Managing Local Order in Conjugated Polymer Blends via Polarity Contrast


The optoelectronic landscape of conjugated polymers is intimately related to their molecular arrangement and packing, with minute changes in local order, such as chain conformation and torsional backbone order/disorder, frequently having a substantial effect on macroscopic properties. While many of these local features can be manipulated via chemical design, the synthesis of a series of compounds is often required to elucidate correlations between chemical structure and macromolecular ordering. Here, we show that blending semiconducting polymers with insulating commodity plastics enables controlled manipulation of the semiconductor backbone planarity. The key is to create a polarity difference between the semiconductor backbone and its side chains, while matching the polarity of the side chains and the additive. We demonstrate the applicability of this approach through judicious comparison of regioregular poly(3-hexylthiophene) (P3HT) with two of its more polar derivatives, namely the diblock copolymer poly(3-hexylthiophene)-block-poly(ethylene oxide) (P3HT-b-PEO) and the graft polymer poly[3-but(ethylene oxide)thiophene] (P3BEOT), as well as their blends with poly(ethylene oxide) (PEO). Proximity between polar side chains and a similarly polar additive reduces steric hindrance between individual chain segments by essentially "expelling" the side chains away from the semiconducting backbones. This process, shown to be facilitated via exposure to polar environments such as humid air/water vapor, facilitates backbone realignment toward specific chain arrangements and, in particular, planar backbone configurations.

Publication DOI:
Divisions: College of Engineering & Physical Sciences > Aston Institute of Materials Research (AIMR)
College of Engineering & Physical Sciences
College of Engineering & Physical Sciences > Aston Polymer Research Group
Additional Information: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see Funding: PDT and HE thank funding from the European Union Seventh Framework Program (FP7/2010 SYNABCO n° 273316 and FP7/2011 under grant agreement ESTABLIS n° 290022).
Uncontrolled Keywords: General Chemistry,General Chemical Engineering,Materials Chemistry
Publication ISSN: 1520-5002
Last Modified: 08 Jul 2024 07:48
Date Deposited: 13 Mar 2019 11:47
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Related URLs: http://pubs.acs ... emmater.8b05259 (Publisher URL)
http://www.scop ... tnerID=8YFLogxK (Scopus URL)
PURE Output Type: Article
Published Date: 2019-09-10
Published Online Date: 2019-03-06
Accepted Date: 2019-03-06
Authors: Dyson, Matthew J
Lariou, Eirini
Martin, Jaime
Li, Ruipeng
Erothu, Harikrishna
Wantz, Guillaume
Topham, Paul D (ORCID Profile 0000-0003-4152-6976)
Dautel, Olivier J.
Hayes, Sophia C.
Stavrinou, Paul N.
Stingelin, Natalie



Version: Accepted Version

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