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Measurement of molecular mixing at a conjugated polymer interface by specular and off-specular neutron scattering

David James, Anthony Higgins Orcid Logo, Paul Rees Orcid Logo, Mark Geoghegan, M. Rowan Brown, Shion-Seng Chang, Dyfrig Môn, Robert Cubitt, Robert Dalgliesh, Philipp Gutfreund, Rowan Brown Orcid Logo

Soft Matter, Volume: 11, Issue: 48, Pages: 9393 - 9403

Swansea University Authors: Anthony Higgins Orcid Logo, Paul Rees Orcid Logo, Rowan Brown Orcid Logo

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DOI (Published version): 10.1039/C5SM02008E

Abstract

Measurements have been performed on thermally equilibrated conjugated-polymer/insulating-polymer bilayers, using specular and off-specular neutron reflectivity. While specular reflectivity is only sensitive to the structure normal to the sample, off-specular measurements can probe the structure of t...

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Published in: Soft Matter
ISSN: 1744-683X 1744-6848
Published: 2015
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URI: https://cronfa.swan.ac.uk/Record/cronfa26063
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Abstract: Measurements have been performed on thermally equilibrated conjugated-polymer/insulating-polymer bilayers, using specular and off-specular neutron reflectivity. While specular reflectivity is only sensitive to the structure normal to the sample, off-specular measurements can probe the structure of the buried polymer/polymer interface in the plane of the sample. Systematic analysis of the scattering from a set of samples with varying insulating-polymer-thickness, using the distorted-wave Born approximation (DWBA), has allowed a robust determination of the intrinsic width at the buried polymer/polymer interface. The quantification of this width (12 Å ± 4 Å) allows us to examine aspects of the conjugated polymer conformation at the interface, by appealing to self-consistent field theory (SCFT) predictions for equilibrium polymer/polymer interfaces in the cases of flexible and semi-flexible chains. This analysis enables us to infer that mixing at this particular interface cannot be described in terms of polymer chain segments that adopt conformations similar to a random walk. Instead, a more plausible explanation is that the conjugated polymer chain segments become significantly oriented in the plane of the interface. It is important to point out that we are only able to reach this conclusion following the extensive analysis of reflectivity data, followed by comparison with SCFT predictions. It is not simply the case that conjugated polymers would be expected to adopt this kind of oriented conformation at the interface, because of their relatively high chain stiffness. It is the combination of a high stiffness and a relatively narrow intrinsic interfacial width that results in a deviation from flexible chain behaviour.
College: Faculty of Science and Engineering
Issue: 48
Start Page: 9393
End Page: 9403