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High-Resolution Chemical Identification of Polymer Blend Thin Films Using Tip-Enhanced Raman Mapping

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Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands
Dutch Polymer Institute, P.O. Box 902, 5600 AX Eindhoven, The Netherlands
§ Department of Physics and Astronomy, University of Glasgow, Glasgow G12 8QQ, Scotland, United Kingdom
*E-mail [email protected]. Tel +31 (0)40 2473132, fax +31 (0)40 2445619.
Cite this: Macromolecules 2011, 44, 8, 2852–2858
Publication Date (Web):March 23, 2011
Copyright © 2011 American Chemical Society

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    Abstract Image

    Nanoscale chemical identification is required for the analysis of functional materials with fine structures. For the first time, high-resolution tip-enhanced Raman mapping (TERM) was applied to a polymer system: poly(methyl methacrylate) (PMMA)/poly(styrene-co-acrylonitrile) (SAN) thin films. Before TERM measurements were performed, the linear enhancement of tip-enhanced Raman spectroscopy (TERS) was optimized in terms of maximum Raman intensity. Up to 15 times of linear enhancement was obtained, as compared to the (conventional) confocal Raman intensity. The enhancement factor of TERS is greater than 1500 if taking the 100 times smaller probing area into account. As a result, a short exposure time was sufficient for high-resolution TERM measurements. Using TERM, the phase separation behavior of PMMA/SAN thin films was monitored by chemical recognition of local composition. The interface width (∼200 nm) at the early stage of phase evolution was visualized. The comparison of TERM images at different stages of the phase separation process revealed an unexpected transition of PMMA from the dispersed phase to the continuous phase. This morphology transition of PMMA/SAN is briefly discussed in terms of the glass transition temperature, interface, and surface tension.

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    AFM height images of films I and II. Estimation of the Flory−Huggins interaction parameter χ. This material is available free of charge via the Internet at

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