Activationless Charge Transfer Drives Photocurrent Generation in Organic Photovoltaic Blends Independent of Energetic Offset

Dong, Yifan; Zheng, Rui; Qian, Deping; Lee, Tack Ho; Bristow, Helen L.; Tuladhar, Pabitra Shakya; Cha, Hyojung; Durrant, James

doi:10.1021/jacs.4c11114

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Activationless Charge Transfer Drives Photocurrent Generation in Organic Photovoltaic Blends Independent of Energetic Offset

Yifan Dong

, Rui Zheng, Deping Qian, Tack Ho Lee

, Helen L. Bristow, Pabitra Shakya Tuladhar, Hyojung Cha, James Durrant

Journal of the American Chemical Society, Volume: 146, Issue: 49, Pages: 33579 - 33586

Swansea University Author: James Durrant

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DOI (Published version): 10.1021/jacs.4c11114

Abstract

Organic photovoltaics (OPVs) have recently shown substantial progress in enhancing device efficiency, driven in particular by advances in the design of nonfullerene acceptors and the reduction of the energy offset driving exciton separation at the donor/acceptor interface. Herein, we employ temperat...

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Published in:	Journal of the American Chemical Society
ISSN:	0002-7863 1520-5126
Published:	American Chemical Society (ACS) 2024
Online Access:	Check full text
URI:	https://cronfa.swan.ac.uk/Record/cronfa68474

first_indexed	2024-12-06T13:48:58Z
last_indexed	2025-01-30T20:25:05Z
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spelling	2025-01-30T14:49:26.6793704 v2 68474 2024-12-06 Activationless Charge Transfer Drives Photocurrent Generation in Organic Photovoltaic Blends Independent of Energetic Offset f3dd64bc260e5c07adfa916c27dbd58a 0000-0001-8353-7345 James Durrant James Durrant true false 2024-12-06 EAAS Organic photovoltaics (OPVs) have recently shown substantial progress in enhancing device efficiency, driven in particular by advances in the design of nonfullerene acceptors and the reduction of the energy offset driving exciton separation at the donor/acceptor interface. Herein, we employ temperature-dependent transient absorption spectroscopy to investigate the activation energy for charge generation and recombination in a range of bulk heterojunction blends with nonfullerene acceptors. Remarkably, we find that in all cases charge generation is almost activationless, in the range of 11–21 meV, independent of energetic offset. Geminate recombination is also observed to be almost activationless, with only the kinetics of bimolecular charge recombination being strongly temperature-dependent, with an activation energy >400 meV. Our observation of essentially activationless charge generation, independent of energy offset, strongly indicates that charge generation in such blends does not follow Marcus theory but can rather be considered an adiabatic process associated with the motion of thermally unrelaxed carriers. Journal Article Journal of the American Chemical Society 146 49 33579 33586 American Chemical Society (ACS) 0002-7863 1520-5126 11 12 2024 2024-12-11 10.1021/jacs.4c11114 COLLEGE NANME Engineering and Applied Sciences School COLLEGE CODE EAAS Swansea University Another institution paid the OA fee The authors gratefully acknowledge financial support from the UKRI GCRF Project SUNRISE (EP/P032591/1) and EPSRC Project ATIP (EP/TO28513/1) and KAUST (OSR-2015-CRG4-2572 and OSR-2018-CRG7-3749.2). H.C. acknowledges financial support from the National Research Foundation of Korea (NRF) Grant funded by the Korea government (MSIT) (RS-2023-00213920). 2025-01-30T14:49:26.6793704 2024-12-06T09:57:05.7651862 Faculty of Science and Engineering School of Engineering and Applied Sciences - Materials Science and Engineering Yifan Dong 0000-0003-2912-3322 1 Rui Zheng 2 Deping Qian 3 Tack Ho Lee 0000-0003-2201-0165 4 Helen L. Bristow 5 Pabitra Shakya Tuladhar 6 Hyojung Cha 7 James Durrant 0000-0001-8353-7345 8 68474__33070__cf036617bb354b94bb22ca472188ef6e.pdf 68474.VOR.pdf 2024-12-06T10:07:28.8174343 Output 2209041 application/pdf Version of Record true © 2024 The Authors. This article is licensed under CC-BY 4.0. true eng https://creativecommons.org/licenses/by/4.0/
title	Activationless Charge Transfer Drives Photocurrent Generation in Organic Photovoltaic Blends Independent of Energetic Offset
spellingShingle	Activationless Charge Transfer Drives Photocurrent Generation in Organic Photovoltaic Blends Independent of Energetic Offset James Durrant
title_short	Activationless Charge Transfer Drives Photocurrent Generation in Organic Photovoltaic Blends Independent of Energetic Offset
title_full	Activationless Charge Transfer Drives Photocurrent Generation in Organic Photovoltaic Blends Independent of Energetic Offset
title_fullStr	Activationless Charge Transfer Drives Photocurrent Generation in Organic Photovoltaic Blends Independent of Energetic Offset
title_full_unstemmed	Activationless Charge Transfer Drives Photocurrent Generation in Organic Photovoltaic Blends Independent of Energetic Offset
title_sort	Activationless Charge Transfer Drives Photocurrent Generation in Organic Photovoltaic Blends Independent of Energetic Offset
author_id_str_mv	f3dd64bc260e5c07adfa916c27dbd58a
author_id_fullname_str_mv	f3dd64bc260e5c07adfa916c27dbd58a_***_James Durrant
author	James Durrant
author2	Yifan Dong Rui Zheng Deping Qian Tack Ho Lee Helen L. Bristow Pabitra Shakya Tuladhar Hyojung Cha James Durrant
format	Journal article
container_title	Journal of the American Chemical Society
container_volume	146
container_issue	49
container_start_page	33579
publishDate	2024
institution	Swansea University
issn	0002-7863 1520-5126
doi_str_mv	10.1021/jacs.4c11114
publisher	American Chemical Society (ACS)
college_str	Faculty of Science and Engineering
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hierarchy_parent_title	Faculty of Science and Engineering
department_str	School of Engineering and Applied Sciences - Materials Science and Engineering{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Materials Science and Engineering
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description	Organic photovoltaics (OPVs) have recently shown substantial progress in enhancing device efficiency, driven in particular by advances in the design of nonfullerene acceptors and the reduction of the energy offset driving exciton separation at the donor/acceptor interface. Herein, we employ temperature-dependent transient absorption spectroscopy to investigate the activation energy for charge generation and recombination in a range of bulk heterojunction blends with nonfullerene acceptors. Remarkably, we find that in all cases charge generation is almost activationless, in the range of 11–21 meV, independent of energetic offset. Geminate recombination is also observed to be almost activationless, with only the kinetics of bimolecular charge recombination being strongly temperature-dependent, with an activation energy >400 meV. Our observation of essentially activationless charge generation, independent of energy offset, strongly indicates that charge generation in such blends does not follow Marcus theory but can rather be considered an adiabatic process associated with the motion of thermally unrelaxed carriers.
published_date	2024-12-11T08:25:55Z
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Activationless Charge Transfer Drives Photocurrent Generation in Organic Photovoltaic Blends Independent of Energetic Offset

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