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Microstructure formation in molecular and polymer semiconductors assisted by nucleation agents

Nature Materials volume 12, pages 628–633 (2013)Cite this article

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Abstract

Additives, including nucleating agents, have been used to regulate the solidification process of (semi-)crystalline polymer solids and thus control both their crystallite dimensions and shape1,2,3,4,5. Here, we demonstrate that minute amounts (0.1–1 wt%) of commercially available nucleating agents can be used to efficiently manipulate the solidification kinetics of a wide range of organic semiconductors—including poly(3-alkylthiophene)s, the fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and 6,13-bis(triisopropyl-silylethynyl) (TIPS) pentacene—when processed from the melt, solution or solid state, without adversely affecting the semiconductors’ electronic properties. Heterogeneous nucleation increases the temperature of and rate of crystallization of poly(3-alkylthiophene)s, permits patterning of crystallites at pre-defined locations in PCBM, and minimizes dewetting of films of TIPS-pentacene formed by inkjet printing. Nucleating agents thus make possible the fabrication of thin-film transistors with uniform electrical characteristics at high yield.

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Figure 1: Controlled nucleation of polythiophenes from the melt and in solution.
Figure 2: Heterogeneous nucleation of PCBM with nucleation agents.
Figure 3: Beneficial features of using nucleation agents in combination with organic semiconductors.
Figure 4: Use of nucleation agents reduces undesirable dewetting effects during inkjet printing of small-molecule semiconducting inks.

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Acknowledgements

N.D.T. acknowledges support from the NSF IRFP (OISE-1201915), NSF ConvEne IGERT Program (NSF-DGE 0801627), and NSF Graduate Research Fellowship. C.G.S., C.J.H. and M.L.C. thank the NSF ICC program (CHE-1026664) and the NSF SOLAR program (CHE-1035292) for additional support of this work. Portions of this research (N.D.T., C.J.H. and M.L.C.) were carried out at the MRL Central Facilities, which are supported by the MRSEC Program of the NSF under Award No. DMR-1121053; a member of the NSF-funded Materials Research Facilities Network (www.mrfn.org). C.G.S. was supported as part of the Center for Energy Efficient Materials, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001009. G.R. and O.R. acknowledge Laboratory Directed Research and Development (LDRD) funding under award number 06RF1201 from NREL. We are also very grateful to the UK’s Engineering and Physical Sciences Research Council (EP/G060738/1), the Dutch Polymer Institute (LATFE programme) and the ACS Petroleum Fund (New Directions Proposal) for financial support. N.S. is furthermore supported by a European Research Council (ERC) Starting Independent Researcher Fellowship under the grant agreement No. 279587. Portions of this research were also carried out at the SSRL, a national user facility operated by Stanford University on behalf of the US Department of Energy, Office of Basic Energy Sciences.

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Authors and Affiliations

  1. Materials Department and Materials Research Laboratory, University of California Santa Barbara, Santa Barbara, California 93117, USA

    Neil D. Treat, Christopher G. Shuttle, Craig J. Hawker & Michael L. Chabinyc

  2. Department of Materials, Imperial College London, London SW7 2AZ, UK

    Neil D. Treat, Jennifer A. Nekuda Malik, Liyang Yu & Natalie Stingelin

  3. Centre for Plastic Electronics, Imperial College London, London SW7 2AZ, UK

    Neil D. Treat, Jennifer A. Nekuda Malik, Liyang Yu, Paul Smith & Natalie Stingelin

  4. Chemical and Materials Science Center, National Renewable Energy Laboratory, 15015 Denver West Parkway, Golden, Colorado 80401, USA

    Obadiah Reid & Garry Rumbles

  5. Department of Materials, Eidgenössische Technische Hochschule (ETH) Zürich, CH-8093 Zürich, Switzerland

    Paul Smith & Natalie Stingelin

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  1. Neil D. Treat
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Contributions

N.D.T. prepared and characterized samples, except for those used in OFETs. L.Y. prepared and characterized the OFETs. J.A.N.M. prepared samples for DSC and TRMC, C.G.S. performed TOF measurements, and O.R. prepared TRMC samples and performed TRMC measurements. N.D.T., N.S., M.L.C., C.J.H, P.S., and G.R. designed the experiments and prepared the manuscript.

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Correspondence to Michael L. Chabinyc or Natalie Stingelin.

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Treat, N., Nekuda Malik, J., Reid, O. et al. Microstructure formation in molecular and polymer semiconductors assisted by nucleation agents. Nature Mater 12, 628–633 (2013). https://doi.org/10.1038/nmat3655

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