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Multicomponent semiconducting polymer systems with low crystallization-induced percolation threshold

Nature Materials volume 5, pages 950–956 (2006)Cite this article

Abstract

Blends and other multicomponent systems are used in various polymer applications to meet multiple requirements that cannot be fulfilled by a single material1,2,3. In polymer optoelectronic devices it is often desirable to combine the semiconducting properties of the conjugated species with the excellent mechanical properties of certain commodity polymers. Here we investigate bicomponent blends comprising semicrystalline regioregular poly(3-hexylthiophene) and selected semicrystalline commodity polymers, and show that, owing to a highly favourable, crystallization-induced phase segregation of the two components, during which the semiconductor is predominantly expelled to the surfaces of cast films, we can obtain vertically stratified structures in a one-step process. Incorporating these as active layers in polymer field-effect transistors, we find that the concentration of the semiconductor can be reduced to values as low as 3 wt% without any degradation in device performance. This is in stark contrast to blends containing an amorphous insulating polymer, for which significant reduction in electrical performance was reported4. Crystalline–crystalline/semiconducting–insulating multicomponent systems offer expanded flexibility for realizing high-performance semiconducting architectures at drastically reduced materials cost with improved mechanical properties and environmental stability, without the need to design all performance requirements into the active semiconducting polymer itself.

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Figure 1: Comparison of field-effect transistor performance—and corresponding grazing-incidence wide-angle X-ray diffractograms—of P3HT/PS blends of 10 wt% P3HT and 90 wt% PS (10:90 P3HT/PS).
Figure 2: Electrical characteristics and phase behaviour of P3HT/PE systems, using highly linear, semicrystalline HDPE; branched, semicrystalline LLDPE and highly branched, nearly amorphous ULDPE as the insulating matrix polymer.
Figure 3: Influence of solidification mechanism of insulating matrix material—crystallizing or vitrifying—on electronic performance and microstructure of blends with P3HT.
Figure 4: GIXD diffractograms of 10:90 P3HT/HDPEMw=120 kdalton films, which are illustrative of the dependence of the crystalline quality of the conjugated P3HT on the sequence in which the two components in such crystalline–crystalline blends solidify.

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Acknowledgements

We are indebted to I. McCulloch, M. Heeney and M. Shkunov (Merck Chemicals, Southampton, UK) for their supply of P3HT homopolymer. We acknowledge funding from the European Science Foundation through the Self-Organised Nanostructures (SONS) initiative. For the GIXD experiments, we acknowledge DanSync for financial support and the BW2/HASYLAB staff for assistance.

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Author notes

  1. Dag W. Breiby & Martin M. Nielsen

    Present address: Centre for Molecular Movies, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen Ø, Denmark

Authors and Affiliations

  1. Cavendish Laboratory, University of Cambridge, JJ Thomson Ave., Cambridge, CB3 0HE, UK

    Shalom Goffri & Henning Sirringhaus

  2. Department of Materials, ETH Zürich, Wolfgang-Pauli Str., CH-8093, Zürich, Switzerland

    Christian Müller, Natalie Stingelin-Stutzmann & Paul Smith

  3. Department of Materials, Queen Mary, University of London, Mile End Rd., London, E1 4NS, UK

    Natalie Stingelin-Stutzmann

  4. Danish Polymer Centre, Risø National Laboratory, 4000, Roskilde, Denmark

    Dag W. Breiby, Jens W. Andreasen & Martin M. Nielsen

  5. Laboratory of Macromolecular and Organic Chemistry, TU Eindhoven, 5600 MB, Eindhoven, PO Box 513, The Netherlands

    Christopher P. Radano & René A. J. Janssen

  6. Department of Chemistry, University of Durham, South Road, Durham, DH1 3LE, UK

    Richard Thompson

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Correspondence to Paul Smith or Henning Sirringhaus.

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Goffri, S., Müller, C., Stingelin-Stutzmann, N. et al. Multicomponent semiconducting polymer systems with low crystallization-induced percolation threshold. Nature Mater 5, 950–956 (2006). https://doi.org/10.1038/nmat1779

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