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Title: Ultrafast Triplet Pair Separation and Triplet Trapping following Singlet Fission in Amorphous Pentacene Films

Abstract

In this work, ultrafast infrared and electronic spectroscopy are used to examine the dynamics of triplet pair separation following singlet fission in amorphous and crystalline films of the model singlet fission chromophore, 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-Pn). Direct probing of correlated triplet pair intermediates through their unique vibrational frequencies, infrared electronic transitions, and indirectly through their visible triplet absorptions reveals that triplet pair separation occurs on similar picosecond timescales in both amorphous and crystalline films despite their markedly different average intermolecular coupling strengths. Although triplet pair separation occurs on similar timescales in both environments, measurements of diffusion-controlled triplet-triplet annihilation reveal that the diffusivity of triplet excited states is an order of magnitude lower in amorphous films. The data reveal the presence of sparse triplet traps in the amorphous environment that inhibit the transport of triplet excitons in comparison to crystalline films. These observations inform recent efforts to develop disordered and polymeric singlet fission sensitizers that contain amorphous regions. In particular, the data suggest that it may be possible to nanostructure amorphous or polymeric singlet fission sensitizers to allow ultrafast triplet pair separation and harvesting in photovoltaic and light emitting applications despite their low triplet exciton diffusivity.

Authors:
 [1];  [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
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  1. Pennsylvania State Univ., University Park, PA (United States)
  2. Univ. of Kentucky, Lexington, KY (United States)
Publication Date:
Research Org.:
Pennsylvania State Univ., University Park, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1839364
Grant/Contract Number:  
SC0019349; DGE-1255832; 1849213
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 124; Journal Issue: 43; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Excitons; Nuclear fission; Absorption; Quantum mechanics; Kinetics

Citation Formats

Munson, Kyle T., Gan, Jianing, Grieco, Christopher, Doucette, Grayson S., Anthony, John E., and Asbury, John B. Ultrafast Triplet Pair Separation and Triplet Trapping following Singlet Fission in Amorphous Pentacene Films. United States: N. p., 2020. Web. doi:10.1021/acs.jpcc.0c07920.
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Munson, Kyle T., Gan, Jianing, Grieco, Christopher, Doucette, Grayson S., Anthony, John E., & Asbury, John B. Ultrafast Triplet Pair Separation and Triplet Trapping following Singlet Fission in Amorphous Pentacene Films. United States. https://doi.org/10.1021/acs.jpcc.0c07920
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Munson, Kyle T., Gan, Jianing, Grieco, Christopher, Doucette, Grayson S., Anthony, John E., and Asbury, John B. Wed . "Ultrafast Triplet Pair Separation and Triplet Trapping following Singlet Fission in Amorphous Pentacene Films". United States. https://doi.org/10.1021/acs.jpcc.0c07920. https://www.osti.gov/servlets/purl/1839364.
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@article{osti_1839364,
title = {Ultrafast Triplet Pair Separation and Triplet Trapping following Singlet Fission in Amorphous Pentacene Films},
author = {Munson, Kyle T. and Gan, Jianing and Grieco, Christopher and Doucette, Grayson S. and Anthony, John E. and Asbury, John B.},
abstractNote = {In this work, ultrafast infrared and electronic spectroscopy are used to examine the dynamics of triplet pair separation following singlet fission in amorphous and crystalline films of the model singlet fission chromophore, 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-Pn). Direct probing of correlated triplet pair intermediates through their unique vibrational frequencies, infrared electronic transitions, and indirectly through their visible triplet absorptions reveals that triplet pair separation occurs on similar picosecond timescales in both amorphous and crystalline films despite their markedly different average intermolecular coupling strengths. Although triplet pair separation occurs on similar timescales in both environments, measurements of diffusion-controlled triplet-triplet annihilation reveal that the diffusivity of triplet excited states is an order of magnitude lower in amorphous films. The data reveal the presence of sparse triplet traps in the amorphous environment that inhibit the transport of triplet excitons in comparison to crystalline films. These observations inform recent efforts to develop disordered and polymeric singlet fission sensitizers that contain amorphous regions. In particular, the data suggest that it may be possible to nanostructure amorphous or polymeric singlet fission sensitizers to allow ultrafast triplet pair separation and harvesting in photovoltaic and light emitting applications despite their low triplet exciton diffusivity.},
doi = {10.1021/acs.jpcc.0c07920},
journal = {Journal of Physical Chemistry. C},
number = 43,
volume = 124,
place = {United States},
year = {Wed Oct 14 00:00:00 EDT 2020},
month = {Wed Oct 14 00:00:00 EDT 2020}
}
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https://doi.org/10.1021/acs.jpcc.0c07920
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