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Spectroscopic properties of poly(9,9-dioctylfluorene) thin films possessing varied fractions of β-phase chain segments: enhanced photoluminescence efficiency via conformation structuring

Journal of polymer science. Part B, Polymer physics, 2016-10, Vol.54 (19), p.1995-2006 [Peer Reviewed Journal]

2016 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. ;ISSN: 0887-6266 ;EISSN: 1099-0488 ;DOI: 10.1002/polb.24106 ;PMID: 28344383

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  • Title:
    Spectroscopic properties of poly(9,9-dioctylfluorene) thin films possessing varied fractions of β-phase chain segments: enhanced photoluminescence efficiency via conformation structuring
  • Author: Perevedentsev, Aleksandr ; Chander, Nathan ; Kim, Ji-Seon ; Bradley, Donal D. C.
  • Subjects: Chains (polymeric) ; conformation ; conjugated polymers ; microstructure ; Molecular conformation ; Parameter modification ; Photoluminescence ; polyfluorene ; Quantum efficiency ; Raman spectroscopy ; Segments ; Spectroscopy ; Thin films
  • Is Part Of: Journal of polymer science. Part B, Polymer physics, 2016-10, Vol.54 (19), p.1995-2006
  • Description: ABSTRACT Poly(9,9‐dioctylfluorene) (PFO) is a widely studied blue‐emitting conjugated polymer, the optoelectronic properties of which are strongly affected by the presence of a well‐defined chain‐extended “β‐phase” conformational isomer. In this study, optical and Raman spectroscopy are used to systematically investigate the properties of PFO thin films featuring a varied fraction of β‐phase chain segments. Results show that the photoluminescence quantum efficiency (PLQE) of PFO films is highly sensitive to both the β‐phase fraction and the method by which it was induced. Notably, a PLQE of ∼69% is measured for PFO films possessing a ∼6% β‐phase fraction induced by immersion in solvent/nonsolvent mixtures; this value is substantially higher than the average PLQE of ∼55% recorded for other β‐phase films. Furthermore, a linear relationship is observed between the intensity ratios of selected Raman peaks and the β‐phase fraction determined by commonly used absorption calibrations, suggesting that Raman spectroscopy can be used as an alternative means to quantify the β‐phase fraction. As a specific example, spatial Raman mapping is used to image a mm‐scale β‐phase stripe patterned in a glassy PFO film, with the extracted β‐phase fraction showing excellent agreement with the results of optical spectroscopy. © 2016 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 1995–2006 The physical geometry, or conformation, of a semi‐flexible macromolecule represents an additional parameter space for modifying its functionalities. A high photoluminescence quantum efficiency of ∼69% is reported for films of poly(9,9‐dioctylfluorene) (PFO)—a blue‐emitting conjugated polymer—possessing a specific fraction of chain‐extended planar “β‐phase” chain segments, thus offering a strategy for improving the brightness and efficiency of PFO‐based light‐emitting devices. Furthermore, Raman spectroscopy is demonstrated to be an additional, highly sensitive tool for quantifying β‐phase fraction.
  • Publisher: United States: Blackwell Publishing Ltd
  • Language: English
  • Identifier: ISSN: 0887-6266
    EISSN: 1099-0488
    DOI: 10.1002/polb.24106
    PMID: 28344383
  • Source: Alma/SFX Local Collection
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