Tuning Triplet-Pair Separation versus Relaxation Using a Diamond Anvil Cell

Grayson S. Doucette; Haw Tyng Huang; Jason M. Munro; Kyle T. Munson; Changyong Park; John E. Anthony; Timothy Strobel; Ismaila Dabo; John V. Badding; John B. Asbury

doi:10.1016/j.xcrp.2019.100005

Tuning Triplet-Pair Separation versus Relaxation Using a Diamond Anvil Cell

Grayson S. Doucette, Haw Tyng Huang, Jason M. Munro, Kyle T. Munson, Changyong Park, John E. Anthony, Timothy Strobel, Ismaila Dabo, John V. Badding, John B. Asbury

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

Abstract

A tradeoff exists between triplet-pair separation versus relaxation that can limit the ability to utilize singlet fission for enhancing solar cell efficiency beyond the Shockley-Queisser limit. Here, we show that this tradeoff can be avoided in crystalline environments by studying a functionalized pentacene compressed in a diamond anvil cell. We demonstrate, using ultrafast transient absorption spectroscopy, that there is a “sweet spot” where the rate of triplet-pair separation can be accelerated by nearly an order of magnitude without causing fast excited state relaxation. X-ray diffraction and computational modeling allow us to quantify the corresponding increase of intermolecular coupling. Our findings suggest that increased coupling enhances excited state relaxation but that crystalline environments can suppress these relaxation processes in pentacene derivatives. The combination of these effects leads to the sweet spot and informs efforts to enhance triplet-pair separation rates in amorphous systems such as polymers.

Original language	English
Article number	100005
Journal	Cell Reports Physical Science
Volume	1
Issue number	1
DOIs	https://doi.org/10.1016/j.xcrp.2019.100005
State	Published - Jan 22 2020

Bibliographical note

Publisher Copyright:
© 2019 The Author(s)

Funding

G.S.D. and J.B.A thank the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences for support of this research through grant DE-SC0019349. K.T.M. is grateful for support from the National Science Foundation Graduate Research Fellowship Program under grant no. DGE-1255832. J.B.A. thanks Ryan D. Pensack and Christopher Grieco for helpful discussions. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. T.S. gratefully acknowledges U.S. Army Research Laboratory under grant no. W911NF-17-1-0604. J.B. thanks salary support for H.T.-H. provided by DARPA under grant no. W31P4Q-13-1-0005. I.D. acknowledges support from the Soltis faculty support award and the Ralph E. Powe junior faculty award from Oak Ridge Associated Universities. J.E.A. thanks the National Science Foundation (CMMI-1255494) for supporting semiconductor synthesis. Portions of this work were performed at HPCAT (Sector 16), Advanced Photon Source (APS), Argonne National Laboratory. HPCAT operations are supported by DOE-NNSA's Office of Experimental Sciences. The Advanced Photon Source is a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. Conceptualization, J.B.A. G.S.D. and H.-T.H.; Methodology, J.B.A. and G.S.D.; Validation, J.B.A. G.S.D. and H.-T.H.; Formal Analysis, J.B.A. G.S.D. H.-T.H. and J.M.M.; Writing – Original Draft, J.B.A. and G.S.D. Writing – Review and Editing, J.B.A. G.S.D. H.-T.H. J.M.M. K.T.M. C.P. T.S. and I.D.; Funding Acquisition, J.B.A.; Supervision, J.B.A. J.B.A. owns equity in Magnitude Instruments, which has an interest in this project. His ownership in this company has been reviewed by the Pennsylvania State University's Individual Conflict of Interest Committee and is currently being managed by the University. G.S.D. and J.B.A thank the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences for support of this research through grant DE-SC0019349 . K.T.M. is grateful for support from the National Science Foundation Graduate Research Fellowship Program under grant no. DGE-1255832 . J.B.A. thanks Ryan D. Pensack and Christopher Grieco for helpful discussions. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. T.S. gratefully acknowledges U.S. Army Research Laboratory under grant no. W911NF-17-1-0604 . J.B. thanks salary support for H.T.-H. provided by DARPA under grant no. W31P4Q-13-1-0005 . I.D. acknowledges support from the Soltis faculty support award and the Ralph E. Powe junior faculty award from Oak Ridge Associated Universities . J.E.A. thanks the National Science Foundation ( CMMI-1255494 ) for supporting semiconductor synthesis. Portions of this work were performed at HPCAT (Sector 16), Advanced Photon Source (APS), Argonne National Laboratory. HPCAT operations are supported by DOE-NNSA’s Office of Experimental Sciences . The Advanced Photon Source is a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357 .

Funders	Funder number
DOE-NNSA's Office of Experimental Sciences
DOE-NNSA’s Office of Experimental Sciences
Soltis faculty
National Science Foundation (NSF)	DGE-1255832
Michigan State University-U.S. Department of Energy (MSU-DOE) Plant Research Laboratory
Defense Advanced Research Projects Agency	W31P4Q-13-1-0005
Office of Science Programs
Office of Basic Energy Sciences	DE-SC0019349
Argonne National Laboratory	DE-AC02-06CH11357
Oak Ridge Associated Universities	CMMI-1255494
Army Research Laboratory	W911NF-17-1-0604
The Pennsylvania State University

Keywords

Diamond Anvil Cell
High-Pressure
Intermolecular Coupling
Pentacene
Singlet Fission
Triplet Pair Separation
Ultrafast Spectroscopy

ASJC Scopus subject areas

General Chemistry
General Engineering
General Energy
General Materials Science
General Physics and Astronomy

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10.1016/j.xcrp.2019.100005

Cite this

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title = "Tuning Triplet-Pair Separation versus Relaxation Using a Diamond Anvil Cell",

abstract = "A tradeoff exists between triplet-pair separation versus relaxation that can limit the ability to utilize singlet fission for enhancing solar cell efficiency beyond the Shockley-Queisser limit. Here, we show that this tradeoff can be avoided in crystalline environments by studying a functionalized pentacene compressed in a diamond anvil cell. We demonstrate, using ultrafast transient absorption spectroscopy, that there is a “sweet spot” where the rate of triplet-pair separation can be accelerated by nearly an order of magnitude without causing fast excited state relaxation. X-ray diffraction and computational modeling allow us to quantify the corresponding increase of intermolecular coupling. Our findings suggest that increased coupling enhances excited state relaxation but that crystalline environments can suppress these relaxation processes in pentacene derivatives. The combination of these effects leads to the sweet spot and informs efforts to enhance triplet-pair separation rates in amorphous systems such as polymers.",

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AU - Huang, Haw Tyng

AU - Munro, Jason M.

AU - Munson, Kyle T.

AU - Park, Changyong

AU - Anthony, John E.

AU - Strobel, Timothy

AU - Dabo, Ismaila

AU - Badding, John V.

AU - Asbury, John B.

PY - 2020/1/22

Y1 - 2020/1/22

N2 - A tradeoff exists between triplet-pair separation versus relaxation that can limit the ability to utilize singlet fission for enhancing solar cell efficiency beyond the Shockley-Queisser limit. Here, we show that this tradeoff can be avoided in crystalline environments by studying a functionalized pentacene compressed in a diamond anvil cell. We demonstrate, using ultrafast transient absorption spectroscopy, that there is a “sweet spot” where the rate of triplet-pair separation can be accelerated by nearly an order of magnitude without causing fast excited state relaxation. X-ray diffraction and computational modeling allow us to quantify the corresponding increase of intermolecular coupling. Our findings suggest that increased coupling enhances excited state relaxation but that crystalline environments can suppress these relaxation processes in pentacene derivatives. The combination of these effects leads to the sweet spot and informs efforts to enhance triplet-pair separation rates in amorphous systems such as polymers.

AB - A tradeoff exists between triplet-pair separation versus relaxation that can limit the ability to utilize singlet fission for enhancing solar cell efficiency beyond the Shockley-Queisser limit. Here, we show that this tradeoff can be avoided in crystalline environments by studying a functionalized pentacene compressed in a diamond anvil cell. We demonstrate, using ultrafast transient absorption spectroscopy, that there is a “sweet spot” where the rate of triplet-pair separation can be accelerated by nearly an order of magnitude without causing fast excited state relaxation. X-ray diffraction and computational modeling allow us to quantify the corresponding increase of intermolecular coupling. Our findings suggest that increased coupling enhances excited state relaxation but that crystalline environments can suppress these relaxation processes in pentacene derivatives. The combination of these effects leads to the sweet spot and informs efforts to enhance triplet-pair separation rates in amorphous systems such as polymers.

KW - Diamond Anvil Cell

KW - High-Pressure

KW - Intermolecular Coupling

KW - Pentacene

KW - Singlet Fission

KW - Triplet Pair Separation

KW - Ultrafast Spectroscopy

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Tuning Triplet-Pair Separation versus Relaxation Using a Diamond Anvil Cell

Abstract

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Keywords

ASJC Scopus subject areas

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