Displacement of polarons by vibrational modes in doped conjugated polymers

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • M. Anderson - , University of Bath (Author)
  • C. Ramanan - , Vrije Universiteit Amsterdam (VU) (Author)
  • C. Fontanesi - , University of Bath, University of Modena and Reggio Emilia (Author)
  • A. Frick - , Vrije Universiteit Amsterdam (VU) (Author)
  • S. Surana - , Interuniversitair Micro-Elektronica Centrum, KU Leuven (Author)
  • D. Cheyns - , Interuniversitair Micro-Elektronica Centrum (Author)
  • M. Furno - , Novaled GmbH (Author)
  • T. Keller - , University of Wuppertal (Author)
  • S. Allard - , University of Wuppertal (Author)
  • U. Scherf - , University of Wuppertal (Author)
  • D. Beljonne - , University of Mons (Author)
  • G. D'Avino - , Université Grenoble Alpes (Author)
  • E. Von Hauff - , Vrije Universiteit Amsterdam (VU) (Author)
  • E. Da Como - , University of Bath (Author)

Abstract

Organic pi-conjugated polymers are deemed to be soft materials with strong electron-phonon coupling, which results in the formation of polarons, i.e., charge carriers dressed by self-localized distortion of the nuclei. Universal signatures for polarons are optical resonances below the band gap and intense vibrational modes (IVMs), both found in the infrared (IR) spectral region. Here, we study p-doped conjugated homo- and copolymers by combining first-principles modelling and optical spectroscopy from the far-IR to the visible. Polaronic IVMs are found to feature absorption intensities comparable to purely electronic transitions and, most remarkably, show only loose resemblance to the Raman or IR-active modes of the neutral polymer. The IVM frequency is dramatically scaled down (up to 50%) compared to the backbone carbon-stretching modes in the pristine polymers. The very large intensity of IVMs is associated with displacement of the excess positive charge along the backbone driven by specific vibrational modes. We propose a quantitative picture for the identification of these polaron shifting modes that solely based on structural information, directly correlates with their IR intensity. This finding finally discloses the elusive microscopic mechanism behind the huge IR intensity of IVMs in doped polymeric semiconductors.

Details

Original languageEnglish
Article number055604
JournalPhysical review materials
Volume1
Issue number5
Publication statusPublished - 30 Oct 2017
Peer-reviewedYes
Externally publishedYes

External IDs

ORCID /0000-0002-6269-0540/work/172082554