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Block copolymers with stable radical and fluorinated groups by ATRP

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Abstract

Polymers with stable radical groups are promising materials for organic electronic devices due to their unique redox activity. Block copolymers with one redox active block could be used in nanostructured devices for electronic applications. We report on the synthesis and characterization of such multifunctional block copolymers in which phase separation on the 10 nm (half pitch) scale is achieved by using fluorinated blocks. Fluorination of one block increases the degree of phase separation and leads to smaller accessible domain sizes. Block copolymers with 60%, 80% and 90% of a stable radical containing block and either fluorinated or non-fluorinated second blocks were made by atom transfer radical polymerization, and their microstructure formation as a function of fluorine content is described after solvent vapor or thermal annealing. Electrical characterization of such a partly fluorinated block copolymer shows their potential for electronic devices.

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Acknowledgments

C. L. acknowledges financial support by the Deutsche Forschungsgemeinschaft (German Research Foundation, Forschungsstipendium Li 2526/2-1). A. M. acknowledges support by a seed grant from the Cornell Center for Materials Research, an NSF MRSEC program (DMR-1120296). AFM measurements were performed at the Cornell NanoScale Facility, a member of the National Nanotechnology Infrastructure Network, which is supported by the National Science Foundation (grant ECCS-0335765). NMR spectroscopy was measured at the Cornell University NMR Facility. EPR spectroscopy was performed at ACERT, which is supported by the National Institute of General Medical Sciences of the National Institutes of Health (Award Number P41GM103521). We composed coin cells in the laboratories of Lynden A. Archer and thank Sampson Lau for assistance and help with the measurements of the charge-discharge behavior. We thank Boris Dzikovski for help with EPR measurements.

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Author notes

  1. Clemens Liedel

    Present address: Department of Colloid Chemistry, Max Planck Institute of Colloids and Interfaces, 14424, Potsdam, Germany

Authors and Affiliations

  1. Materials Science and Engineering, Cornell University, 214 Bard Hall, Ithaca, New York, 14853, USA

    Clemens Liedel & Christopher K. Ober

  2. Applied and Engineering Physics, Cornell University, 271 Clark Hall, Ithaca, New York, 14853, USA

    Austin Moehle & Gregory D. Fuchs

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  1. Clemens Liedel
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Correspondence to Christopher K. Ober.

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For supplementary material for this article, please visit http://dx.doi.org/10.1557/mrc.2015.50

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Liedel, C., Moehle, A., Fuchs, G.D. et al. Block copolymers with stable radical and fluorinated groups by ATRP. MRS Communications 5, 441–446 (2015). https://doi.org/10.1557/mrc.2015.50

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