A New Frontier in Exciton Transport: Transient Delocalization.

Delocalizations; Disordered medium; Exciton state; Exciton transport; Exciton-phonon couplings; Harvesting devices; Light-harvesting; Localized exciton; Recent researches; Transport mechanism; Materials Science (all); Physical and Theoretical Chemistry; General Materials Science

Abstract :

[en] Efficient exciton transport is crucial to the application of organic semiconductors (OSCs) in light-harvesting devices. While the physics of exciton transport in highly disordered media is well-explored, the description of transport in structurally and energetically ordered OSCs is less established, despite such materials being favorable for devices. In this Perspective we describe and highlight recent research pointing toward a highly efficient exciton transport mechanism which occurs in ordered OSCs, transient delocalization. Here, exciton-phonon couplings play a critical role in allowing localized exciton states to temporarily access higher-energy delocalized states whereupon they move large distances. The mechanism shows great promise for facilitating long-range exciton transport and may allow for improved device efficiencies and new device architectures. However, many fundamental questions on transient delocalization remain to be answered. These questions and suggested next steps are summarized.

Disciplines :

Chemistry

Author, co-author :

Sneyd, Alexander J; Department of Physics, Cavendish Laboratory, University of Cambridge, Cambridge CB3 0HE, United Kingdom

Beljonne, David ; Université de Mons - UMONS

Rao, Akshay ; Department of Physics, Cavendish Laboratory, University of Cambridge, Cambridge CB3 0HE, United Kingdom

Language :

English

Title :

A New Frontier in Exciton Transport: Transient Delocalization.

Publication date :

28 July 2022

Journal title :

Journal of Physical Chemistry Letters

eISSN :

1948-7185

Publisher :

American Chemical Society, United States

Volume :

Issue :

Pages :

6820 - 6830

Peer reviewed :

Peer Reviewed verified by ORBi

Additional URL :

https://pubs.acs.org/doi/pdf/10.1021/acs.jpclett.2c01133

Research unit :

S817 - Chimie des matériaux nouveaux

Research institute :

Complexys
Matériaux

Funders :

Engineering and Physical Sciences Research Council
H2020 European Research Council

Funding text :

This work has received funding from the European Research Council under the European Union’s Horizon 2020 research and innovation programme (grant agreement number 758826). We acknowledge support from the Engineering and Physical Sciences Research Council (UK) via grant EP/W017091/1. A.J.S. acknowledges the Royal Society Te Apa̅rangi; the Cambridge Commonwealth European and International Trust; the Winton Programme for the Physics of Sustainability; and St John’s College, University of Cambridge for their financial support. D.B. is a Research Director of the Belgian ‘Fonds de la Recherche Scientifique’ (F.R.S.-FNRS).

Available on ORBi UMONS :

since 13 January 2023

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Bibliography

Mikhnenko, O. V.; Blom, P. W. M.; Nguyen, T.-Q. Exciton Diffusion in Organic Semiconductors. Energy Environ. Sci. 2015, 8 (7), 1867-1888, 10.1039/C5EE00925A
Menke, S. M.; Holmes, R. J. Exciton Diffusion in Organic Photovoltaic Cells. Energy and Environmental Science 2014, 7, 499-512, 10.1039/C3EE42444H
Tamai, Y.; Ohkita, H.; Benten, H.; Ito, S. Exciton Diffusion in Conjugated Polymers: From Fundamental Understanding to Improvement in Photovoltaic Conversion Efficiency. J. Phys. Chem. Lett. 2015, 6 (17), 3417-3428, 10.1021/acs.jpclett.5b01147
Wadsworth, A.; Hamid, Z.; Kosco, J.; Gasparini, N.; McCulloch, I. The Bulk Heterojunction in Organic Photovoltaic, Photodetector, and Photocatalytic Applications. Adv. Mater. 2020, 32, 2001763, 10.1002/adma.202001763
Kohler, A.; Bassler, H. Electronic Processes in Organic Semiconductors; 2015.
Jin, X.-H.; Price, M. B.; Finnegan, J. R.; Boott, C. E.; Richter, J. M.; Rao, A.; Menke, S. M.; Friend, R. H.; Whittell, G. R.; Manners, I. Long-Range Exciton Transport in Conjugated Polymer Nanofibers Prepared by Seeded Growth. Science (80-.) 2018, 360 (6391), 897-900, 10.1126/science.aar8104
Wan, Y.; Stradomska, A.; Knoester, J.; Huang, L. Direct Imaging of Exciton Transport in Tubular Porphyrin Aggregates by Ultrafast Microscopy. J. Am. Chem. Soc. 2017, 139 (21), 7287-7293, 10.1021/jacs.7b01550
Caram, J. R.; Doria, S.; Eisele, D. M.; Freyria, F. S.; Sinclair, T. S.; Rebentrost, P.; Lloyd, S.; Bawendi, M. G. Room-Temperature Micron-Scale Exciton Migration in a Stabilized Emissive Molecular Aggregate. Nano Lett. 2016, 16 (11), 6808-6815, 10.1021/acs.nanolett.6b02529
Chenu, A.; Scholes, G. D. Coherence in Energy Transfer and Photosynthesis. Annu. Rev. Phys. Chem. 2015, 66, 69-96, 10.1146/annurev-physchem-040214-121713
Brixner, T.; Hildner, R.; Köhler, J.; Lambert, C.; Würthner, F. Exciton Transport in Molecular Aggregates-From Natural Antennas to Synthetic Chromophore Systems. Adv. Energy Mater. 2017, 7 (16), 1700236, 10.1002/aenm.201700236
Aragó, J.; Troisi, A. Regimes of Exciton Transport in Molecular Crystals in the Presence of Dynamic Disorder. Adv. Funct. Mater. 2016, 26 (14), 2316-2325, 10.1002/adfm.201503888
Scholes, G. D. Long-Range Resonance Energy Transfer in Molecular Systems. Annu. Rev. Phys. Chem. 2003, 54, 57-87, 10.1146/annurev.physchem.54.011002.103746
Dexter, D. L. A Theory of Sensitized Luminescence in Solids. J. Chem. Phys. 1953, 21 (5), 836, 10.1063/1.1699044
Skourtis, S. S.; Liu, C.; Antoniou, P.; Virshup, A. M.; Beratan, D. N. Dexter Energy Transfer Pathways. Proc. Natl. Acad. Sci. U. S. A. 2016, 113 (29), 8115-8120, 10.1073/pnas.1517189113
Bai, S.; Zhang, P.; Antoniou, P.; Skourtis, S. S.; Beratan, D. N. Quantum Interferences Among Dexter Energy Transfer Pathways. Faraday Discuss. 2019, 216, 301-318, 10.1039/C9FD00007K
Olaya-Castro, A.; Scholes, G. D. Energy Transfer from Förster-Dexter Theory to Quantum Coherent Light-Harvesting. Int. Rev. Phys. Chem. 2011, 30 (1), 49-77, 10.1080/0144235X.2010.537060
Athanasopoulos, S.; Emelianova, E. V.; Walker, A. B.; Beljonne, D. Exciton Diffusion in Energetically Disordered Organic Materials. Phys. Rev. B 2009, 80 (19), 195209, 10.1103/PhysRevB.80.195209
Dubin, F.; Melet, R.; Barisien, T.; Grousson, R.; Legrand, L.; Schott, M.; Voliotis, V. Macroscopic Coherence of a Single Exciton State in an Organic Quantum Wire. Nat. Phys. 2006, 2 (1), 32-35, 10.1038/nphys196
Cao, J.; Cogdell, R. J.; Coker, D. F.; Duan, H.-G.; Hauer, J.; Kleinekathöfer, U.; C Jansen, T. L.; Mančal, T.; Dwayne Miller, R. J.; Ogilvie, J. P.; Prokhorenko, V. I.; Renger, T.; Tan, H.-S.; Tempelaar, R.; Thorwart, M.; Thyrhaug, E.; Westenhoff, S.; Zigmantas, D. Quantum Biology Revisited. Sci. Adv. 2020, 6 (14), 4888, 10.1126/sciadv.aaz4888
Pandya, R.; Chen, R. Y. S.; Gu, Q.; Gorman, J.; Auras, F.; Sung, J.; Friend, R.; Kukura, P.; Schnedermann, C.; Rao, A. Femtosecond Transient Absorption Microscopy of Singlet Exciton Motion in Side-Chain Engineered Perylene-Diimide Thin Films. J. Phys. Chem. A 2020, 124 (13), 2721-2730, 10.1021/acs.jpca.0c00346
Liu, S.; Yuan, J.; Deng, W.; Luo, M.; Xie, Y.; Liang, Q.; Zou, Y.; He, Z.; Wu, H.; Cao, Y. High-Efficiency Organic Solar Cells with Low Non-Radiative Recombination Loss and Low Energetic Disorder. Nat. Photonics 2020, 14 (5), 300-305, 10.1038/s41566-019-0573-5
Dumele, O.; Chen, J.; Passarelli, J. V.; Stupp, S. I. Supramolecular Energy Materials. Adv. Mater. 2020, 32 (17), 1907247, 10.1002/adma.201907247
Fukui, T.; Garcia-Hernandez, J. D.; MacFarlane, L. R.; Lei, S.; Whittell, G. R.; Manners, I. Seeded Self-Assembly of Charge-Terminated Poly(3-Hexylthiophene) Amphiphiles Based on the Energy Landscape. J. Am. Chem. Soc. 2020, 142, 15038-15048, 10.1021/jacs.0c06185
Ogi, S.; Sugiyasu, K.; Manna, S.; Samitsu, S.; Takeuchi, M. Living Supramolecular Polymerization Realized through a Biomimetic Approach. Nat. Chem. 2014, 6 (3), 188-195, 10.1038/nchem.1849
Schnedermann, C.; Sung, J.; Pandya, R.; Dev Verma, S.; Chen, R. Y. S.; Gauriot, N.; Bretscher, H. M.; Kukura, P.; Rao, A. Ultrafast Tracking of Exciton and Charge Carrier Transport in Optoelectronic Materials on the Nanometer Scale. J. Phys. Chem. Lett. 2019, 10 (21), 6727-6733, 10.1021/acs.jpclett.9b02437
Zhu, T.; Snaider, J. M.; Yuan, L.; Huang, L. Ultrafast Dynamic Microscopy of Carrier and Exciton Transport. Annu. Rev. Phys. Chem. 2019, 70, 219-244, 10.1146/annurev-physchem-042018-052605
Wang, L.; Qiu, J.; Bai, X.; Xu, J. Surface Hopping Methods for Nonadiabatic Dynamics in Extended Systems. Wiley Interdiscip. Rev. Comput. Mol. Sci. 2020, 10 (2), e1435 10.1002/wcms.1435
Giannini, S.; Carof, A.; Ellis, M.; Yang, H.; Ziogos, O. G.; Ghosh, S.; Blumberger, J. Quantum Localization and Delocalization of Charge Carriers in Organic Semiconducting Crystals. Nat. Commun. 2019, 10 (1), 1-12, 10.1038/s41467-019-11775-9
Huix-Rotllant, M.; Tamura, H.; Burghardt, I. Concurrent Effects of Delocalization and Internal Conversion Tune Charge Separation at Regioregular Polythiophene-Fullerene Heterojunctions. J. Phys. Chem. Lett. 2015, 6 (9), 1702-1708, 10.1021/acs.jpclett.5b00336
Binder, R.; Burghardt, I. First-Principles Quantum Simulations of Exciton Diffusion on a Minimal Oligothiophene Chain at Finite Temperature. Faraday Discuss. 2020, 221 (0), 406-427, 10.1039/C9FD00066F
Fratini, S.; Nikolka, M.; Salleo, A.; Schweicher, G.; Sirringhaus, H. Charge Transport in High-Mobility Conjugated Polymers and Molecular Semiconductors. Nat. Mater. 2020, 19 (5), 491-502, 10.1038/s41563-020-0647-2
Giannini, S.; Blumberger, J. Charge Transport in Organic Semiconductors: The Perspective from Nonadiabatic Molecular Dynamics. Acc. Chem. Res. 2022, 55 (6), 819-830, 10.1021/acs.accounts.1c00675
Giannini, S.; Ziogos, O. G.; Carof, A.; Ellis, M.; Blumberger, J. Flickering Polarons Extending over Ten Nanometres Mediate Charge Transport in High-Mobility Organic Crystals. Adv. Theory Simulations 2020, 3 (9), 2000093, 10.1002/adts.202000093
Sneyd, A. J.; Fukui, T.; Paleček, D.; Prodhan, S.; Wagner, I.; Zhang, Y.; Sung, J.; Collins, S. M.; A Slater, T. J.; Andaji-Garmaroudi, Z.; MacFarlane, L. R.; Diego Garcia-Hernandez, J.; Wang, L.; Whittell, G. R.; Hodgkiss, J. M.; Chen, K.; Beljonne, D.; Manners, I.; Friend, R. H.; Rao, A. Efficient Energy Transport in an Organic Semiconductor Mediated by Transient Exciton Delocalization. Sci. Adv. 2021, 7, eabh4232, 10.1126/sciadv.abh4232
Tamai, Y.; Matsuura, Y.; Ohkita, H.; Benten, H.; Ito, S. One-Dimensional Singlet Exciton Diffusion in Poly(3-Hexylthiophene) Crystalline Domains. J. Phys. Chem. Lett. 2014, 5 (2), 399-403, 10.1021/jz402299a
Shaw, P. E.; Ruseckas, A.; Samuel, I. D. W. Exciton Diffusion Measurements in Poly(3-Hexylthiophene). Adv. Mater. 2008, 20 (18), 3516-3520, 10.1002/adma.200800982
Masri, Z.; Ruseckas, A.; Emelianova, E. V.; Wang, L.; Bansal, A. K.; Matheson, A.; Lemke, H. T.; Nielsen, M. M.; Nguyen, H.; Coulembier, O.; Dubois, P.; Beljonne, D.; Samuel, I. D. W. Molecular Weight Dependence of Exciton Diffusion in Poly(3-Hexylthiophene). Adv. Energy Mater. 2013, 3 (11), 1445-1453, 10.1002/aenm.201300210
Nelson, T. R.; White, A. J.; Bjorgaard, J. A.; Sifain, A. E.; Zhang, Y.; Nebgen, B.; Fernandez-Alberti, S.; Mozyrsky, D.; Roitberg, A. E.; Tretiak, S. Non-Adiabatic Excited-State Molecular Dynamics: Theory and Applications for Modeling Photophysics in Extended Molecular Materials. Chem. Rev. 2020, 120 (4), 2215-2287, 10.1021/acs.chemrev.9b00447
Nelson, T. R.; Ondarse-Alvarez, D.; Oldani, N.; Rodriguez-Hernandez, B.; Alfonso-Hernandez, L.; Galindo, J. F.; Kleiman, V. D.; Fernandez-Alberti, S.; Roitberg, A. E.; Tretiak, S. Coherent Exciton-Vibrational Dynamics and Energy Transfer in Conjugated Organics. Nat. Commun. 2018, 9 (1), 2316, 10.1038/s41467-018-04694-8
Ciuchi, S.; Fratini, S.; Mayou, D. Transient Localization in Crystalline Organic Semiconductors. Phys. Rev. B-Condens. Matter Mater. Phys. 2011, 83 (8), 081202, 10.1103/PhysRevB.83.081202
Fratini, S.; Mayou, D.; Ciuchi, S. The Transient Localization Scenario for Charge Transport in Crystalline Organic Materials. Adv. Funct. Mater. 2016, 26 (14), 2292-2315, 10.1002/adfm.201502386
Prodhan, S.; Giannini, S.; Wang, L.; Beljonne, D. Long-Range Interactions Boost Singlet Exciton Diffusion in Nanofibers of π-Extended Polymer Chains. J. Phys. Chem. Lett. 2021, 12 (34), 8188-8193, 10.1021/acs.jpclett.1c02275
Giannini, S.; Peng, W.-T.; Cupellini, L.; Padula, D.; Carof, A.; Blumberger, J. Exciton Transport in Molecular Organic Semiconductors Boosted by Transient Quantum Delocalization. Nat. Commun. 2022, 13 (1), 2755, 10.1038/s41467-022-30308-5
Nalbach, P.; Eckel, J.; Thorwart, M. Quantum Coherent Biomolecular Energy Transfer with Spatially Correlated Fluctuations. New J. Phys. 2010, 12 (6), 065043, 10.1088/1367-2630/12/6/065043
Chin, A. W.; Prior, J.; Rosenbach, R.; Caycedo-Soler, F.; Huelga, S. F.; Plenio, M. B. The Role of Non-Equilibrium Vibrational Structures in Electronic Coherence and Recoherence in Pigment-Protein Complexes. Nat. Phys. 2013, 9 (2), 113-118, 10.1038/nphys2515
Seiler, H.; Krynski, M.; Zahn, D.; Hammer, S.; Windsor, Y. W.; Vasileiadis, T.; Pflaum, J.; Ernstorfer, R.; Rossi, M.; Schwoerer, H. Nuclear Dynamics of Singlet Exciton Fission in Pentacene Single Crystals. Sci. Adv. 2021, 7 (26), 869-894, 10.1126/sciadv.abg0869
Alvertis, A. M.; Pandya, R.; Muscarella, L. A.; Sawhney, N.; Nguyen, M.; Ehrler, B.; Rao, A.; Friend, R. H.; Chin, A. W.; Monserrat, B. Impact of Exciton Delocalization on Exciton-Vibration Interactions in Organic Semiconductors. Phys. Rev. B 2020, 102, 081122, 10.1103/PhysRevB.102.081122
Ruseckas, A.; Samuel, I. D. W. Engineering Highways for Excitons. Joule 2021, 5 (11), 2762-2764, 10.1016/j.joule.2021.10.015
Spano, F. C. The Spectral Signatures of Frenkel Polarons in H-and J-Aggregates. Acc. Chem. Res. 2010, 43, 429, 10.1021/ar900233v
Hestand, N. J.; Spano, F. C. Expanded Theory of H-and J-Molecular Aggregates: The Effects of Vibronic Coupling and Intermolecular Charge Transfer. Chem. Rev. 2018, 118 (15), 7069-7163, 10.1021/acs.chemrev.7b00581
Smith, S. L.; Chin, A. W. Ultrafast Charge Separation and Nongeminate Electron-Hole Recombination in Organic Photovoltaics. Phys. Chem. Chem. Phys. 2014, 16 (38), 20305-20309, 10.1039/C4CP01791A
Gélinas, S.; Rao, A.; Kumar, A.; Smith, S. L.; Chin, A. W.; Clark, J.; Van Der Poll, T. S.; Bazan, G. C.; Friend, R. H. Ultrafast Long-Range Charge Separation in Organic Semiconductor Photovoltaic Diodes. Science (80-.) 2014, 343 (6170), 512-516, 10.1126/science.1246249
Schweicher, G.; D'Avino, G.; Ruggiero, M. T.; Harkin, D. J.; Broch, K.; Venkateshvaran, D.; Liu, G.; Richard, A.; Ruzié, C.; Armstrong, J.; Kennedy, A. R.; Shankland, K.; Takimiya, K.; Geerts, Y. H.; Zeitler, J. A.; Fratini, S.; Sirringhaus, H. Chasing the "Killer" Phonon Mode for the Rational Design of Low-Disorder, High-Mobility Molecular Semiconductors. Adv. Mater. 2019, 31 (43), 1902407, 10.1002/adma.201902407
Venkateshvaran, D.; Nikolka, M.; Sadhanala, A.; Lemaur, V.; Zelazny, M.; Kepa, M.; Hurhangee, M.; Kronemeijer, A. J.; Pecunia, V.; Nasrallah, I.; Romanov, I.; Broch, K.; McCulloch, I.; Emin, D.; Olivier, Y.; Cornil, J.; Beljonne, D.; Sirringhaus, H. Approaching Disorder-Free Transport in High-Mobility Conjugated Polymers. Nature 2014, 515 (7527), 384-388, 10.1038/nature13854
Yamagata, H.; Norton, J.; Hontz, E.; Olivier, Y.; Beljonne, D.; Brédas, J. L.; Silbey, R. J.; Spano, F. C. The Nature of Singlet Excitons in Oligoacene Molecular Crystals. J. Chem. Phys. 2011, 134 (20), 204703, 10.1063/1.3590871
Deotare, P. B.; Chang, W.; Hontz, E.; Congreve, D. N.; Shi, L.; Reusswig, P. D.; Modtland, B.; Bahlke, M. E.; Lee, C. K.; Willard, A. P.; Bulovic, V.; Van Voorhis, T.; Baldo, M. A. Nanoscale Transport of Charge-Transfer States in Organic Donor-Acceptor Blends. Nat. Mater. 2015, 14 (11), 1130-1134, 10.1038/nmat4424