Triplet Harvesting from Intramolecular Singlet Fission in Polytetracene

Pun, Andrew B.; Sanders, Samuel N.; Kumarasamy, Elango; Sfeir, Matthew Y.; Congreve, Daniel N.; Campos, Luis M.

doi:10.1002/adma.201701416

Triplet Harvesting from Intramolecular Singlet Fission in Polytetracene

Journal Article · Thu Sep 14 00:00:00 EDT 2017 · Advanced Materials

DOI:https://doi.org/10.1002/adma.201701416· OSTI ID:1390391

Pun, Andrew B. ^[1]; Sanders, Samuel N. ^[1]; Kumarasamy, Elango ^[1]; Sfeir, Matthew Y. ^[2]; Congreve, Daniel N. ^[3]; ^[1]

Department of Chemistry Columbia University New York NY 10027 USA
Center for Functional Nanomaterials Brookhaven National Laboratory Upton NY 11973 USA
Energy Frontier Research Center for Excitonics Massachusetts Institute of Technology Cambridge MA 02139 USA

Abstract

Singlet fission (SF), a promising mechanism of multiple exciton generation, has only recently been engineered as a fast, efficient, intramolecular process (iSF). The challenge now lies in designing and optimizing iSF materials that can be practically applied in high‐performance optoelectronic devices. However, most of the reported iSF systems, such as those based on donor–acceptor polymers or pentacene, have low triplet energies, which limits their applications. Tetracene‐based materials can overcome significant challenges, as the tetracene triplet state is practically useful, ≈1.2 eV. Here, the synthesis and excited state dynamics of a conjugated tetracene homopolymer are studied. This polymer undergoes ultrafast iSF in solution, generating high‐energy triplets on a sub‐picosecond time scale. Magnetic‐field‐dependent photocurrent measurements of polytetracene‐based devices demonstrate the first example of iSF‐generated triplet extraction in devices, exhibiting the potential of iSF materials for use in next‐generation devices.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0001088; SC0012704; AC02-05CH11231

OSTI ID:: 1390391

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 41 Vol. 29; ISSN 0935-9648

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (65)

Tuneable Singlet Exciton Fission and Triplet-Triplet Annihilation in an Orthogonal Pentacene Dimer Lukman, Steven; Musser, Andrew J.; Chen, Kai Advanced Functional Materials, Vol. 25, Issue 34 https://doi.org/10.1002/adfm.201501537	journal	August 2015
Nanostructured Hybrid Solar Cells: Dependence of the Open Circuit Voltage on the Interfacial Composition Treat, Neil D.; Campos, Luis M.; Dimitriou, Michael D. Advanced Materials, Vol. 22, Issue 44 https://doi.org/10.1002/adma.201001967	journal	September 2010
Inverted Polymer Solar Cells Integrated with a Low-Temperature-Annealed Sol-Gel-Derived ZnO Film as an Electron Transport Layer Sun, Yanming; Seo, Jung Hwa; Takacs, Christopher J. Advanced Materials, Vol. 23, Issue 14, p. 1679-1683 https://doi.org/10.1002/adma.201004301	journal	February 2011
Triplet Exciton Dissociation in Singlet Exciton Fission Photovoltaics Jadhav, Priya J.; Brown, Patrick R.; Thompson, Nicholas Advanced Materials, Vol. 24, Issue 46 https://doi.org/10.1002/adma.201202397	journal	September 2012
Highly Efficient Organic Solar Cells with Improved Vertical Donor-Acceptor Compositional Gradient Via an Inverted Off-Center Spinning Method Huang, Jiang; Carpenter, Joshua H.; Li, Chang-Zhi Advanced Materials, Vol. 28, Issue 5 https://doi.org/10.1002/adma.201504014	journal	December 2015
Singlet Fission of Non-polycyclic Aromatic Molecules in Organic Photovoltaics Kawata, So; Pu, Yong-Jin; Saito, Ayaka Advanced Materials, Vol. 28, Issue 8 https://doi.org/10.1002/adma.201504281	journal	December 2015
Two Birds with One Stone: Tailoring Singlet Fission for Both Triplet Yield and Exciton Diffusion Length Zhu, Tong; Wan, Yan; Guo, Zhi Advanced Materials, Vol. 28, Issue 34 https://doi.org/10.1002/adma.201600968	journal	June 2016
Sub-Picosecond Singlet Exciton Fission in Cyano-Substituted Diaryltetracenes Margulies, Eric A.; Wu, Yi-Lin; Gawel, Przemyslaw Angewandte Chemie International Edition, Vol. 54, Issue 30 https://doi.org/10.1002/anie.201501355	journal	June 2015
Intramolecular Singlet Fission in Oligoacene Heterodimers Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B. Angewandte Chemie International Edition, Vol. 55, Issue 10 https://doi.org/10.1002/anie.201510632	journal	February 2016
Solar cell efficiency tables (version 48): Solar cell efficiency tables (version 48) Green, Martin A.; Emery, Keith; Hishikawa, Yoshihiro Progress in Photovoltaics: Research and Applications, Vol. 24, Issue 7 https://doi.org/10.1002/pip.2788	journal	June 2016
Third generation photovoltaics: Ultra-high conversion efficiency at low cost Green, Martin A. Progress in Photovoltaics: Research and Applications, Vol. 9, Issue 2 https://doi.org/10.1002/pip.360	journal	January 2001
Singlet Fission in Polypentacene Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B. Chem, Vol. 1, Issue 3 https://doi.org/10.1016/j.chempr.2016.08.016	journal	September 2016
Evidence for exciton fission and fusion in a covalently linked tetracene dimer Müller, Astrid M.; Avlasevich, Yuri S.; Müllen, Klaus Chemical Physics Letters, Vol. 421, Issue 4-6 https://doi.org/10.1016/j.cplett.2006.01.117	journal	April 2006
Properties of Poly- and Oligopentacenes Synthesized from Modular Building Blocks Kumarasamy, Elango; Sanders, Samuel N.; Pun, Andrew B. Macromolecules, Vol. 49, Issue 4 https://doi.org/10.1021/acs.macromol.5b02711	journal	February 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
A Silicon–Singlet Fission Tandem Solar Cell Exceeding 100% External Quantum Efficiency with High Spectral Stability Pazos-Outón, Luis M.; Lee, Ju Min; Futscher, Moritz H. ACS Energy Letters, Vol. 2, Issue 2 https://doi.org/10.1021/acsenergylett.6b00678	journal	January 2017
The Dynamics of Singlet Fission in Crystalline Tetracene and Covalent Analogs Burdett, Jonathan J.; Bardeen, Christopher J. Accounts of Chemical Research, Vol. 46, Issue 6 https://doi.org/10.1021/ar300191w	journal	January 2013
The Role of Chromophore Coupling in Singlet Fission Johnson, Justin C.; Nozik, Arthur J.; Michl, Josef Accounts of Chemical Research, Vol. 46, Issue 6 https://doi.org/10.1021/ar300193r	journal	January 2013
The Quantum Coherent Mechanism for Singlet Fission: Experiment and Theory Chan, Wai-Lun; Berkelbach, Timothy C.; Provorse, Makenzie R. Accounts of Chemical Research, Vol. 46, Issue 6 https://doi.org/10.1021/ar300286s	journal	April 2013
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
Singlet Exciton Fission in Polycrystalline Pentacene: From Photophysics toward Devices Wilson, Mark W. B.; Rao, Akshay; Ehrler, Bruno Accounts of Chemical Research, Vol. 46, Issue 6 https://doi.org/10.1021/ar300345h	journal	May 2013
The Spectral Signatures of Frenkel Polarons in H- and J-Aggregates Spano, Frank C. Accounts of Chemical Research, Vol. 43, Issue 3 https://doi.org/10.1021/ar900233v	journal	March 2010
Singlet Fission Smith, Millicent B.; Michl, Josef Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr1002613	journal	November 2010
Efficient Singlet Fission Discovered in a Disordered Acene Film Roberts, Sean T.; McAnally, R. Eric; Mastron, Joseph N. Journal of the American Chemical Society, Vol. 134, Issue 14 https://doi.org/10.1021/ja300504t	journal	March 2012
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
The Low-Lying Electronic States of Pentacene and Their Roles in Singlet Fission Zeng, Tao; Hoffmann, Roald; Ananth, Nandini Journal of the American Chemical Society, Vol. 136, Issue 15 https://doi.org/10.1021/ja500887a	journal	April 2014
Mechanism of Singlet Fission in Thin Films of 1,3-Diphenylisobenzofuran Schrauben, Joel N.; Ryerson, Joseph L.; Michl, Josef Journal of the American Chemical Society, Vol. 136, Issue 20 https://doi.org/10.1021/ja501337b	journal	May 2014
Exciton Delocalization Drives Rapid Singlet Fission in Nanoparticles of Acene Derivatives Pensack, Ryan D.; Tilley, Andrew J.; Parkin, Sean R. Journal of the American Chemical Society, Vol. 137, Issue 21 https://doi.org/10.1021/ja512668r	journal	May 2015
Photoconductive Cathode Interlayer for Highly Efficient Inverted Polymer Solar Cells Nian, Li; Zhang, Wenqiang; Zhu, Na Journal of the American Chemical Society, Vol. 137, Issue 22 https://doi.org/10.1021/jacs.5b02168	journal	June 2015
Quantitative Intramolecular Singlet Fission in Bipentacenes Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B. Journal of the American Chemical Society, Vol. 137, Issue 28 https://doi.org/10.1021/jacs.5b04986	journal	July 2015
Singlet Fission in a Covalently Linked Cofacial Alkynyltetracene Dimer Korovina, Nadezhda V.; Das, Saptaparna; Nett, Zachary Journal of the American Chemical Society, Vol. 138, Issue 2 https://doi.org/10.1021/jacs.5b10550	journal	January 2016
Exciton Correlations in Intramolecular Singlet Fission Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B. Journal of the American Chemical Society, Vol. 138, Issue 23 https://doi.org/10.1021/jacs.6b00657	journal	June 2016
Singlet Fission via an Excimer-Like Intermediate in 3,6-Bis(thiophen-2-yl)diketopyrrolopyrrole Derivatives Mauck, Catherine M.; Hartnett, Patrick E.; Margulies, Eric A. Journal of the American Chemical Society, Vol. 138, Issue 36 https://doi.org/10.1021/jacs.6b05627	journal	August 2016
Fast Singlet Exciton Decay in Push–Pull Molecules Containing Oxidized Thiophenes Busby, Erik; Xia, Jianlong; Low, Jonathan Z. The Journal of Physical Chemistry B, Vol. 119, Issue 24 https://doi.org/10.1021/jp511704r	journal	December 2014
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
Singlet Exciton Fission in Nanostructured Organic Solar Cells Jadhav, Priya J.; Mohanty, Aseema; Sussman, Jason Nano Letters, Vol. 11, Issue 4 https://doi.org/10.1021/nl104202j	journal	April 2011
Solution-Processable Singlet Fission Photovoltaic Devices Yang, Le; Tabachnyk, Maxim; Bayliss, Sam L. Nano Letters, Vol. 15, Issue 1 https://doi.org/10.1021/nl503650a	journal	December 2014
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
Singlet exciton fission in solution Walker, Brian J.; Musser, Andrew J.; Beljonne, David Nature Chemistry, Vol. 5, Issue 12 https://doi.org/10.1038/nchem.1801	journal	November 2013
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
Cooperative singlet and triplet exciton transport in tetracene crystals visualized by ultrafast microscopy Wan, Yan; Guo, Zhi; Zhu, Tong Nature Chemistry, Vol. 7, Issue 10 https://doi.org/10.1038/nchem.2348	journal	September 2015
In situ measurement of exciton energy in hybrid singlet-fission solar cells Ehrler, Bruno; Walker, Brian J.; Böhm, Marcus L. Nature Communications, Vol. 3, Issue 1 https://doi.org/10.1038/ncomms2012	journal	January 2012
A design strategy for intramolecular singlet fission mediated by charge-transfer states in donor–acceptor organic materials Busby, Erik; Xia, Jianlong; Wu, Qin Nature Materials, Vol. 14, Issue 4 https://doi.org/10.1038/nmat4175	journal	January 2015
Single-junction polymer solar cells with high efficiency and photovoltage He, Zhicai; Xiao, Biao; Liu, Feng Nature Photonics, Vol. 9, Issue 3 https://doi.org/10.1038/nphoton.2015.6	journal	February 2015
Quintet multiexciton dynamics in singlet fission Tayebjee, Murad J. Y.; Sanders, Samuel N.; Kumarasamy, Elango Nature Physics, Vol. 13, Issue 2 https://doi.org/10.1038/nphys3909	journal	October 2016
The influence of side chains on the structures and properties of functionalized pentacenes Chen, Jihua; Subramanian, Sankar; Parkin, Sean R. Journal of Materials Chemistry, Vol. 18, Issue 17 https://doi.org/10.1039/b717082c	journal	January 2008
Photostability of pentacene and 6,13-disubstituted pentacene derivatives: a theoretical and experimental mechanistic study Northrop, Brian H.; Houk, K. N.; Maliakal, Ashok Photochemical & Photobiological Sciences, Vol. 7, Issue 12 https://doi.org/10.1039/b813752h	journal	January 2008
The exciton dynamics in tetracene thin films Tayebjee, Murad J. Y.; Clady, Raphaël G. C. R.; Schmidt, Timothy W. Physical Chemistry Chemical Physics, Vol. 15, Issue 35 https://doi.org/10.1039/c3cp52609g	journal	January 2013
Laser Generation of Excitons and Fluorescence in Anthracene Crystals Singh, S.; Jones, W. J.; Siebrand, W. The Journal of Chemical Physics, Vol. 42, Issue 1 https://doi.org/10.1063/1.1695695	journal	January 1965
Detailed Balance Limit of Efficiency of p‐n Junction Solar Cells Shockley, William; Queisser, Hans J. Journal of Applied Physics, Vol. 32, Issue 3, p. 510-519 https://doi.org/10.1063/1.1736034	journal	March 1961
Modeling disorder in polymer aggregates: The optical spectroscopy of regioregular poly(3-hexylthiophene) thin films Spano, Frank C. The Journal of Chemical Physics, Vol. 122, Issue 23 https://doi.org/10.1063/1.1914768	journal	June 2005
Efficient photovoltaic energy conversion in tetracene-C60 based heterojunctions Chu, Chih-Wei; Shao, Yan; Shrotriya, Vishal Applied Physics Letters, Vol. 86, Issue 24 https://doi.org/10.1063/1.1946184	journal	June 2005
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
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
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
Enhanced external quantum efficiency in an organic photovoltaic cell via singlet fission exciton sensitizer Reusswig, P. D.; Congreve, D. N.; Thompson, N. J. Applied Physics Letters, Vol. 101, Issue 11 https://doi.org/10.1063/1.4752445	journal	September 2012
Hybrid pentacene/a-silicon solar cells utilizing multiple carrier generation via singlet exciton fission Ehrler, Bruno; Musselman, Kevin P.; Böhm, Marcus L. Applied Physics Letters, Vol. 101, Issue 15 https://doi.org/10.1063/1.4757612	journal	October 2012
Slow light enhanced singlet exciton fission solar cells with a 126% yield of electrons per photon Thompson, Nicholas J.; Congreve, Daniel N.; Goldberg, David Applied Physics Letters, Vol. 103, Issue 26 https://doi.org/10.1063/1.4858176	journal	December 2013
Singlet fission efficiency in tetracene-based organic solar cells Wu, Tony C.; Thompson, Nicholas J.; Congreve, Daniel N. Applied Physics Letters, Vol. 104, Issue 19 https://doi.org/10.1063/1.4876600	journal	May 2014
Singlet fission in pentacene dimers Zirzlmeier, Johannes; Lehnherr, Dan; Coto, Pedro B. Proceedings of the National Academy of Sciences, Vol. 112, Issue 17 https://doi.org/10.1073/pnas.1422436112	journal	April 2015
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
Observing the Multiexciton State in Singlet Fission and Ensuing Ultrafast Multielectron Transfer Chan, W. -L.; Ligges, M.; Jailaubekov, A. Science, Vol. 334, Issue 6062 https://doi.org/10.1126/science.1213986	journal	December 2011
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
Photoinduced Electron Transfer from a Conducting Polymer to Buckminsterfullerene Sariciftci, N. S.; Smilowitz, L.; Heeger, A. J. Science, Vol. 258, Issue 5087, p. 1474-1476 https://doi.org/10.1126/science.258.5087.1474	journal	November 1992
Polymer Photovoltaic Cells: Enhanced Efficiencies via a Network of Internal Donor-Acceptor Heterojunctions Yu, G.; Gao, J.; Hummelen, J. C. Science, Vol. 270, Issue 5243, p. 1789-1791 https://doi.org/10.1126/science.270.5243.1789	journal	December 1995

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