳ 125 °C.
Figure 2: SAXS curves of PS-block-P4VP(MSA)1.0(PDP)1.5 at different temperatures.
Figure 3: The optical measurements of PS-block-P4VP(MSA)1.0(PDP)1.5 as a function of temperature.

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Acknowledgements

Saulius Nevas from Metrology Research Institute and Matti Kaivola from Helsinki University of Technology are acknowledged for numerous discussions and experimental assistance. Beamtime on the BM26B beamline (DUBBLE) has kindly been made available by The Netherlands Organization for Scientific Research (NWO) and we acknowledge Wim Bras for experimental assistance and discussions. The financial support from the Academy of Finland and the National Technology Agency (Finland) are gratefully acknowledged. This work was carried out in the Centre of Excellence of Finnish Academy (Bio- and Nanopolymers Research Group, 77317).

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Authors and Affiliations

  1. Department of Engineering Physics and Mathematics and Center for New Materials, Helsinki University of Technology, PO Box 2200, Espoo, FIN-02015 HUT, Finland

    Sami Valkama, Harri Kosonen, Janne Ruokolainen & Olli Ikkala

  2. VTT Information Technology, Microelectronics, Technical Research Centre of Finland, PO Box 1208, Espoo, FIN-02044 VTT, Finland

    Harri Kosonen & Tomi Haatainen

  3. Department of Physical Sciences, University of Helsinki, PO Box 64, Helsinki, FIN-00014, Finland

    Mika Torkkeli & Ritva Serimaa

  4. Laboratory of Polymer Chemistry, Dutch Polymer Institute, University of Groningen, Nijenborgh 4, Groningen, 9747 AG, The Netherlands

    Gerrit ten Brinke

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  1. Sami Valkama
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Correspondence to Gerrit ten Brinke or Olli Ikkala.

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Valkama, S., Kosonen, H., Ruokolainen, J. et al. Self-assembled polymeric solid films with temperature-induced large and reversible photonic-bandgap switching. Nature Mater 3, 872–876 (2004). https://doi.org/10.1038/nmat1254

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