4.8 Article

Inversion of Circular Dichroism Signals in Chiral Polythiophene Films Induced by End-On-Oriented Surface-Segregated Monolayers

Journal

ACS APPLIED MATERIALS & INTERFACES
Volume 13, Issue 6, Pages 7510-7516

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsami.0c22099

Keywords

organic semiconductor thin-film; molecular chirality; circular dichroism; polymer chain orientation; surface-segregated monolayer; optical anisotropy

Funding

  1. Japan Society for the Promotion of Science (JSPS) [19J10529]
  2. Grants-in-Aid for Scientific Research [19J10529] Funding Source: KAKEN

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The study found that surface-segregated monolayers (SSMs) can induce changes in the packing of polymer aggregates in films, leading to a dramatic change in excitonic interactions of chiral semiconducting polymers.
A chiral polythiophene surfactant based on poly(3-(S)-2-methylbutylthiophene) ((S)-P3MBT) with a semifluoroalkyl group at one end of the main chain was synthesized and used to form surface-segregated monolayers (SSMs). Films of pure (S)-P3MBT mainly adopted the edge-on orientation, whereas (S)-P3MBT films with a SSM of the polymer surfactant (S)-P3MBT-F-17 contained a large proportion of end-on-oriented polythiophene, both at the surface and inside the films. The thin films with the SSM showed circular dichroism signals, with the sign opposite to those observed in (S)-P3MBT films. These findings suggest that the orientation-controlled SSM layers induced changes in the packing of the polymer aggregates in the films, resulting in a dramatic change in the excitonic interactions of the chiral semiconducting polymers.

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