Issue 48, 2022

Competing single-chain folding and multi-chain aggregation pathways control solution-phase aggregate morphology of organic semiconducting polymers

Abstract

Understanding the solution-phase behaviour of organic semiconducting polymers is important for systematically improving the performance of devices based on solution-processed thin films of these molecules. Conventional polymer theory predicts that polymer conformations become more compact as solvent quality decreases, but recent experiments have shown the high-performance organic-semiconducting polymer P(NDI2OD-T2) to form extended rod-like aggregates much larger than a single chain in poor solvents, with the formation of these extended aggregates correlated with enhanced electron mobility in films deposited from these solutions. We explain the unexpected formation of extended aggregates using a novel coarse-grained simulation model of P(NDI2OD-T2) that we have developed to study the effect of solvent quality on its solution-phase behaviour. In poor solvents, we find that aggregation through only a few monomers gives effectively inseparable chains, leading to the formation of extended structures of partially overlapping chains via non-equilibrium assembly. This behaviour requires that multi-chain aggregation occurs faster than chain folding, which we show is the case for the chain lengths and concentrations shown experimentally to form rod-like aggregates. This kinetically controlled process introduces a dependence of aggregate structure on concentration, chain length, and chain flexibility, which we show is able to reconcile experimental findings and is generalisable to the solution-phase assembly of other semiflexible polymers.

Graphical abstract: Competing single-chain folding and multi-chain aggregation pathways control solution-phase aggregate morphology of organic semiconducting polymers

Supplementary files

Article information

Article type
Paper
Submitted
31 ago 2022
Accepted
24 nov 2022
First published
24 nov 2022

Nanoscale, 2022,14, 18070-18086

Competing single-chain folding and multi-chain aggregation pathways control solution-phase aggregate morphology of organic semiconducting polymers

B. J. Boehm, C. R. McNeill and D. M. Huang, Nanoscale, 2022, 14, 18070 DOI: 10.1039/D2NR04750K

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements