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Title: Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State

Abstract

The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. We investigate the role of intermolecular interactions in triplet separation dynamics after singlet fission. We use transient absorption spectroscopy to determine the singlet fission rate and triplet yield in two polymers differing only by side-chain motif in both solution and the solid state. Whereas solid-state films show singlet fission rates identical to those measured in solution, the average lifetime of the triplet population increases dramatically and is strongly dependent on side-chain identity. These results show that it may be necessary to carefully engineer the solid-state microstructure of these 'singlet fission polymers' to produce the long-lived triplets needed to realize efficient photovoltaic devices.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [4];  [1]; ORCiD logo [3]
+ Show Author Affiliations
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States)
  2. Imperial College, London (United Kingdom)
  3. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  4. Imperial College, London (United Kingdom); King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia)
Publication Date:
Research Org.:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1413905
Report Number(s):
NREL/JA-5900-70338
Journal ID: ISSN 1948-7185; TRN: US1800468
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 8; Journal Issue: 24; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; singlet fission; intermolecular interactions; separation dynamics; solid-state microstructure

Citation Formats

Pace, Natalie A., Zhang, Weimin, Arias, Dylan H., McCulloch, Iain, Rumbles, Garry, and Johnson, Justin C. Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State. United States: N. p., 2017. Web. doi:10.1021/acs.jpclett.7b02750.
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Pace, Natalie A., Zhang, Weimin, Arias, Dylan H., McCulloch, Iain, Rumbles, Garry, & Johnson, Justin C. Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State. United States. https://doi.org/10.1021/acs.jpclett.7b02750
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Pace, Natalie A., Zhang, Weimin, Arias, Dylan H., McCulloch, Iain, Rumbles, Garry, and Johnson, Justin C. Thu . "Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State". United States. https://doi.org/10.1021/acs.jpclett.7b02750. https://www.osti.gov/servlets/purl/1413905.
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@article{osti_1413905,
title = {Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State},
author = {Pace, Natalie A. and Zhang, Weimin and Arias, Dylan H. and McCulloch, Iain and Rumbles, Garry and Johnson, Justin C.},
abstractNote = {The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. We investigate the role of intermolecular interactions in triplet separation dynamics after singlet fission. We use transient absorption spectroscopy to determine the singlet fission rate and triplet yield in two polymers differing only by side-chain motif in both solution and the solid state. Whereas solid-state films show singlet fission rates identical to those measured in solution, the average lifetime of the triplet population increases dramatically and is strongly dependent on side-chain identity. These results show that it may be necessary to carefully engineer the solid-state microstructure of these 'singlet fission polymers' to produce the long-lived triplets needed to realize efficient photovoltaic devices.},
doi = {10.1021/acs.jpclett.7b02750},
journal = {Journal of Physical Chemistry Letters},
number = 24,
volume = 8,
place = {United States},
year = {Thu Nov 30 00:00:00 EST 2017},
month = {Thu Nov 30 00:00:00 EST 2017}
}
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https://doi.org/10.1021/acs.jpclett.7b02750
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    Works referencing / citing this record:

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    • The Journal of Chemical Physics, Vol. 151, Issue 4
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    Dynamics of singlet fission and electron injection in self-assembled acene monolayers on titanium dioxide
    journal, January 2018

    • Pace, Natalie A.; Arias, Dylan H.; Granger, Devin B.
    • Chemical Science, Vol. 9, Issue 11
    • DOI: 10.1039/c7sc04688j

    Vibronic fingerprint of singlet fission in hexacene
    journal, August 2019

    • Deng, Gang-Hua; Wei, Qianshun; Han, Jian
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    Efficient triplet pair separation from intramolecular singlet fission in dibenzopentalene derivatives
    journal, May 2019

    Solution-Processable, Solid State Donor-Acceptor Materials for Singlet Fission
    journal, September 2018

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    Sensitizer-free photon up conversion in (HQ) 2 ZnCl 4 and HQCl crystals: systems involving resonant energy transfer and triplet–triplet annihilation
    journal, January 2020

    • Samet, Amira; Pillet, Sebastien; Abid, Younes
    • Physical Chemistry Chemical Physics, Vol. 22, Issue 3
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    Lessons from intramolecular singlet fission with covalently bound chromophores
    journal, January 2020

    • Korovina, Nadezhda V.; Pompetti, Nicholas F.; Johnson, Justin C.
    • The Journal of Chemical Physics, Vol. 152, Issue 4
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    Resolving population dynamics and interactions of multiple triplet excitons one molecule at a time
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    Dynamics of singlet fission and electron injection in self-assembled acene monolayers on titanium dioxide
    journal, January 2018

    • Pace, Natalie A.; Arias, Dylan H.; Granger, Devin B.
    • Chemical Science, Vol. 9, Issue 11
    • DOI: 10.1039/c7sc04688j
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