Vibronically coherent ultrafast triplet-pair formation and subsequent thermally activated dissociation control efficient endothermic singlet fission

Stern, Hannah L.; Cheminal, Alexandre; Yost, Shane R.; Broch, Katharina; Bayliss, Sam L.; Chen, Kai; Tabachnyk, Maxim; Thorley, Karl; Greenham, Neil; Hodgkiss, Justin M.; Anthony, John; Head-Gordon, Martin; Musser, Andrew J.; Rao, Akshay; Friend, Richard H.

doi:10.1038/nchem.2856

Vibronically coherent ultrafast triplet-pair formation and subsequent thermally activated dissociation control efficient endothermic singlet fission

Journal Article · Mon Sep 11 00:00:00 EDT 2017 · Nature Chemistry

DOI:https://doi.org/10.1038/nchem.2856· OSTI ID:1899327

Stern, Hannah L. ^[1]; ^[1]; Yost, Shane R. ^[2]; Broch, Katharina ^[1]; Bayliss, Sam L. ^[1]; Chen, Kai ^[3]; ^[1]; Thorley, Karl ^[4]; Greenham, Neil ^[1]; Hodgkiss, Justin M. ^[3]; ^[4]; Head-Gordon, Martin ^[2]; Musser, Andrew J. ^[5]; ^[1]; ^[1]

Univ. of Cambridge (United Kingdom)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
MacDiarmid Institute for Advanced Materials and Nanotechnology, Wellington (New Zealand); Victoria Univ. of Wellington (New Zealand)
Univ. of Kentucky, Lexington, KY (United States)
Univ. of Cambridge (United Kingdom); Univ. of Sheffield (United Kingdom)

Singlet exciton fission (SF), the conversion of one spin-singlet exciton (S₁) into two spin-triplet excitons (T₁), could provide a means to overcome the Shockley-Queisser limit in photovoltaics. SF as measured by the decay of S₁ has been shown to occur efficiently and independently of temperature even when the energy of S1 is as much as 200 meV less than 2T₁. Here, we study films of TIPS-tetracene using transient optical spectroscopy and show that the initial rise of the triplet pair state (TT) occurs in 300 fs, matched by rapid loss of S1 stimulated emission, and that this process is mediated by the strong coupling of electronic and vibrational degrees of freedom. This is followed by a slower 10 ps morphology-dependent phase of S1 decay and TT growth. Here we observe the TT to be thermally dissociated on 10-100 ns timescales to form free triplets. This provides a model for "temperature independent", efficient TT formation and thermally activated TT separation.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR); Engineering and Physical Sciences Research Council; Miller Institute for Basic Research; Heising–Simons Foundation

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1899327

Journal Information:: Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 12 Vol. 9; ISSN 1755-4330

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (34)

Bimolecular radiationless transitions in crystalline tetracene Swenberg, C. E.; Stacy, W. T. Chemical Physics Letters, Vol. 2, Issue 5 https://doi.org/10.1016/0009-2614(68)80087-9	journal	September 1968
Picosecond vibrational cooling in mixed molecular crystals studied with a new coherent raman scattering technique Chang, Ta-Chau; Dlott, Dana D. Chemical Physics Letters, Vol. 147, Issue 1 https://doi.org/10.1016/0009-2614(88)80216-1	journal	May 1988
Slow Intramolecular Vibrational Relaxation Leads to Long-Lived Excited-State Wavepackets Rafiq, Shahnawaz; Scholes, Gregory D. The Journal of Physical Chemistry A, Vol. 120, Issue 34 https://doi.org/10.1021/acs.jpca.6b07796	journal	August 2016
How Morphology Affects Singlet Fission in Crystalline Tetracene Piland, Geoffrey B.; Bardeen, Christopher J. The Journal of Physical Chemistry Letters, Vol. 6, Issue 10 https://doi.org/10.1021/acs.jpclett.5b00569	journal	May 2015
Observation of Two Triplet-Pair Intermediates in Singlet Exciton Fission Pensack, Ryan D.; Ostroumov, Evgeny E.; Tilley, Andrew J. The Journal of Physical Chemistry Letters, Vol. 7, Issue 13 https://doi.org/10.1021/acs.jpclett.6b00947	journal	June 2016
A Direct Mechanism of Ultrafast Intramolecular Singlet Fission in Pentacene Dimers Fuemmeler, Eric G.; Sanders, Samuel N.; Pun, Andrew B. ACS Central Science, Vol. 2, Issue 5 https://doi.org/10.1021/acscentsci.6b00063	journal	May 2016
Singlet Fission Smith, Millicent B.; Michl, Josef Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr1002613	journal	November 2010
Electronic Structure Study of Singlet Fission in Tetracene Derivatives Casanova, David Journal of Chemical Theory and Computation, Vol. 10, Issue 1 https://doi.org/10.1021/ct4007635	journal	November 2013
Exciton Fission and Charge Generation via Triplet Excitons in Pentacene/C ₆₀ Bilayers Rao, Akshay; Wilson, Mark W. B.; Hodgkiss, Justin M. Journal of the American Chemical Society, Vol. 132, Issue 36 https://doi.org/10.1021/ja1042462	journal	September 2010
Ultrafast Dynamics of Exciton Fission in Polycrystalline Pentacene Wilson, Mark W. B.; Rao, Akshay; Clark, Jenny Journal of the American Chemical Society, Vol. 133, Issue 31 https://doi.org/10.1021/ja201688h	journal	August 2011
Quantum Beats in Crystalline Tetracene Delayed Fluorescence Due to Triplet Pair Coherences Produced by Direct Singlet Fission Burdett, Jonathan J.; Bardeen, Christopher J. Journal of the American Chemical Society, Vol. 134, Issue 20 https://doi.org/10.1021/ja301683w	journal	May 2012
Singlet Exciton Fission in Polycrystalline Thin Films of a Slip-Stacked Perylenediimide Eaton, Samuel W.; Shoer, Leah E.; Karlen, Steven D. Journal of the American Chemical Society, Vol. 135, Issue 39 https://doi.org/10.1021/ja4053174	journal	September 2013
Temperature-Independent Singlet Exciton Fission in Tetracene Wilson, Mark W. B.; Rao, Akshay; Johnson, Kerr Journal of the American Chemical Society, Vol. 135, Issue 44 https://doi.org/10.1021/ja408854u	journal	October 2013
Triplet vs Singlet Energy Transfer in Organic Semiconductors: The Tortoise and the Hare Yost, Shane R.; Hontz, Eric; Yeganeh, Sina The Journal of Physical Chemistry C, Vol. 116, Issue 33 https://doi.org/10.1021/jp304433t	journal	August 2012
Broad-Band Impulsive Vibrational Spectroscopy of Excited Electronic States in the Time Domain Liebel, Matz; Kukura, Philipp The Journal of Physical Chemistry Letters, Vol. 4, Issue 8 https://doi.org/10.1021/jz4004203	journal	March 2013
Transient Grating Photoluminescence Spectroscopy: An Ultrafast Method of Gating Broadband Spectra Chen, Kai; Gallaher, Joseph K.; Barker, Alex J. The Journal of Physical Chemistry Letters, Vol. 5, Issue 10 https://doi.org/10.1021/jz5006362	journal	May 2014
Tetracene Derivatives as Potential Red Emitters for Organic LEDs Odom, Susan A.; Parkin, Sean R.; Anthony, John E. Organic Letters, Vol. 5, Issue 23 https://doi.org/10.1021/ol035415e	journal	November 2003
The energy barrier in singlet fission can be overcome through coherent coupling and entropic gain Chan, Wai-Lun; Ligges, Manuel; Zhu, X-Y. Nature Chemistry, Vol. 4, Issue 10 https://doi.org/10.1038/nchem.1436	journal	August 2012
A transferable model for singlet-fission kinetics Yost, Shane R.; Lee, Jiye; Wilson, Mark W. B. Nature Chemistry, Vol. 6, Issue 6 https://doi.org/10.1038/nchem.1945	journal	May 2014
Real-time observation of multiexcitonic states in ultrafast singlet fission using coherent 2D electronic spectroscopy Bakulin, Artem A.; Morgan, Sarah E.; Kehoe, Tom B. Nature Chemistry, Vol. 8, Issue 1 https://doi.org/10.1038/nchem.2371	journal	October 2015
Dynamics of the triplet-pair state reveals the likely coexistence of coherent and incoherent singlet fission in crystalline hexacene Monahan, Nicholas R.; Sun, Dezheng; Tamura, Hiroyuki Nature Chemistry, Vol. 9, Issue 4 https://doi.org/10.1038/nchem.2665	journal	December 2016
The entangled triplet pair state in acene and heteroacene materials Yong, Chaw Keong; Musser, Andrew J.; Bayliss, Sam L. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15953	journal	July 2017
Evidence for conical intersection dynamics mediating ultrafast singlet exciton fission Musser, Andrew J.; Liebel, Matz; Schnedermann, Christoph Nature Physics, Vol. 11, Issue 4 https://doi.org/10.1038/nphys3241	journal	March 2015
Polymorphism influences singlet fission rates in tetracene thin films Arias, Dylan H.; Ryerson, Joseph L.; Cook, Jasper D. Chemical Science, Vol. 7, Issue 2 https://doi.org/10.1039/C5SC03535J	journal	January 2016
Theory of Magnetic Field Effects on the Mutual Annihilation of Triplet Excitons Merrifield, R. E. The Journal of Chemical Physics, Vol. 48, Issue 9 https://doi.org/10.1063/1.1669777	journal	May 1968
Solar conversion efficiency of photovoltaic and photoelectrolysis cells with carrier multiplication absorbers Hanna, M. C.; Nozik, A. J. Journal of Applied Physics, Vol. 100, Issue 7 https://doi.org/10.1063/1.2356795	journal	October 2006
Excited state dynamics in solid and monomeric tetracene: The roles of superradiance and exciton fission Burdett, Jonathan J.; Müller, Astrid M.; Gosztola, David The Journal of Chemical Physics, Vol. 133, Issue 14 https://doi.org/10.1063/1.3495764	journal	October 2010
The dependence of singlet exciton relaxation on excitation density and temperature in polycrystalline tetracene thin films: Kinetic evidence for a dark intermediate state and implications for singlet fission Burdett, Jonathan J.; Gosztola, David; Bardeen, Christopher J. The Journal of Chemical Physics, Vol. 135, Issue 21 https://doi.org/10.1063/1.3664630	journal	December 2011
Microscopic theory of singlet exciton fission. I. General formulation Berkelbach, Timothy C.; Hybertsen, Mark S.; Reichman, David R. The Journal of Chemical Physics, Vol. 138, Issue 11 https://doi.org/10.1063/1.4794425	journal	March 2013
Electronic resonance with anticorrelated pigment vibrations drives photosynthetic energy transfer outside the adiabatic framework Tiwari, Vivek; Peters, William K.; Jonas, David M. Proceedings of the National Academy of Sciences, Vol. 110, Issue 4 https://doi.org/10.1073/pnas.1211157110	journal	December 2012
Identification of a triplet pair intermediate in singlet exciton fission in solution Stern, Hannah L.; Musser, Andrew J.; Gelinas, Simon Proceedings of the National Academy of Sciences, Vol. 112, Issue 25 https://doi.org/10.1073/pnas.1503471112	journal	June 2015
Morphology Effectively Controls Singlet-Triplet Exciton Relaxation and Charge Transport in Organic Semiconductors Thorsmølle, V. K.; Averitt, R. D.; Demsar, J. Physical Review Letters, Vol. 102, Issue 1 https://doi.org/10.1103/PhysRevLett.102.017401	journal	January 2009
Vibrationally Coherent Crossing and Coupling of Electronic States during Internal Conversion in β -Carotene Liebel, M.; Schnedermann, C.; Kukura, P. Physical Review Letters, Vol. 112, Issue 19 https://doi.org/10.1103/PhysRevLett.112.198302	journal	May 2014
Magnetic effects on triplet exciton interactions Merrifield, R. E. Pure and Applied Chemistry, Vol. 27, Issue 3 https://doi.org/10.1351/pac197127030481	journal	January 1971

Cited By (8)

Anisotropic Singlet Fission in Single Crystalline Hexacene Sun, Dezheng; Deng, Gang-Hua; Xu, Bolei iScience, Vol. 19 https://doi.org/10.1016/j.isci.2019.08.053	journal	September 2019
Spin density encodes intramolecular singlet exciton fission in pentacene dimers Krishnapriya, K. C.; Roy, Palas; Puttaraju, Boregowda Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-018-07736-3	journal	January 2019
Tensor network simulation of multi-environmental open quantum dynamics via machine learning and entanglement renormalisation Schröder, Florian A. Y. N.; Turban, David H. P.; Musser, Andrew J. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09039-7	journal	March 2019
A molecular movie of ultrafast singlet fission Schnedermann, Christoph; Alvertis, Antonios M.; Wende, Torsten Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-12220-7	journal	September 2019
Unveiling how intramolecular stacking modes of covalently linked dimers dictate photoswitching properties Lu, Ru-Qiang; Yan, Xiao-Yun; Zhu, Lei Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-13428-3	journal	December 2019
Davydov splitting and singlet fission in excitonically coupled pentacene dimers Basel, Bettina Sabine; Hetzer, Constantin; Zirzlmeier, Johannes Chemical Science, Vol. 10, Issue 13 https://doi.org/10.1039/c9sc00384c	journal	January 2019
Influence of the heavy-atom effect on singlet fission: a study of platinum-bridged pentacene dimers Basel, Bettina S.; Young, Ryan M.; Krzyaniak, Matthew D. Chemical Science, Vol. 10, Issue 48 https://doi.org/10.1039/c9sc04410h	journal	January 2019
Order enables efficient electron-hole separation at an organic heterojunction with a small energy loss. Menke, S. Matthew; Cheminal, Alexandre; Conaghan, Patrick Springer Science and Business Media LLC https://doi.org/10.17863/cam.18578	journalarticle	January 2018

Similar Records

Transport of Spin-Entangled Triplet Excitons Generated by Singlet Fission

Journal Article · Tue Nov 06 23:00:00 EST 2018 · Journal of Physical Chemistry Letters · OSTI ID:1485559

Cooperative Singlet and Triplet Exciton Transport in Tetracene Crystals Visualized by Ultrafast Microscopys

Journal Article · Mon Sep 14 00:00:00 EDT 2015 · Nature Chemistry · OSTI ID:1225469

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
excited states
materials chemistry
solar cells

Vibronically coherent ultrafast triplet-pair formation and subsequent thermally activated dissociation control efficient endothermic singlet fission

Citation Formats

References (34)

Cited By (8)

Linked Research (1)

Similar Records

Related Subjects