Managing Local Order in Conjugated Polymer Blends via Polarity Contrast

Matthew J Dyson, Eirini Lariou, Jaime Martin, Ruipeng Li, Harikrishna Erothu, Guillaume Wantz, Paul D Topham, Olivier J. Dautel, Sophia C. Hayes, Paul N. Stavrinou, Natalie Stingelin

Research output: Contribution to journalArticlepeer-review


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.

Original languageEnglish
Pages (from-to)6540-6547
Number of pages8
JournalChemistry of Materials
Issue number17
Early online date6 Mar 2019
Publication statusPublished - 10 Sept 2019

Bibliographical note

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).


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