Issue 31, 2023

Accumulation and ordering of P3HT oligomers at the liquid–vapor interface with implications for thin-film morphology

Abstract

The morphology of semiconducting polymer thin films is known to have a profound effect on their opto-electronic properties. Although considerable efforts have been made to control and understand the processes which influence the structures of these systems, it remains largely unclear what physical factors determine the arrangement of polymer chains in spin-cast films. Here, we investigate the role that the liquid–vapor interfaces in chlorobenzene solutions of poly(3-hexylthiophene) [P3HT] play in the conformational geometries adopted by the polymers. Using all-atom molecular dynamics (MD), and supported by toy-model simulations, we demonstrate that, with increasing concentration, P3HT oligomers in solution exhibit a strong propensity for the liquid–vapor interface. Due to the differential solubility of the backbone and side chains of the oligomers, in the vicinity of this interface, hexyl chains and the thiophene rings, have a clear orientational preference with respect to the liquid surface. At high concentrations, we additionally establish a substantial degree of inter-oligomer alignment and thiophene ring stacking near the interface. Our results broadly concur with the limited existing experimental evidence and we suggest that the interfacial structure can act as a template for film structure. We argue that the differences in solvent affinity of the side chain and backbone moieties are the driving force for the anisotropic orientations of the polymers near the interface. This finer grained description contrasts with the usual monolithic characterization of polymer units. Since this phenomenon can be controlled by concurrent chemical design and the choice of solvents, this work establishes a fabrication principle which may be useful to develop more highly functional polymer films.

Graphical abstract: Accumulation and ordering of P3HT oligomers at the liquid–vapor interface with implications for thin-film morphology

Supplementary files

Article information

Article type
Paper
Submitted
11 Jun 2023
Accepted
18 Jul 2023
First published
20 Jul 2023

Phys. Chem. Chem. Phys., 2023,25, 20808-20816

Author version available

Accumulation and ordering of P3HT oligomers at the liquid–vapor interface with implications for thin-film morphology

J. K. Sowa, T. C. Allen and P. J. Rossky, Phys. Chem. Chem. Phys., 2023, 25, 20808 DOI: 10.1039/D3CP02718J

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