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 journalArticle

Abstract

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
Volume31
Issue number17
Early online date6 Mar 2019
DOIs
Publication statusPublished - 10 Sep 2019

Fingerprint

Conjugated polymers
Polymer blends
Polyethylene oxides
Semiconducting polymers
Semiconductor materials
Thiophenes
Ethylene Oxide
Order disorder transitions
Graft copolymers
Steam
Thiophene
Optoelectronic devices
Water vapor
Block copolymers
Conformations
Ethylene
Plastics
Derivatives
Oxides
Air

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 https://pubs.acs.org/doi/10.1021/acs.chemmater.8b05259

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).

Cite this

Dyson, M. J., Lariou, E., Martin, J., Li, R., Erothu, H., Wantz, G., ... Stingelin, N. (2019). Managing Local Order in Conjugated Polymer Blends via Polarity Contrast. Chemistry of Materials, 31(17), 6540-6547. https://doi.org/10.1021/acs.chemmater.8b05259
Dyson, Matthew J ; Lariou, Eirini ; Martin, Jaime ; Li, Ruipeng ; Erothu, Harikrishna ; Wantz, Guillaume ; Topham, Paul D ; Dautel, Olivier J. ; Hayes, Sophia C. ; Stavrinou, Paul N. ; Stingelin, Natalie. / Managing Local Order in Conjugated Polymer Blends via Polarity Contrast. In: Chemistry of Materials. 2019 ; Vol. 31, No. 17. pp. 6540-6547.
@article{a1e373b22f2b45d6bc3cadfc685b4cd7,
title = "Managing Local Order in Conjugated Polymer Blends via Polarity Contrast",
abstract = "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.",
author = "Dyson, {Matthew J} and Eirini Lariou and Jaime Martin and Ruipeng Li and Harikrishna Erothu and Guillaume Wantz and Topham, {Paul D} and Dautel, {Olivier J.} and Hayes, {Sophia C.} and Stavrinou, {Paul N.} and Natalie Stingelin",
note = "This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright {\circledC} American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.chemmater.8b05259 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).",
year = "2019",
month = "9",
day = "10",
doi = "10.1021/acs.chemmater.8b05259",
language = "English",
volume = "31",
pages = "6540--6547",
journal = "Chemistry of Materials",
issn = "0897-4756",
publisher = "American Chemical Society",
number = "17",

}

Dyson, MJ, Lariou, E, Martin, J, Li, R, Erothu, H, Wantz, G, Topham, PD, Dautel, OJ, Hayes, SC, Stavrinou, PN & Stingelin, N 2019, 'Managing Local Order in Conjugated Polymer Blends via Polarity Contrast', Chemistry of Materials, vol. 31, no. 17, pp. 6540-6547. https://doi.org/10.1021/acs.chemmater.8b05259

Managing Local Order in Conjugated Polymer Blends via Polarity Contrast. / Dyson, Matthew J; Lariou, Eirini; Martin, Jaime; Li, Ruipeng; Erothu, Harikrishna; Wantz, Guillaume; Topham, Paul D; Dautel, Olivier J.; Hayes, Sophia C.; Stavrinou, Paul N.; Stingelin, Natalie.

In: Chemistry of Materials, Vol. 31, No. 17, 10.09.2019, p. 6540-6547.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Managing Local Order in Conjugated Polymer Blends via Polarity Contrast

AU - Dyson, Matthew J

AU - Lariou, Eirini

AU - Martin, Jaime

AU - Li, Ruipeng

AU - Erothu, Harikrishna

AU - Wantz, Guillaume

AU - Topham, Paul D

AU - Dautel, Olivier J.

AU - Hayes, Sophia C.

AU - Stavrinou, Paul N.

AU - Stingelin, Natalie

N1 - 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 https://pubs.acs.org/doi/10.1021/acs.chemmater.8b05259 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).

PY - 2019/9/10

Y1 - 2019/9/10

N2 - 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.

AB - 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.

UR - http://pubs.acs.org/doi/10.1021/acs.chemmater.8b05259

UR - http://www.scopus.com/inward/record.url?scp=85072840803&partnerID=8YFLogxK

U2 - 10.1021/acs.chemmater.8b05259

DO - 10.1021/acs.chemmater.8b05259

M3 - Article

VL - 31

SP - 6540

EP - 6547

JO - Chemistry of Materials

JF - Chemistry of Materials

SN - 0897-4756

IS - 17

ER -

Dyson MJ, Lariou E, Martin J, Li R, Erothu H, Wantz G et al. Managing Local Order in Conjugated Polymer Blends via Polarity Contrast. Chemistry of Materials. 2019 Sep 10;31(17):6540-6547. https://doi.org/10.1021/acs.chemmater.8b05259