Advances in Singlet Fission Chromophore Design Enabled by Vibrational Spectroscopies
Abstract
Singlet fission leads to the formation of two separate triplet T1 excitons from an initial singlet S1 exciton through 1(TT) and 1(T...T), multiexcitonic intermediates that retain singlet character. Its ability to achieve external quantum efficiencies higher than 100% made it an attractive candidate for optoelectronic device applications. However, singlet fission has not been applied widely despite having been investigated by a myriad of spectroscopic methods, in part due to our poor understanding of how to optimize molecular structure and packing in chromophores well-suited to large-scale production. Vibrational spectroscopies provide a solution, because they directly probe nuclear motions, allowing us to monitor evolving structural changes in molecules undergoing singlet fission, thus providing us with roadmaps to design molecules suitable for optoelectronic applications. This Perspective reviews the contributions and analyzes the future directions of vibrational spectroscopies to the advancement in our knowledge about the mechanisms and rational designing of chromophores undergoing efficient singlet fission.
- Authors:
-
- Univ. of Minnesota, Minneapolis, MN (United States)
- Publication Date:
- Research Org.:
- Univ. of Minnesota, Minneapolis, MN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1856840
- Alternate Identifier(s):
- OSTI ID: 1865868; OSTI ID: 1866240
- Grant/Contract Number:
- SC0018203
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 124; Journal Issue: 46; 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; Infrared spectroscopy; Molecules; Raman spectroscopy; Chromophores
Citation Formats
Bera, Kajari, Kwang, Siu Yi, and Frontiera, Renee R. Advances in Singlet Fission Chromophore Design Enabled by Vibrational Spectroscopies. United States: N. p., 2020.
Web. doi:10.1021/acs.jpcc.0c06725.
Bera, Kajari, Kwang, Siu Yi, & Frontiera, Renee R. Advances in Singlet Fission Chromophore Design Enabled by Vibrational Spectroscopies. United States. https://doi.org/10.1021/acs.jpcc.0c06725
Bera, Kajari, Kwang, Siu Yi, and Frontiera, Renee R. Tue .
"Advances in Singlet Fission Chromophore Design Enabled by Vibrational Spectroscopies". United States. https://doi.org/10.1021/acs.jpcc.0c06725. https://www.osti.gov/servlets/purl/1856840.
@article{osti_1856840,
title = {Advances in Singlet Fission Chromophore Design Enabled by Vibrational Spectroscopies},
author = {Bera, Kajari and Kwang, Siu Yi and Frontiera, Renee R.},
abstractNote = {Singlet fission leads to the formation of two separate triplet T1 excitons from an initial singlet S1 exciton through 1(TT) and 1(T...T), multiexcitonic intermediates that retain singlet character. Its ability to achieve external quantum efficiencies higher than 100% made it an attractive candidate for optoelectronic device applications. However, singlet fission has not been applied widely despite having been investigated by a myriad of spectroscopic methods, in part due to our poor understanding of how to optimize molecular structure and packing in chromophores well-suited to large-scale production. Vibrational spectroscopies provide a solution, because they directly probe nuclear motions, allowing us to monitor evolving structural changes in molecules undergoing singlet fission, thus providing us with roadmaps to design molecules suitable for optoelectronic applications. This Perspective reviews the contributions and analyzes the future directions of vibrational spectroscopies to the advancement in our knowledge about the mechanisms and rational designing of chromophores undergoing efficient singlet fission.},
doi = {10.1021/acs.jpcc.0c06725},
journal = {Journal of Physical Chemistry. C},
number = 46,
volume = 124,
place = {United States},
year = {Tue Oct 27 00:00:00 EDT 2020},
month = {Tue Oct 27 00:00:00 EDT 2020}
}
Works referenced in this record:
Solar conversion efficiency of photovoltaic and photoelectrolysis cells with carrier multiplication absorbers
journal, October 2006
- Hanna, M. C.; Nozik, A. J.
- Journal of Applied Physics, Vol. 100, Issue 7
Femtosecond Raman Microscopy Reveals Structural Dynamics Leading to Triplet Separation in Rubrene Singlet Fission
journal, November 2017
- Bera, Kajari; Douglas, Christopher J.; Frontiera, Renee R.
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 23
Enhanced Triplet Formation in Polycrystalline Tetracene Films by Femtosecond Optical-Pulse Shaping
journal, December 2010
- Grumstrup, Erik M.; Johnson, Justin C.; Damrauer, Niels H.
- Physical Review Letters, Vol. 105, Issue 25
Harnessing singlet exciton fission to break the Shockley–Queisser limit
journal, October 2017
- Rao, Akshay; Friend, Richard H.
- Nature Reviews Materials, Vol. 2, Issue 11
Recent Advances in Singlet Fission
journal, April 2013
- Smith, Millicent B.; Michl, Josef
- Annual Review of Physical Chemistry, Vol. 64, Issue 1
Real-time observation of multiexcitonic states in ultrafast singlet fission using coherent 2D electronic spectroscopy
journal, October 2015
- Bakulin, Artem A.; Morgan, Sarah E.; Kehoe, Tom B.
- Nature Chemistry, Vol. 8, Issue 1
Quintet multiexciton dynamics in singlet fission
journal, October 2016
- Tayebjee, Murad J. Y.; Sanders, Samuel N.; Kumarasamy, Elango
- Nature Physics, Vol. 13, Issue 2
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
Visualization of exciton transport in ordered and disordered molecular solids
journal, April 2014
- Akselrod, Gleb M.; Deotare, Parag B.; Thompson, Nicholas J.
- Nature Communications, Vol. 5, Issue 1
Charge-Transfer Excitations Steer the Davydov Splitting and Mediate Singlet Exciton Fission in Pentacene
journal, May 2013
- Beljonne, D.; Yamagata, H.; Brédas, J. L.
- Physical Review Letters, Vol. 110, Issue 22
Singlet fission in pentacene through multi-exciton quantum states
journal, June 2010
- Zimmerman, Paul M.; Zhang, Zhiyong; Musgrave, Charles B.
- Nature Chemistry, Vol. 2, Issue 8
Electron spin polarization generated by transport of singlet and quintet multiexcitons to spin-correlated triplet pairs during singlet fissions
journal, January 2020
- Matsuda, Saki; Oyama, Shinya; Kobori, Yasuhiro
- Chemical Science, Vol. 11, Issue 11
Sensitization of silicon by singlet exciton fission in tetracene
journal, July 2019
- Einzinger, Markus; Wu, Tony; Kompalla, Julia F.
- Nature, Vol. 571, Issue 7763
Exciton Transport in Singlet Fission Materials: A New Hare and Tortoise Story
journal, October 2018
- Zhu, Tong; Huang, Libai
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 22
Magnetic effects on triplet exciton interactions
journal, January 1971
- Merrifield, R. E.
- Pure and Applied Chemistry, Vol. 27, Issue 3
Spatial separation of triplet excitons drives endothermic singlet fission
journal, March 2020
- Korovina, Nadezhda V.; Chang, Christopher H.; Johnson, Justin C.
- Nature Chemistry, Vol. 12, Issue 4
Unified model for singlet fission within a non-conjugated covalent pentacene dimer
journal, May 2017
- Basel, Bettina S.; Zirzlmeier, Johannes; Hetzer, Constantin
- Nature Communications, Vol. 8, Issue 1
Leveraging excited-state coherence for synthetic control of ultrafast dynamics
journal, June 2020
- Paulus, Bryan C.; Adelman, Sara L.; Jamula, Lindsey L.
- Nature, Vol. 582, Issue 7811
Emerging Design Principles for Enhanced Solar Energy Utilization with Singlet Fission
journal, January 2019
- Gish, Melissa K.; Pace, Natalie A.; Rumbles, Garry
- The Journal of Physical Chemistry C, Vol. 123, Issue 7
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
Observation of long-range exciton diffusion in highly ordered organic semiconductors
journal, October 2010
- Najafov, H.; Lee, B.; Zhou, Q.
- Nature Materials, Vol. 9, Issue 11
Triplet excitons and Delayed Fluorescence in Anthracene Crystals
journal, May 1963
- Kepler, R. G.; Caris, J. C.; Avakian, P.
- Physical Review Letters, Vol. 10, Issue 9
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
Enhancing Singlet Fission Dynamics by Suppressing Destructive Interference between Charge-Transfer Pathways
journal, May 2017
- Castellanos, Maria A.; Huo, Pengfei
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 11
Ultrafast terahertz spectroscopy for measuring carrier dynamics in nanoscale photovoltaic materials
conference, February 2010
- Esenturk, Okan; Lane, Paul A.; Melinger, Joseph S.
- OPTO, SPIE Proceedings
Charge Transfer–Mediated Singlet Fission
journal, April 2015
- Monahan, N.; Zhu, X. -Y.
- Annual Review of Physical Chemistry, Vol. 66, Issue 1
Singlet fission in rubrene single crystal: direct observation by femtosecond pump–probe spectroscopy
journal, January 2012
- Ma, Lin; Zhang, Keke; Kloc, Christian
- Physical Chemistry Chemical Physics, Vol. 14, Issue 23
Molecular design for efficient singlet fission
journal, March 2018
- Ito, Soichi; Nagami, Takanori; Nakano, Masayoshi
- Journal of Photochemistry and Photobiology C: Photochemistry Reviews, Vol. 34
Observing the Multiexciton State in Singlet Fission and Ensuing Ultrafast Multielectron Transfer
journal, December 2011
- Chan, W. -L.; Ligges, M.; Jailaubekov, A.
- Science, Vol. 334, Issue 6062
Vibronic fingerprint of singlet fission in hexacene
journal, August 2019
- Deng, Gang-Hua; Wei, Qianshun; Han, Jian
- The Journal of Chemical Physics, Vol. 151, Issue 5
Evidence for exciton fission and fusion in a covalently linked tetracene dimer
journal, April 2006
- Müller, Astrid M.; Avlasevich, Yuri S.; Müllen, Klaus
- Chemical Physics Letters, Vol. 421, Issue 4-6
Singlet Fission for Dye-Sensitized Solar Cells: Can a Suitable Sensitizer Be Found?
journal, December 2006
- Paci, Irina; Johnson, Justin C.; Chen, Xudong
- Journal of the American Chemical Society, Vol. 128, Issue 51
A Direct Mechanism of Ultrafast Intramolecular Singlet Fission in Pentacene Dimers
journal, May 2016
- Fuemmeler, Eric G.; Sanders, Samuel N.; Pun, Andrew B.
- ACS Central Science, Vol. 2, Issue 5
Resonance Raman Spectroscopy of the T 1 Triplet Excited State of Oligothiophenes
journal, August 2015
- Wang, Chen; Angelella, Maria; Doyle, Samantha J.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 18
Vibronically coherent ultrafast triplet-pair formation and subsequent thermally activated dissociation control efficient endothermic singlet fission
journal, September 2017
- Stern, Hannah L.; Cheminal, Alexandre; Yost, Shane R.
- Nature Chemistry, Vol. 9, Issue 12
Coherent charge-phonon correlations and exciton dynamics in orthorhombic CH 3 NH 3 PbI 3 measured by ultrafast multi-THz spectroscopy
journal, December 2019
- Lan, Yang; Tao, Xixi; Kong, Xianghua
- The Journal of Chemical Physics, Vol. 151, Issue 21
Charge transfer dynamics in a singlet fission organic molecule and organometal perovskite bilayer structure
journal, January 2020
- Guo, Deqiang; Ma, Lin; Zhou, Zilin
- Journal of Materials Chemistry A, Vol. 8, Issue 11
Near-IR Femtosecond Transient Absorption Spectroscopy of Ultrafast Polaron and Triplet Exciton Formation in Polythiophene Films with Different Regioregularities
journal, November 2009
- Guo, Jiamo; Ohkita, Hideo; Benten, Hiroaki
- Journal of the American Chemical Society, Vol. 131, Issue 46
Distinct properties of the triplet pair state from singlet fission
journal, July 2017
- Trinh, M. Tuan; Pinkard, Andrew; Pun, Andrew B.
- Science Advances, Vol. 3, Issue 7
Theoretical Modeling of Singlet Fission
journal, April 2018
- Casanova, David
- Chemical Reviews, Vol. 118, Issue 15
Theoretical Studies of Singlet Fission: Searching for Materials and Exploring Mechanisms
journal, February 2018
- Japahuge, Achini; Zeng, Tao
- ChemPlusChem, Vol. 83, Issue 4
Singlet Fission
journal, November 2010
- Smith, Millicent B.; Michl, Josef
- Chemical Reviews, Vol. 110, Issue 11
External Quantum Efficiency Above 100% in a Singlet-Exciton-Fission-Based Organic Photovoltaic Cell
journal, April 2013
- Congreve, D. N.; Lee, J.; Thompson, N. J.
- Science, Vol. 340, Issue 6130
Triplet Pair States in Singlet Fission
journal, January 2019
- Miyata, Kiyoshi; Conrad-Burton, Felisa S.; Geyer, Florian L.
- Chemical Reviews, Vol. 119, Issue 6
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
Femtosecond stimulated Raman evidence for charge-transfer character in pentacene singlet fission
journal, January 2018
- Hart, Stephanie M.; Silva, W. Ruchira; Frontiera, Renee R.
- Chemical Science, Vol. 9, Issue 5
Triplet-Pair States in Organic Semiconductors
journal, June 2019
- Musser, Andrew J.; Clark, Jenny
- Annual Review of Physical Chemistry, Vol. 70, Issue 1
High-Yield Singlet Fission in a Zeaxanthin Aggregate Observed by Picosecond Resonance Raman Spectroscopy
journal, October 2010
- Wang, Chen; Tauber, Michael J.
- Journal of the American Chemical Society, Vol. 132, Issue 40
Resonance Raman Spectra of a Perylene Bis(dicarboximide) Chromophore in Ground and Lowest Triplet States
journal, September 2013
- Angelella, Maria; Wang, Chen; Tauber, Michael J.
- The Journal of Physical Chemistry A, Vol. 117, Issue 38
Singlet Fission: Progress and Prospects in Solar Cells
journal, December 2016
- Xia, Jianlong; Sanders, Samuel N.; Cheng, Wei
- Advanced Materials, Vol. 29, Issue 20
Evidence for Singlet Fission Driven by Vibronic Coherence in Crystalline Tetracene
journal, March 2017
- Morrison, Adrian F.; Herbert, John M.
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 7
Triplet Excitons of Carotenoids Formed by Singlet Fission in a Membrane
journal, September 2011
- Wang, Chen; Schlamadinger, Diana E.; Desai, Varsha
- ChemPhysChem, Vol. 12, Issue 16
Singlet Fission in Covalent Terrylenediimide Dimers: Probing the Nature of the Multiexciton State Using Femtosecond Mid-Infrared Spectroscopy
journal, June 2018
- Chen, Michelle; Bae, Youn Jue; Mauck, Catherine M.
- Journal of the American Chemical Society, Vol. 140, Issue 29
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
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
Spatially Offset Femtosecond Stimulated Raman Spectroscopy: Observing Exciton Transport through a Vibrational Lens
journal, May 2020
- Kwang, Siu Yi; Frontiera, Renee R.
- The Journal of Physical Chemistry Letters, Vol. 11, Issue 11
Laser Generation of Excitons and Fluorescence in Anthracene Crystals
journal, January 1965
- Singh, S.; Jones, W. J.; Siebrand, W.
- The Journal of Chemical Physics, Vol. 42, Issue 1
Effect of Vibronic Coupling on Correlated Triplet Pair Formation in the Singlet Fission Process of Linked Tetracene Dimers
journal, April 2020
- Shizu, Katsuyuki; Adachi, Chihaya; Kaji, Hironori
- The Journal of Physical Chemistry A, Vol. 124, Issue 18
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
A molecular movie of ultrafast singlet fission
journal, September 2019
- Schnedermann, Christoph; Alvertis, Antonios M.; Wende, Torsten
- Nature Communications, Vol. 10, Issue 1
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