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:
-
- Pennsylvania State Univ., University Park, PA (United States)
- 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.
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
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.
@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}
}
Works referenced in this record:
Vibrational Probe of the Structural Origins of Slow Recombination in Halide Perovskites
journal, February 2019
- Munson, Kyle T.; Doucette, Grayson S.; Kennehan, Eric R.
- The Journal of Physical Chemistry C, Vol. 123, Issue 12
Efficient Singlet Fission Discovered in a Disordered Acene Film
journal, March 2012
- Roberts, Sean T.; McAnally, R. Eric; Mastron, Joseph N.
- Journal of the American Chemical Society, Vol. 134, Issue 14
Singlet fission of hot excitons in π -conjugated polymers
journal, June 2015
- Zhai, Yaxin; Sheng, Chuanxiang; Vardeny, Z. Valy
- Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 373, Issue 2044
Striking the right balance of intermolecular coupling for high-efficiency singlet fission
journal, January 2018
- Pensack, Ryan D.; Tilley, Andrew J.; Grieco, Christopher
- Chemical Science, Vol. 9, Issue 29
Enhanced external quantum efficiency in an organic photovoltaic cell via singlet fission exciton sensitizer
journal, September 2012
- Reusswig, P. D.; Congreve, D. N.; Thompson, N. J.
- Applied Physics Letters, Vol. 101, Issue 11
Triplet Transfer Mediates Triplet Pair Separation during Singlet Fission in 6,13-Bis(triisopropylsilylethynyl)-Pentacene
journal, October 2017
- Grieco, Christopher; Doucette, Grayson S.; Munro, Jason M.
- Advanced Functional Materials, Vol. 27, Issue 46
Tuning Triplet-Pair Separation versus Relaxation Using a Diamond Anvil Cell
journal, January 2020
- Doucette, Grayson S.; Huang, Haw-Tyng; Munro, Jason M.
- Cell Reports Physical Science, Vol. 1, Issue 1
Recent Advances in Singlet Fission
journal, April 2013
- Smith, Millicent B.; Michl, Josef
- Annual Review of Physical Chemistry, Vol. 64, Issue 1
Direct Observation of Correlated Triplet Pair Dynamics during Singlet Fission Using Ultrafast Mid-IR Spectroscopy
journal, January 2018
- Grieco, Christopher; Kennehan, Eric R.; Kim, Hwon
- The Journal of Physical Chemistry C, Vol. 122, Issue 4
Crystalline silicon solar cells with tetracene interlayers: the path to silicon-singlet fission heterojunction devices
journal, January 2018
- MacQueen, Rowan W.; Liebhaber, Martin; Niederhausen, Jens
- Materials Horizons, Vol. 5, Issue 6
Triplet diffusion leads to triplet–triplet annihilation in organic phosphorescent emitters
journal, December 2013
- Zhang, Yifan; Forrest, Stephen R.
- Chemical Physics Letters, Vol. 590
Triplet diffusion in singlet exciton fission sensitized pentacene solar cells
journal, October 2013
- Tabachnyk, Maxim; Ehrler, Bruno; Bayliss, Sam
- Applied Physics Letters, Vol. 103, Issue 15
Sensitization of silicon by singlet exciton fission in tetracene
journal, July 2019
- Einzinger, Markus; Wu, Tony; Kompalla, Julia F.
- Nature, Vol. 571, Issue 7763
New insights into the design of conjugated polymers for intramolecular singlet fission
journal, July 2018
- Hu, Jiahua; Xu, Ke; Shen, Lei
- Nature Communications, Vol. 9, Issue 1
Exciton Delocalization Drives Rapid Singlet Fission in Nanoparticles of Acene Derivatives
journal, May 2015
- Pensack, Ryan D.; Tilley, Andrew J.; Parkin, Sean R.
- Journal of the American Chemical Society, Vol. 137, Issue 21
Watching Electrons Move in Real Time: Ultrafast Infrared Spectroscopy of a Polymer Blend Photovoltaic Material
journal, December 2007
- Barbour, Larry W.; Hegadorn, Maureen; Asbury, John B.
- Journal of the American Chemical Society, Vol. 129, Issue 51
Slow charge transfer from pentacene triplet states at the Marcus optimum
journal, November 2019
- Pace, Natalie A.; Korovina, Nadezhda V.; Clikeman, Tyler T.
- Nature Chemistry, Vol. 12, Issue 1
Substituent Effects on Singlet Exciton Fission in Polycrystalline Thin Films of Cyano-Substituted Diaryltetracenes
journal, September 2017
- Margulies, Eric A.; Kerisit, Nicolas; Gawel, Przemyslaw
- The Journal of Physical Chemistry C, Vol. 121, Issue 39
Light Absorption and Energy Transfer in the Antenna Complexes of Photosynthetic Organisms
journal, March 2016
- Mirkovic, Tihana; Ostroumov, Evgeny E.; Anna, Jessica M.
- Chemical Reviews, Vol. 117, Issue 2
Competition between Singlet Fission and Charge Separation in Solution-Processed Blend Films of 6,13-Bis(triisopropylsilylethynyl)pentacene with Sterically-Encumbered Perylene-3,4:9,10-bis(dicarboximide)s
journal, December 2011
- Ramanan, Charusheela; Smeigh, Amanda L.; Anthony, John E.
- Journal of the American Chemical Society, Vol. 134, Issue 1
Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State
journal, December 2017
- Pace, Natalie A.; Zhang, Weimin; Arias, Dylan H.
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 24
Ultrafast Dynamics of Exciton Fission in Polycrystalline Pentacene
journal, August 2011
- Wilson, Mark W. B.; Rao, Akshay; Clark, Jenny
- Journal of the American Chemical Society, Vol. 133, Issue 31
Harnessing Molecular Vibrations to Probe Triplet Dynamics During Singlet Fission
journal, November 2017
- Grieco, Christopher; Kennehan, Eric R.; Rimshaw, Adam
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 23
Observation of Two Triplet-Pair Intermediates in Singlet Exciton Fission
journal, June 2016
- Pensack, Ryan D.; Ostroumov, Evgeny E.; Tilley, Andrew J.
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 13
Robust singlet fission in pentacene thin films with tuned charge transfer interactions
journal, March 2018
- Broch, K.; Dieterle, J.; Branchi, F.
- Nature Communications, Vol. 9, Issue 1
Correlated Pair States Formed by Singlet Fission and Exciton–Exciton Annihilation
journal, December 2015
- Scholes, Gregory D.
- The Journal of Physical Chemistry A, Vol. 119, Issue 51
Two temperature regimes of triplet transfer in the dissociation of the correlated triplet pair after singlet fission
journal, June 2019
- Lee, Tia S.; Lin, YunHui L.; Kim, Hwon
- Canadian Journal of Chemistry, Vol. 97, Issue 6
Investigating the Role of the Organic Cation in Formamidinium Lead Iodide Perovskite Using Ultrafast Spectroscopy
journal, February 2018
- Taylor, Victoria C. A.; Tiwari, Devendra; Duchi, Marta
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 4
Effects of Crystal Morphology on Singlet Exciton Fission in Diketopyrrolopyrrole Thin Films
journal, February 2016
- Hartnett, Patrick E.; Margulies, Eric A.; Mauck, Catherine M.
- The Journal of Physical Chemistry B, Vol. 120, Issue 7
Singlet exciton fission in solution
journal, November 2013
- Walker, Brian J.; Musser, Andrew J.; Beljonne, David
- Nature Chemistry, Vol. 5, Issue 12
Direct Observation of a Photochemical Alkyne–Allene Reaction and of a Twisted and Rehybridized Intramolecular Charge-Transfer State in a Donor–Acceptor Dyad
journal, November 2017
- Dereka, Bogdan; Svechkarev, Denis; Rosspeintner, Arnulf
- Journal of the American Chemical Society, Vol. 139, Issue 46
Heavy-atom effects on intramolecular singlet fission in a conjugated polymer
journal, July 2019
- Musser, Andrew J.; Al-Hashimi, Mohammed; Heeney, Martin
- The Journal of Chemical Physics, Vol. 151, Issue 4
Relating the Physical Structure and Optoelectronic Function of Crystalline TIPS-Pentacene
journal, December 2014
- Sharifzadeh, Sahar; Wong, Cathy Y.; Wu, Hao
- Advanced Functional Materials, Vol. 25, Issue 13
Molecular insights and concepts to engineer singlet fission energy conversion devices
journal, January 2020
- Casillas, Rubén; Papadopoulos, Ilias; Ullrich, Tobias
- Energy & Environmental Science, Vol. 13, Issue 9
Ultrafast Singlet Fission in a Push–Pull Low-Bandgap Polymer Film
journal, December 2015
- Kasai, Yukitomo; Tamai, Yasunari; Ohkita, Hideo
- Journal of the American Chemical Society, Vol. 137, Issue 51
Singlet Fission
journal, November 2010
- Smith, Millicent B.; Michl, Josef
- Chemical Reviews, Vol. 110, Issue 11
Dynamics of the triplet-pair state reveals the likely coexistence of coherent and incoherent singlet fission in crystalline hexacene
journal, December 2016
- Monahan, Nicholas R.; Sun, Dezheng; Tamura, Hiroyuki
- Nature Chemistry, Vol. 9, Issue 4
Absence of Singlet Fission and Carrier Multiplication in a Model Conjugated Polymer: Tracking the Triplet Population through Phosphorescence
journal, January 2012
- Bange, Sebastian; Scherf, Ullrich; Lupton, John M.
- Journal of the American Chemical Society, Vol. 134, Issue 4
Engineering Molecular Ligand Shells on Quantum Dots for Quantitative Harvesting of Triplet Excitons Generated by Singlet Fission
journal, July 2019
- Allardice, Jesse R.; Thampi, Arya; Dowland, Simon
- Journal of the American Chemical Society, Vol. 141, Issue 32
A design strategy for intramolecular singlet fission mediated by charge-transfer states in donor–acceptor organic materials
journal, January 2015
- Busby, Erik; Xia, Jianlong; Wu, Qin
- Nature Materials, Vol. 14, Issue 4
Sub-Picosecond Singlet Exciton Fission in Cyano-Substituted Diaryltetracenes
journal, June 2015
- Margulies, Eric A.; Wu, Yi-Lin; Gawel, Przemyslaw
- Angewandte Chemie International Edition, Vol. 54, Issue 30
Understanding Polymorphism in Organic Semiconductor Thin Films through Nanoconfinement
journal, November 2014
- Diao, Ying; Lenn, Kristina M.; Lee, Wen-Ya
- Journal of the American Chemical Society, Vol. 136, Issue 49
Decoherence and the Transition from Quantum to Classical
journal, October 1991
- Zurek, Wojciech H.
- Physics Today, Vol. 44, Issue 10
Triplet Energy Transfer Governs the Dissociation of the Correlated Triplet Pair in Exothermic Singlet Fission
journal, June 2018
- Lee, Tia S.; Lin, YunHui L.; Kim, Hwon
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 14
Dynamic Exchange During Triplet Transport in Nanocrystalline TIPS-Pentacene Films
journal, December 2016
- Grieco, Christopher; Doucette, Grayson S.; Pensack, Ryan D.
- Journal of the American Chemical Society, Vol. 138, Issue 49
Triplet Separation Drives Singlet Fission after Femtosecond Correlated Triplet Pair Production in Rubrene
journal, August 2017
- Breen, Ilana; Tempelaar, Roel; Bizimana, Laurie A.
- Journal of the American Chemical Society, Vol. 139, Issue 34
Detailed Balance Limit of Efficiency of p‐n Junction Solar Cells
journal, March 1961
- Shockley, William; Queisser, Hans J.
- Journal of Applied Physics, Vol. 32, Issue 3, p. 510-519
Solution-processable, crystalline material for quantitative singlet fission
journal, January 2017
- Pensack, Ryan D.; Grieco, Christopher; Purdum, Geoffrey E.
- Materials Horizons, Vol. 4, Issue 5
Singlet Fission: From Coherences to Kinetics
journal, June 2014
- Piland, Geoffrey B.; Burdett, Jonathan J.; Dillon, Robert J.
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 13
Crystallinity determination in polymers and a quantitative comparison for polyethylene
journal, May 1969
- Richardson, M. J.
- British Polymer Journal, Vol. 1, Issue 3
Dynamic Ligand Surface Chemistry of Excited PbS Quantum Dots
journal, March 2020
- Kennehan, Eric R.; Munson, Kyle T.; Doucette, Grayson S.
- The Journal of Physical Chemistry Letters, Vol. 11, Issue 6
Vibrational probe of the origin of singlet exciton fission in TIPS-pentacene solutions
journal, October 2019
- Grieco, Christopher; Doucette, Grayson S.; Munson, Kyle T.
- The Journal of Chemical Physics, Vol. 151, Issue 15
Solution-Processable Singlet Fission Photovoltaic Devices
journal, December 2014
- Yang, Le; Tabachnyk, Maxim; Bayliss, Sam L.
- Nano Letters, Vol. 15, Issue 1
Quantitative Intramolecular Singlet Fission in Bipentacenes
journal, July 2015
- Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B.
- Journal of the American Chemical Society, Vol. 137, Issue 28
Activated Singlet Exciton Fission in a Semiconducting Polymer
journal, August 2013
- Musser, Andrew J.; Al-Hashimi, Mohammed; Maiuri, Margherita
- Journal of the American Chemical Society, Vol. 135, Issue 34
A transferable model for singlet-fission kinetics
journal, May 2014
- Yost, Shane R.; Lee, Jiye; Wilson, Mark W. B.
- Nature Chemistry, Vol. 6, Issue 6
Triplet Dynamics in Pentacene Crystals: Applications to Fission-Sensitized Photovoltaics
journal, December 2013
- Poletayev, Andrey D.; Clark, Jenny; Wilson, Mark W. B.
- Advanced Materials, Vol. 26, Issue 6
Evidence for conical intersection dynamics mediating ultrafast singlet exciton fission
journal, March 2015
- Musser, Andrew J.; Liebel, Matz; Schnedermann, Christoph
- Nature Physics, Vol. 11, Issue 4