Triplet Excitons in Pentacene Are Intrinsically Difficult to Dissociate via Charge Transfer

Pace, Natalie A.; Clikeman, Tyler T.; Strauss, Steven H.; Boltalina, Olga V.; Johnson, Justin C.; Rumbles, Garry; Reid, Obadiah G.

doi:10.1021/acs.jpcc.0c08537

Triplet Excitons in Pentacene Are Intrinsically Difficult to Dissociate via Charge Transfer

Journal Article · Tue Nov 17 00:00:00 EST 2020 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.0c08537· OSTI ID:1755735

^[1]; Clikeman, Tyler T. ^[2]; ^[2]; Boltalina, Olga V. ^[2]; ^[1]; ^[1]; ^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States)
Colorado State Univ., Fort Collins, CO (United States)

Singlet fission (SF) has the potential to bypass the Shockley–Queisser limit for solar cell efficiency through the production of two electron–hole pairs per photon. However, in polycrystalline pentacene this goal is hindered by slow charge transfer from triplets (=10⁷ s^–1) after SF. In this paper we demonstrate that slow charge transfer is an intrinsic property of triplet states in this material and most likely not connected with the triplet pair states that may result from singlet fission. We compare two perylene diimide/pentacene charge transfer systems that differ only by triplet generation mechanism: SF versus intersystem crossing (ISC), sensitized by using a soluble lead phthalocyanine derivative. We use time-resolved microwave conductivity (TRMC) to measure the charge yield in each system and transient absorption (TA) to follow the triplet population dynamics. These experiments are described by a single global kinetic model, with most of its parameters fixed via control experiments. While we observe modest differences in the charge-transfer rate constants between each sample, 4–10× as a function of triplet generation mechanism, all samples remain far below the predicted diffusion-limited rate constant of 10⁷–10⁸ s^–1.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1755735

Report Number(s):: NREL/JA--5900-77951; MainId:31860; UUID:1b689ae7-c372-4b73-9d2a-e81077cf0ce1; MainAdminID:19063

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 48 Vol. 124; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (43)

Triplet Dynamics in Pentacene Crystals: Applications to Fission-Sensitized Photovoltaics Poletayev, Andrey D.; Clark, Jenny; Wilson, Mark W. B. Advanced Materials, Vol. 26, Issue 6 https://doi.org/10.1002/adma.201302427	journal	December 2013
Triplet Harvesting from Intramolecular Singlet Fission in Polytetracene Pun, Andrew B.; Sanders, Samuel N.; Kumarasamy, Elango Advanced Materials, Vol. 29, Issue 41 https://doi.org/10.1002/adma.201701416	journal	September 2017
Core Perylene Diimide Designs via Direct Bay- and ortho -(Poly)trifluoromethylation: Synthesis, Isolation, X-ray Structures, Optical and Electronic Properties : Core Perylene Diimide Designs Clikeman, Tyler T.; Bukovsky, Eric V.; Wang, Xue-Bin European Journal of Organic Chemistry, Vol. 2015, Issue 30 https://doi.org/10.1002/ejoc.201501024	journal	September 2015
The polarizability of tetracene in its first excited singlet state Varma, C. A. G. O.; Oosterhoff, L. J. Chemical Physics Letters, Vol. 8, Issue 1 https://doi.org/10.1016/0009-2614(71)80560-2	journal	January 1971
Titanyl phthalocyanine and its soluble derivatives: Highly efficient photosensitizers for singlet oxygen production Zhang, Xian-Fu; Wang, Yun; Niu, Lihong Journal of Photochemistry and Photobiology A: Chemistry, Vol. 209, Issue 2-3 https://doi.org/10.1016/j.jphotochem.2009.12.002	journal	January 2010
Spin-Vibronic Mechanism for Intersystem Crossing Penfold, Thomas J.; Gindensperger, Etienne; Daniel, Chantal Chemical Reviews, Vol. 118, Issue 15 https://doi.org/10.1021/acs.chemrev.7b00617	journal	March 2018
Photoinduced Carrier Generation and Recombination Dynamics of a Trilayer Cascade Heterojunction Composed of Poly(3-hexylthiophene), Titanyl Phthalocyanine, and C ₆₀ Park, Jaehong; Reid, Obadiah G.; Rumbles, Garry The Journal of Physical Chemistry B, Vol. 119, Issue 24 https://doi.org/10.1021/acs.jpcb.5b00110	journal	December 2014
Resonance Energy Transfer Enables Efficient Planar Heterojunction Organic Solar Cells Reid, Obadiah G.; Rumbles, Garry The Journal of Physical Chemistry C, Vol. 120, Issue 1 https://doi.org/10.1021/acs.jpcc.5b10276	journal	December 2015
Emerging Design Principles for Enhanced Solar Energy Utilization with Singlet Fission Gish, Melissa K.; Pace, Natalie A.; Rumbles, Garry The Journal of Physical Chemistry C, Vol. 123, Issue 7 https://doi.org/10.1021/acs.jpcc.8b10876	journal	January 2019
Robust Processing of Small-Molecule:Fullerene Organic Solar Cells via Use of Nucleating Agents Treat, Neil D.; Reid, Obadiah G.; Fearn, Sarah ACS Applied Energy Materials, Vol. 1, Issue 5 https://doi.org/10.1021/acsaem.8b00082	journal	April 2018
Singlet Exciton Fission Photovoltaics Lee, Jiye; Jadhav, Priya; Reusswig, Philip D. Accounts of Chemical Research, Vol. 46, Issue 6 https://doi.org/10.1021/ar300288e	journal	April 2013
Charge Mobilities in Organic Semiconducting Materials Determined by Pulse-Radiolysis Time-Resolved Microwave Conductivity: π-Bond-Conjugated Polymers versus π−π-Stacked Discotics Warman, John M.; de Haas, Matthijs P.; Dicker, Gerald Chemistry of Materials, Vol. 16, Issue 23 https://doi.org/10.1021/cm049577w	journal	November 2004
Electrochemistry of main-group phthalocyanines Lever, A. B. P.; Minor, P. C. Inorganic Chemistry, Vol. 20, Issue 11 https://doi.org/10.1021/ic50225a088	journal	November 1981
Parameters Influencing the Efficiency of Electron Injection in Dye-Sensitized Solar Cells Koops, Sara E.; O’Regan, Brian C.; Barnes, Piers R. F. Journal of the American Chemical Society, Vol. 131, Issue 13 https://doi.org/10.1021/ja8091278	journal	April 2009
Direct Observation of the Reduction of Aryl Halides by a Photoexcited Perylene Diimide Radical Anion Zeman, Charles J.; Kim, Soojin; Zhang, Fang Journal of the American Chemical Society, Vol. 142, Issue 5 https://doi.org/10.1021/jacs.9b13027	journal	January 2020
Electron Transfer from the Singlet and Triplet Excited States of Ru(dcbpy) ₂ (NCS) ₂ into Nanocrystalline TiO ₂ Thin Films Kallioinen, Jani; Benkö, Gábor; Sundström, Villy The Journal of Physical Chemistry B, Vol. 106, Issue 17 https://doi.org/10.1021/jp0143443	journal	May 2002
Contactless Determination of the Photoconductivity Action Spectrum, Exciton Diffusion Length, and Charge Separation Efficiency in Polythiophene-Sensitized TiO ₂ Bilayers Kroeze, Jessica E.; Savenije, Tom J.; Vermeulen, Martien J. W. The Journal of Physical Chemistry B, Vol. 107, Issue 31 https://doi.org/10.1021/jp0217738	journal	August 2003
Liquid Crystalline Metal-Free Phthalocyanines Designed for Charge and Exciton Transport Tant, Julien; Geerts, Yves Henri; Lehmann, Matthias The Journal of Physical Chemistry B, Vol. 109, Issue 43 https://doi.org/10.1021/jp054778o	journal	November 2005
Highly Photoactive Titanyl Phthalocyanine Polymorphs as Textured Donor Layers in Organic Solar Cells Placencia, Diogenes; Wang, Weining; Gantz, Jeremy The Journal of Physical Chemistry C, Vol. 115, Issue 38 https://doi.org/10.1021/jp2052085	journal	September 2011
Revealing the Dynamics of Charge Carriers in Polymer:Fullerene Blends Using Photoinduced Time-Resolved Microwave Conductivity Savenije, Tom J.; Ferguson, Andrew J.; Kopidakis, Nikos The Journal of Physical Chemistry C, Vol. 117, Issue 46 https://doi.org/10.1021/jp406706u	journal	October 2013
Pd(II) Phthalocyanine-Sensitized Triplet−Triplet Annihilation from Rubrene Singh-Rachford, Tanya N.; Castellano, Felix N. The Journal of Physical Chemistry A, Vol. 112, Issue 16 https://doi.org/10.1021/jp7111878	journal	April 2008
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
Harvesting singlet fission for solar energy conversion via triplet energy transfer Tritsch, John R.; Chan, Wai-Lun; Wu, Xiaoxi Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3679	journal	October 2013
Microstructure formation in molecular and polymer semiconductors assisted by nucleation agents Treat, Neil D.; Nekuda Malik, Jennifer A.; Reid, Obadiah Nature Materials, Vol. 12, Issue 7 https://doi.org/10.1038/nmat3655	journal	June 2013
Slow charge transfer from pentacene triplet states at the Marcus optimum Pace, Natalie A.; Korovina, Nadezhda V.; Clikeman, Tyler T. Nature Chemistry, Vol. 12, Issue 1 https://doi.org/10.1038/s41557-019-0367-x	journal	November 2019
Sensitization of silicon by singlet exciton fission in tetracene Einzinger, Markus; Wu, Tony; Kompalla, Julia F. Nature, Vol. 571, Issue 7763 https://doi.org/10.1038/s41586-019-1339-4	journal	July 2019
Femtosecond to nanosecond excited state dynamics of vapor deposited copper phthalocyanine thin films Caplins, Benjamin W.; Mullenbach, Tyler K.; Holmes, Russell J. Physical Chemistry Chemical Physics, Vol. 18, Issue 16 https://doi.org/10.1039/C6CP00958A	journal	January 2016
Dynamics of singlet fission and electron injection in self-assembled acene monolayers on titanium dioxide Pace, Natalie A.; Arias, Dylan H.; Granger, Devin B. Chemical Science, Vol. 9, Issue 11 https://doi.org/10.1039/C7SC04688J	journal	January 2018
Triplet excitons: improving exciton diffusion length for enhanced organic photovoltaics Luppi, Bruno T.; Majak, Darren; Gupta, Manisha Journal of Materials Chemistry A, Vol. 7, Issue 6 https://doi.org/10.1039/C8TA10037C	journal	January 2019
Optical limiter using a lead phthalocyanine Shirk, James S.; Pong, Richard G. S.; Bartoli, F. J. Applied Physics Letters, Vol. 63, Issue 14 https://doi.org/10.1063/1.110635	journal	October 1993
Very-high-efficiency double-heterostructure copper phthalocyanine/C60 photovoltaic cells Peumans, P.; Forrest, S. R. Applied Physics Letters, Vol. 79, Issue 1 https://doi.org/10.1063/1.1384001	journal	July 2001
Excited state polarizabilities of conjugated molecules calculated using time dependent density functional theory Grozema, F. C.; Telesca, R.; Jonkman, H. T. The Journal of Chemical Physics, Vol. 115, Issue 21 https://doi.org/10.1063/1.1415085	journal	December 2001
On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I Marcus, R. A. The Journal of Chemical Physics, Vol. 24, Issue 5 https://doi.org/10.1063/1.1742723	journal	May 1956
Excited state lifetime and intersystem crossing rate of asymmetric pentaazadentate porphyrin-like metal complexes Byeon, Clare C.; McKerns, Michael M.; Sun, Wenfang Applied Physics Letters, Vol. 84, Issue 25 https://doi.org/10.1063/1.1763983	journal	June 2004
Electrodeless measurement of charge carrier mobility in pentacene by microwave and optical spectroscopy techniques Saeki, Akinori; Seki, Shu; Tagawa, Seiichi Journal of Applied Physics, Vol. 100, Issue 2 https://doi.org/10.1063/1.2214638	journal	July 2006
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
Dissociation processes of singlet and triplet excitons in organic photovoltaic cells Xu, Zhihua; Wu, Yue; Hu, Bin Applied Physics Letters, Vol. 89, Issue 13 https://doi.org/10.1063/1.2357584	journal	September 2006
High efficiency organic multilayer photodetectors based on singlet exciton fission Lee, J.; Jadhav, P.; Baldo, M. A. Applied Physics Letters, Vol. 95, Issue 3 https://doi.org/10.1063/1.3182787	journal	July 2009
Quantitative analysis of time-resolved microwave conductivity data Reid, Obadiah G.; Moore, David T.; Li, Zhen Journal of Physics D: Applied Physics, Vol. 50, Issue 49 https://doi.org/10.1088/1361-6463/aa9559	journal	November 2017
Localization length scales of triplet excitons in singlet fission materials Bayliss, Sam L.; Thorley, Karl J.; Anthony, John E. Physical Review B, Vol. 92, Issue 11 https://doi.org/10.1103/PhysRevB.92.115432	journal	September 2015
Magnetic Field Effect on Triplet Exciton Quenching in Organic Crystals Ern, V.; Merrifield, R. E. Physical Review Letters, Vol. 21, Issue 9 https://doi.org/10.1103/PhysRevLett.21.609	journal	August 1968
Distinct properties of the triplet pair state from singlet fission Trinh, M. Tuan; Pinkard, Andrew; Pun, Andrew B. Science Advances, Vol. 3, Issue 7 https://doi.org/10.1126/sciadv.1700241	journal	July 2017
External Quantum Efficiency Above 100% in a Singlet-Exciton-Fission-Based Organic Photovoltaic Cell Congreve, D. N.; Lee, J.; Thompson, N. J. Science, Vol. 340, Issue 6130 https://doi.org/10.1126/science.1232994	journal	April 2013

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