Modeling ultrafast exciton migration within the electron donor domains of bulk heterojunction organic photovoltaics

Bednarz, Mateusz; Lapin, Joel; McGillicuddy, Ryan; Pelzer, Kenley M.; Engel, Gregory S.; Griffin, Graham B.

doi:10.1021/acs.jpcc.6b11332

Title: Modeling ultrafast exciton migration within the electron donor domains of bulk heterojunction organic photovoltaics

Journal Article · Tue Feb 21 00:00:00 EST 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b11332· OSTI ID:1352534

Bednarz, Mateusz ^[1]; Lapin, Joel ^[1]; McGillicuddy, Ryan ^[2];

^[3];

^[2];

^[1]

DePaul Univ., Chicago, IL (United States)
The Univ. of Chicago, Chicago, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

Recent experimental studies revealed that charge carriers harvested by bulk heterojunction organic photovoltaics can be collected on ultrafast time scales. To investigate ultrafast exciton mobility, we construct simple, nonatomistic models of a common polymeric electron donor material. We first explore the relationship between the magnitude of energetic noise in the model Hamiltonian and the spatial extent of resulting eigenstates. We then employ a quantum master equation approach to simulate migration of chromophore-localized initial excited states. Excitons initially localized on a single chromophore at the center of the model delocalize down polymer chains and across pi-stacked chromophores through a coherent, wavelike mechanism during the first few tens of femtoseconds. We explore the dependence of this coherent delocalization on coupling strength and on the magnitude of energetic noise. At longer times we observe continued migration toward a uniform population distribution that proceeds through an incoherent, diffusive mechanism. A series of simulations modeling exciton harvesting in domains of varying size demonstrates that smaller domains enhance ultrafast exciton harvesting yield. Finally, our nonatomistic model falls short of quantitative accuracy but demonstrates that excitons are mobile within electron donor domains on ultrafast time scales and that coherent exciton transport can enhance ultrafast exciton harvesting.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: DePaul University; USDOE Office of Science (SC), Basic Energy Sciences (BES); Materials Sciences and Engineering Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1352534

Journal Information:: Journal of Physical Chemistry. C, Vol. 121, Issue 10; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 2 works

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References (61)

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
Molecular Understanding of Organic Solar Cells: The Challenges Brédas, Jean-Luc; Norton, Joseph E.; Cornil, Jérôme Accounts of Chemical Research, Vol. 42, Issue 11 https://doi.org/10.1021/ar900099h	journal	November 2009
Conjugated Polymer-Based Organic Solar Cells Günes, Serap; Neugebauer, Helmut; Sariciftci, Niyazi Serdar Chemical Reviews, Vol. 107, Issue 4, p. 1324-1338 https://doi.org/10.1021/cr050149z	journal	April 2007
Charge generation in polymer–fullerene bulk-heterojunction solar cells Gao, Feng; Inganäs, Olle Phys. Chem. Chem. Phys., Vol. 16, Issue 38 https://doi.org/10.1039/C4CP01814A	journal	January 2014
Zwischenmolekulare Energiewanderung und Fluoreszenz Förster, Th. Annalen der Physik, Vol. 437, Issue 1-2, p. 55-75 https://doi.org/10.1002/andp.19484370105	journal	January 1948
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
Transient Absorption Imaging of P3HT:PCBM Photovoltaic Blend: Evidence For Interfacial Charge Transfer State Grancini, Giulia; Polli, Dario; Fazzi, Daniele The Journal of Physical Chemistry Letters, Vol. 2, Issue 9 https://doi.org/10.1021/jz200389b	journal	April 2011
Nanoscale transport of charge-transfer states in organic donor–acceptor blends Deotare, P. B.; Chang, W.; Hontz, E. Nature Materials, Vol. 14, Issue 11 https://doi.org/10.1038/nmat4424	journal	September 2015
Ultrafast dynamics of charge carrier photogeneration and geminate recombination in conjugated polymer:fullerene solar cells Müller, J. G.; Lupton, J. M.; Feldmann, J. Physical Review B, Vol. 72, Issue 19 https://doi.org/10.1103/PhysRevB.72.195208	journal	November 2005
Charge Carrier Formation in Polythiophene/Fullerene Blend Films Studied by Transient Absorption Spectroscopy Ohkita, Hideo; Cook, Steffan; Astuti, Yeni Journal of the American Chemical Society, Vol. 130, Issue 10 https://doi.org/10.1021/ja076568q	journal	March 2008
Charge Photogeneration in Organic Solar Cells Clarke, Tracey M.; Durrant, James R. Chemical Reviews, Vol. 110, Issue 11, p. 6736-6767 https://doi.org/10.1021/cr900271s	journal	November 2010
A high efficiency solution processed polymer inverted triple-junction solar cell exhibiting a power conversion efficiency of 11.83% Yusoff, Abd. Rashid bin Mohd; Kim, Dongcheon; Kim, Hyeong Pil Energy & Environmental Science, Vol. 8, Issue 1 https://doi.org/10.1039/C4EE03048F	journal	January 2015
An Efficient Triple-Junction Polymer Solar Cell Having a Power Conversion Efficiency Exceeding 11% Chen, Chun-Chao; Chang, Wei-Hsuan; Yoshimura, Ken Advanced Materials, Vol. 26, Issue 32 https://doi.org/10.1002/adma.201402072	journal	July 2014
Charge carrier photogeneration and decay dynamics in the poly(2,7-carbazole) copolymer PCDTBT and in bulk heterojunction composites with ${PC}_{70} BM$ Tong, Minghong; Coates, Nelson E.; Moses, Daniel Physical Review B, Vol. 81, Issue 12 https://doi.org/10.1103/PhysRevB.81.125210	journal	March 2010
Coherence and Uncertainty in Nanostructured Organic Photovoltaics Kaake, Loren G.; Moses, Daniel; Heeger, Alan J. The Journal of Physical Chemistry Letters, Vol. 4, Issue 14 https://doi.org/10.1021/jz4010569	journal	June 2013
Direct observation of ultrafast long-range charge separation at polymer–fullerene heterojunctions Provencher, Françoise; Bérubé, Nicolas; Parker, Anthony W. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5288	journal	July 2014
The fate of electron–hole pairs in polymer:fullerene blends for organic photovoltaics Causa', Martina; De Jonghe-Risse, Jelissa; Scarongella, Mariateresa Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12556	journal	September 2016
Tracing photoinduced electron transfer process in conjugated polymer/fullerene bulk heterojunctions in real time Brabec, Christoph J.; Zerza, Gerald; Cerullo, Giulio Chemical Physics Letters, Vol. 340, Issue 3-4 https://doi.org/10.1016/S0009-2614(01)00431-6	journal	June 2001
Photoinduced Carrier Generation in P3HT/PCBM Bulk Heterojunction Materials Hwang, In-Wook; Moses, Daniel; Heeger, Alan J. The Journal of Physical Chemistry C, Vol. 112, Issue 11 https://doi.org/10.1021/jp075565x	journal	February 2008
Ultrafast photogeneration of charged polarons in conjugated polymers Miranda, Paulo B.; Moses, Daniel; Heeger, Alan J. Physical Review B, Vol. 64, Issue 8 https://doi.org/10.1103/PhysRevB.64.081201	journal	August 2001
Ultrafast excitation transfer and trapping in a thin polymer film Grage, Mette M. -L.; Zaushitsyn, Yuri; Yartsev, Arkady Physical Review B, Vol. 67, Issue 20 https://doi.org/10.1103/PhysRevB.67.205207	journal	May 2003
Exciton Formation, Relaxation, and Decay in PCDTBT Banerji, Natalie; Cowan, Sarah; Leclerc, Mario Journal of the American Chemical Society, Vol. 132, Issue 49 https://doi.org/10.1021/ja105290e	journal	December 2010
Near-IR Femtosecond Transient Absorption Spectroscopy of Ultrafast Polaron and Triplet Exciton Formation in Polythiophene Films with Different Regioregularities Guo, Jiamo; Ohkita, Hideo; Benten, Hiroaki Journal of the American Chemical Society, Vol. 131, Issue 46 https://doi.org/10.1021/ja906621a	journal	November 2009
Ultrafast Charge Generation in an Organic Bilayer Film Kaake, Loren G.; Zhong, Chengmei; Love, John A. The Journal of Physical Chemistry Letters, Vol. 5, Issue 11 https://doi.org/10.1021/jz500695f	journal	May 2014
Ultrafast Long-Range Charge Separation in Organic Semiconductor Photovoltaic Diodes Gelinas, S.; Rao, A.; Kumar, A. Science, Vol. 343, Issue 6170 https://doi.org/10.1126/science.1246249	journal	December 2013
Ultrafast charge separation and nongeminate electron–hole recombination in organic photovoltaics Smith, Samuel L.; Chin, Alex W. Phys. Chem. Chem. Phys., Vol. 16, Issue 38 https://doi.org/10.1039/C4CP01791A	journal	January 2014
Unequal Partnership: Asymmetric Roles of Polymeric Donor and Fullerene Acceptor in Generating Free Charge Savoie, Brett M.; Rao, Akshay; Bakulin, Artem A. Journal of the American Chemical Society, Vol. 136, Issue 7 https://doi.org/10.1021/ja411859m	journal	February 2014
Theoretical Study of the Organic Photovoltaic Electron Acceptor PCBM: Morphology, Electronic Structure, and Charge Localization Cheung, David L.; Troisi, Alessandro The Journal of Physical Chemistry C, Vol. 114, Issue 48 https://doi.org/10.1021/jp1049167	journal	July 2010
Role of intermolecular charge delocalization on electron transport in fullerene aggregates Tamura, Hiroyuki; Tsukada, Masaru Physical Review B, Vol. 85, Issue 5 https://doi.org/10.1103/PhysRevB.85.054301	journal	February 2012
Environment-assisted quantum transport Rebentrost, Patrick; Mohseni, Masoud; Kassal, Ivan New Journal of Physics, Vol. 11, Issue 3 https://doi.org/10.1088/1367-2630/11/3/033003	journal	March 2009
Dephasing-assisted transport: quantum networks and biomolecules Plenio, M. B.; Huelga, S. F. New Journal of Physics, Vol. 10, Issue 11 https://doi.org/10.1088/1367-2630/10/11/113019	journal	November 2008
Theoretical examination of quantum coherence in a photosynthetic system at physiological temperature Ishizaki, A.; Fleming, G. R. Proceedings of the National Academy of Sciences, Vol. 106, Issue 41 https://doi.org/10.1073/pnas.0908989106	journal	October 2009
Quantum entanglement in photosynthetic light-harvesting complexes Sarovar, Mohan; Ishizaki, Akihito; Fleming, Graham R. Nature Physics, Vol. 6, Issue 6 https://doi.org/10.1038/nphys1652	journal	April 2010
Inhomogeneous dephasing masks coherence lifetimes in ensemble measurements Pelzer, Kenley M.; Griffin, Graham B.; Gray, Stephen K. The Journal of Chemical Physics, Vol. 136, Issue 16 https://doi.org/10.1063/1.4704591	journal	April 2012
Comment on “Coherence and Uncertainty in Nanostructured Organic Photovoltaics” Mukamel, Shaul The Journal of Physical Chemistry A, Vol. 117, Issue 40 https://doi.org/10.1021/jp4071086	journal	September 2013
Exciton Migration in Molecular Crystals Grover, M.; Silbey, R. The Journal of Chemical Physics, Vol. 54, Issue 11 https://doi.org/10.1063/1.1674761	journal	June 1971
H- and J-Aggregate Behavior in Polymeric Semiconductors Spano, Frank C.; Silva, Carlos Annual Review of Physical Chemistry, Vol. 65, Issue 1 https://doi.org/10.1146/annurev-physchem-040513-103639	journal	April 2014
Interplay between intrachain and interchain interactions in semiconducting polymer assemblies: The HJ-aggregate model Yamagata, H.; Spano, F. C. The Journal of Chemical Physics, Vol. 136, Issue 18 https://doi.org/10.1063/1.4705272	journal	May 2012
A Strategy for Revealing the Packing in Semicrystalline π-Conjugated Polymers: Crystal Structure of Bulk Poly-3-hexyl-thiophene (P3HT) Dudenko, Dmytro; Kiersnowski, Adam; Shu, Jie Angewandte Chemie International Edition, Vol. 51, Issue 44 https://doi.org/10.1002/anie.201205075	journal	October 2012
Temperature and Molecular Weight Dependent Hierarchical Equilibrium Structures in Semiconducting Poly(3-hexylthiophene) Wu, Zhiyong; Petzold, Albrecht; Henze, Thomas Macromolecules, Vol. 43, Issue 10 https://doi.org/10.1021/ma902566h	journal	May 2010
Two-dimensional charge transport in self-organized, high-mobility conjugated polymers Sirringhaus, H.; Brown, P. J.; Friend, R. H. Nature, Vol. 401, Issue 6754, p. 685-688 https://doi.org/10.1038/44359	journal	October 1999
Effects of Postproduction Treatment on Plastic Solar Cells Padinger, F.; Rittberger, R. S.; Sariciftci, N. S. Advanced Functional Materials, Vol. 13, Issue 1, p. 85-88 https://doi.org/10.1002/adfm.200390011	journal	January 2003
Strongly confined polaron excitations in charged organic semiconductors Knupfer, M.; Fink, J.; Fichou, D. Physical Review B, Vol. 63, Issue 16 https://doi.org/10.1103/PhysRevB.63.165203	journal	April 2001
A photochemical study of poly(3-hexylthiophene) Holdcroft, Steven Macromolecules, Vol. 24, Issue 17 https://doi.org/10.1021/ma00017a017	journal	August 1991
Relation between absorption and crystallinity of poly(3-hexylthiophene)/fullerene films for plastic solar cells Zhokhavets, Uladzimir; Erb, Tobias; Gobsch, Gerhard Chemical Physics Letters, Vol. 418, Issue 4-6 https://doi.org/10.1016/j.cplett.2005.11.020	journal	February 2006
Effect of interchain interactions on the absorption and emission of poly(3-hexylthiophene) Brown, Peter J.; Thomas, D. Steve; Köhler, Anna Physical Review B, Vol. 67, Issue 6 https://doi.org/10.1103/PhysRevB.67.064203	journal	February 2003
Experimental determination of excitonic levels in α-oligothiophenes Kouki, Fayçal; Spearman, Peter; Valat, Pierre The Journal of Chemical Physics, Vol. 113, Issue 1 https://doi.org/10.1063/1.481804	journal	July 2000
Excitonic coupling in polythiophenes: Comparison of different calculation methods Beenken, Wichard J. D.; Pullerits, Tõnu The Journal of Chemical Physics, Vol. 120, Issue 5 https://doi.org/10.1063/1.1636460	journal	February 2004
Ultrafast Energy Transfer in Ultrathin Organic Donor/Acceptor Blend Kandada, Ajay Ram Srimath; Grancini, Giulia; Petrozza, Annamaria Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep02073	journal	June 2013
Electron and energy transfer in donor–acceptor systems with conjugated molecular bridges Albinsson, Bo; Eng, Mattias P.; Pettersson, Karin Physical Chemistry Chemical Physics, Vol. 9, Issue 44 https://doi.org/10.1039/b706122f	journal	January 2007
Measures and implications of electronic coherence in photosynthetic light-harvesting Smyth, Cathal; Fassioli, Francesca; Scholes, Gregory D. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 370, Issue 1972 https://doi.org/10.1098/rsta.2011.0420	journal	August 2012
An exactly solvable model for coherent and incoherent exciton motion Haken, H.; Strobl, G. Zeitschrift für Physik A Hadrons and nuclei, Vol. 262, Issue 2 https://doi.org/10.1007/BF01399723	journal	April 1973
Morphological and charge transport properties of amorphous and crystalline P3HT and PBTTT: insights from theory Alberga, Domenico; Perrier, Aurélie; Ciofini, Ilaria Physical Chemistry Chemical Physics, Vol. 17, Issue 28 https://doi.org/10.1039/C5CP02769A	journal	January 2015
Structural variability and dynamics of the P3HT/PCBM interface and its effects on the electronic structure and the charge-transfer rates in solar cells Liu, Tao; Cheung, David L.; Troisi, Alessandro Physical Chemistry Chemical Physics, Vol. 13, Issue 48 https://doi.org/10.1039/c1cp23084k	journal	January 2011
Absolute Rate of Charge Separation and Recombination in a Molecular Model of the P3HT/PCBM Interface Liu, Tao; Troisi, Alessandro The Journal of Physical Chemistry C, Vol. 115, Issue 5 https://doi.org/10.1021/jp109130y	journal	December 2010
Hot Exciton Dissociation in a Conjugated Polymer Arkhipov, V. I.; Emelianova, E. V.; Bässler, H. Physical Review Letters, Vol. 82, Issue 6 https://doi.org/10.1103/PhysRevLett.82.1321	journal	February 1999
Hot exciton dissociation in conjugated polymers Basko, D. M.; Conwell, E. M. Physical Review B, Vol. 66, Issue 15 https://doi.org/10.1103/PhysRevB.66.155210	journal	October 2002
Charge Transfer State Versus Hot Exciton Dissociation in Polymer−Fullerene Blended Solar Cells Lee, Jiye; Vandewal, Koen; Yost, Shane R. Journal of the American Chemical Society, Vol. 132, Issue 34 https://doi.org/10.1021/ja1045742	journal	August 2010
Control of the nanoscale crystallinity and phase separation in polymer solar cells Chu, Chih-Wei; Yang, Hoichang; Hou, Wei-Jen Applied Physics Letters, Vol. 92, Issue 10 https://doi.org/10.1063/1.2891884	journal	March 2008
Distance Dependence of Exciton Dissociation at a Phthalocyanine–C ₆₀ Interface Dutton, G. J.; Robey, S. W. The Journal of Physical Chemistry C, Vol. 117, Issue 48 https://doi.org/10.1021/jp4104917	journal	November 2013
Long-range exciton dissociation in organic solar cells Caruso, D.; Troisi, A. Proceedings of the National Academy of Sciences, Vol. 109, Issue 34 https://doi.org/10.1073/pnas.1206172109	journal	August 2012

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