Energetics and Escape of Interchain-Delocalized Ion Pairs in Nonpolar Media

Burke, John H.; Bird, Matthew J.

doi:10.1002/adma.201806863

Title: Energetics and Escape of Interchain-Delocalized Ion Pairs in Nonpolar Media

Journal Article · 29 January 2019 · Advanced Materials

DOI: https://doi.org/10.1002/adma.201806863 · OSTI ID:1493186

Burke, John H. ^[1];

^[2]

Univ. of Vermont, Burlington, VT (United States). Dept. of Chemistry
Brookhaven National Laboratory, Upton NY (United States). Chemistry Division

The electron acceptor F4TCNQ p-dopes aggregates “nanowires” of poly(3-hexylthiophene) in nonpolar solvents but does not dope unaggregated chains. The standard free energy change for the charge transfer to form an ion pair is ΔG°_et = -0.21 eV. The dissociation constant to produce free ions in toluene by DC conductivity is K°_d = 1 × 10^-8 ± 50% (ΔG°_d = 0.48 ± 0.05 eV). This remarkably large K°d, for ions in such a low polarity medium, may reflect interchain delocalization of the hole. The particular characteristics of this material system enables determination of both ΔG°_et and ΔG°_d, to find the overall free energy change from the two neutral species to completely separated ions in nonpolar media. It is endergonic by +0.27 ± 0.05 eV in contrast to -0.6 eV estimated from reported HOMO LUMO differences, illustrating the challenges that persist in determining such energetics. Steady state microwave conductivity experiments on doped aggregates confirm that holes in the aggregates cannot easily escape their dopant counterion, but at higher dopant concentrations, holes become mobile. These results provide insight into the mechanisms of charge separation involving intermolecularly delocalized charges in nonpolar media, an integral process in organic photovoltaic devices and doped molecular films.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704

OSTI ID:: 1493186

Report Number(s):: BNL--211239-2019-JAAM

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 12 Vol. 31; ISSN 0935-9648

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

How High Local Charge Carrier Mobility and an Energy Cascade in a Three-Phase Bulk Heterojunction Enable >90% Quantum Efficiency Burke, Timothy M.; McGehee, Michael D. Advanced Materials, Vol. 26, Issue 12 https://doi.org/10.1002/adma.201304241	journal	December 2013
Beyond Langevin Recombination: How Equilibrium Between Free Carriers and Charge Transfer States Determines the Open-Circuit Voltage of Organic Solar Cells Burke, Timothy M.; Sweetnam, Sean; Vandewal, Koen Advanced Energy Materials, Vol. 5, Issue 11 https://doi.org/10.1002/aenm.201500123	journal	April 2015
The study of the transient conductivity of pulse irradiated dielectric liquids on a nanosecond timescale using microwaves Infelta, Pierre P.; de Haas, Matthijs P.; Warman, John M. Radiation Physics and Chemistry (1977), Vol. 10, Issue 5-6 https://doi.org/10.1016/0146-5724(77)90044-9	journal	January 1977
Photon-induced molecular charge separation studied by nanosecond time-resolved microwave conductivity De Haas, Matthijs P.; Warman, John M. Chemical Physics, Vol. 73, Issue 1-2 https://doi.org/10.1016/0301-0104(82)85148-3	journal	December 1982
Photon-induced molecular charge separation studied by nanosecond time-resolved microwave conductivity de Haas, Matthijs P.; Warman, John M. Chemical Physics, Vol. 83, Issue 3 https://doi.org/10.1016/0301-0104(84)85024-7	journal	January 1984
Geminate pair dissociation in random organic systems Barth, S.; Hertel, D.; Tak, Y. -H. Chemical Physics Letters, Vol. 274, Issue 1-3 https://doi.org/10.1016/S0009-2614(97)00649-0	journal	August 1997
The chemical and structural origin of efficient p-type doping in P3HT Duong, Duc T.; Wang, Chenchen; Antono, Erin Organic Electronics, Vol. 14, Issue 5 https://doi.org/10.1016/j.orgel.2013.02.028	journal	May 2013
Ternary organic solar cells offer 14% power conversion efficiency Xiao, Zuo; Jia, Xue; Ding, Liming Science Bulletin, Vol. 62, Issue 23 https://doi.org/10.1016/j.scib.2017.11.003	journal	December 2017
Comparison of the Conductivity Properties of the Tetrabutylammonium Salt of Tetrakis(pentafluorophenyl)borate Anion with Those of Traditional Supporting Electrolyte Anions in Nonaqueous Solvents LeSuer, Robert J.; Buttolph, Catherine; Geiger, William E. Analytical Chemistry, Vol. 76, Issue 21 https://doi.org/10.1021/ac040087x	journal	November 2004
Nucleation, Growth, and Alignment of Poly(3-hexylthiophene) Nanofibers for High-Performance OFETs Persson, Nils E.; Chu, Ping-Hsun; McBride, Michael Accounts of Chemical Research, Vol. 50, Issue 4 https://doi.org/10.1021/acs.accounts.6b00639	journal	February 2017
Charge-Transfer–Solvent Interaction Predefines Doping Efficiency in p-Doped P3HT Films Müller, Lars; Nanova, Diana; Glaser, Tobias Chemistry of Materials, Vol. 28, Issue 12 https://doi.org/10.1021/acs.chemmater.6b01629	journal	June 2016
The Aggregation of Poly(3-hexylthiophene) into Nanowires: With and without Chemical Doping McFarland, Frederick M.; Ellis, Clara M.; Guo, Song The Journal of Physical Chemistry C, Vol. 121, Issue 8 https://doi.org/10.1021/acs.jpcc.7b00816	journal	February 2017
Entropy and Disorder Enable Charge Separation in Organic Solar Cells Hood, Samantha N.; Kassal, Ivan The Journal of Physical Chemistry Letters, Vol. 7, Issue 22 https://doi.org/10.1021/acs.jpclett.6b02178	journal	October 2016
Delocalization Drives Free Charge Generation in Conjugated Polymer Films Pace, Natalie A.; Reid, Obadiah G.; Rumbles, Garry ACS Energy Letters, Vol. 3, Issue 3 https://doi.org/10.1021/acsenergylett.8b00108	journal	February 2018
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
Ion Pairing Marcus, Yizhak; Hefter, Glenn Chemical Reviews, Vol. 106, Issue 11 https://doi.org/10.1021/cr040087x	journal	November 2006
The Disperse Charge-Carrier Kinetics in Regioregular Poly(3-hexylthiophene) Dicker, Gerald; de Haas, Matthijs P.; Warman, John M. The Journal of Physical Chemistry B, Vol. 108, Issue 46 https://doi.org/10.1021/jp046853l	journal	November 2004
Mechanism of Mobile Charge Carrier Generation in Blends of Conjugated Polymers and Fullerenes: Significance of Charge Delocalization and Excess Free Energy Murthy, D. H. K.; Gao, M.; Vermeulen, M. J. W. The Journal of Physical Chemistry C, Vol. 116, Issue 16 https://doi.org/10.1021/jp3007014	journal	April 2012
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
Mobility of Holes in Oligo- and Polyfluorenes of Defined Lengths Bird, Matthew J.; Reid, Obadiah G.; Cook, Andrew R. The Journal of Physical Chemistry C, Vol. 118, Issue 12 https://doi.org/10.1021/jp5010874	journal	March 2014
J-Aggregate Behavior in Poly-3-hexylthiophene Nanofibers Niles, Edwards T.; Roehling, John D.; Yamagata, Hajime The Journal of Physical Chemistry Letters, Vol. 3, Issue 2 https://doi.org/10.1021/jz201509h	journal	January 2012
Aggregates Promote Efficient Charge Transfer Doping of Poly(3-hexylthiophene) Gao, Jian; Niles, Edwards T.; Grey, John K. The Journal of Physical Chemistry Letters, Vol. 4, Issue 17 https://doi.org/10.1021/jz401555x	journal	August 2013
Effect of Crystallization on the Electronic Energy Levels and Thin Film Morphology of P3HT:PCBM Blends Tsoi, Wing C.; Spencer, Steve J.; Yang, Li Macromolecules, Vol. 44, Issue 8 https://doi.org/10.1021/ma102841e	journal	April 2011
High electrical conductivity in doped polyacetylene Basescu, N.; Liu, Z. -X.; Moses, D. Nature, Vol. 327, Issue 6121 https://doi.org/10.1038/327403a0	journal	June 1987
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
Charge-transfer crystallites as molecular electrical dopants Méndez, Henry; Heimel, Georg; Winkler, Stefanie Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9560	journal	October 2015
Controlling microstructure in poly(3-hexylthiophene) nanofibers Roehling, John D.; Arslan, Ilke; Moulé, Adam J. J. Mater. Chem., Vol. 22, Issue 6 https://doi.org/10.1039/C2JM13633C	journal	January 2012
Comparison of solution-mixed and sequentially processed P3HT:F4TCNQ films: effect of doping-induced aggregation on film morphology Jacobs, Ian E.; Aasen, Erik W.; Oliveira, Julia L. J. Mater. Chem. C, Vol. 4, Issue 16 https://doi.org/10.1039/C5TC04207K	journal	January 2016
The impact of aggregation on the p-doping kinetics of poly(3-hexylthiophene) McFarland, Frederick M.; Bonnette, Lindsey R.; Acres, Elisha A. Journal of Materials Chemistry C, Vol. 5, Issue 23 https://doi.org/10.1039/C7TC00189D	journal	January 2017
Aggregation of P3HT as a preferred pathway for its chemical doping with F ₄ -TCNQ Tang, Kan; McFarland, Frederick M.; Travis, Skye Chemical Communications, Vol. 54, Issue 84 https://doi.org/10.1039/C8CC05472J	journal	January 2018
Polymorphism controls the degree of charge transfer in a molecularly doped semiconducting polymer Jacobs, Ian E.; Cendra, Camila; Harrelson, Thomas F. Materials Horizons, Vol. 5, Issue 4 https://doi.org/10.1039/C8MH00223A	journal	January 2018
Suppression of geminate charge recombination in organic photovoltaic devices with a cascaded energy heterojunction Groves, Chris Energy & Environmental Science, Vol. 6, Issue 5 https://doi.org/10.1039/c3ee24455e	journal	January 2013
Controlled p -doping of zinc phthalocyanine by coevaporation with tetrafluorotetracyanoquinodimethane: A direct and inverse photoemission study Gao, Weiying; Kahn, Antoine Applied Physics Letters, Vol. 79, Issue 24 https://doi.org/10.1063/1.1424067	journal	December 2001
Development of a microwave transmission setup for time-resolved measurements of the transient complex conductivity in bulk samples Schins, J. M.; Prins, P.; Grozema, F. C. Review of Scientific Instruments, Vol. 76, Issue 8 https://doi.org/10.1063/1.2008978	journal	August 2005
Hole mobility on isolated chains of poly(3-hexylthiophene) by microwave conductivity measurement Liu, Ching-Yang; Chen, Show-An The Journal of Chemical Physics, Vol. 130, Issue 20 https://doi.org/10.1063/1.3141986	journal	May 2009
Charge-carrier dynamics in polythiophene films studied by in-situ measurement of flash-photolysis time-resolved microwave conductivity (FP-TRMC) and transient optical spectroscopy (TOS) Saeki, A.; Seki, S.; Sunagawa, T. Philosophical Magazine, Vol. 86, Issue 9 https://doi.org/10.1080/14786430500380159	journal	March 2006
Charge Mobility in Discotic Materials Studied by Pr-Trmc Warman, John M.; Van De Craats, Anick M. Molecular Crystals and Liquid Crystals, Vol. 396, Issue 1 https://doi.org/10.1080/15421400390213186	journal	January 2003
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
Electrodeless time-resolved microwave conductivity study of charge-carrier photogeneration in regioregular poly(3-hexylthiophene) thin films Dicker, Gerald; de Haas, Matthijs P.; Siebbeles, Laurens D. A. Physical Review B, Vol. 70, Issue 4 https://doi.org/10.1103/PhysRevB.70.045203	journal	July 2004
Analytic model of carrier mobility in doped disordered organic semiconductors Arkhipov, V. I.; Emelianova, E. V.; Heremans, P. Physical Review B, Vol. 72, Issue 23 https://doi.org/10.1103/PhysRevB.72.235202	journal	December 2005
Comprehensive picture of p -type doping of P3HT with the molecular acceptor F 4 TCNQ Pingel, P.; Neher, D. Physical Review B, Vol. 87, Issue 11 https://doi.org/10.1103/PhysRevB.87.115209	journal	March 2013
Impact of doping on the density of states and the mobility in organic semiconductors Zuo, Guangzheng; Abdalla, Hassan; Kemerink, Martijn Physical Review B, Vol. 93, Issue 23 https://doi.org/10.1103/PhysRevB.93.235203	journal	June 2016
Electrical Conductivity in Doped Polyacetylene Chiang, C. K.; Fincher, C. R.; Park, Y. W. Physical Review Letters, Vol. 39, Issue 17, p. 1098-1101 https://doi.org/10.1103/PhysRevLett.39.1098	journal	October 1977
Solitons in conducting polymers Heeger, A. J.; Kivelson, S.; Schrieffer, J. R. Reviews of Modern Physics, Vol. 60, Issue 3 https://doi.org/10.1103/RevModPhys.60.781	journal	July 1988
Electrical Conductivity in Doped Polyacetylene. Chiang, C. K.; Fincher, C. R.; Park, Y. W. Physical Review Letters, Vol. 40, Issue 22 https://doi.org/10.1103/physrevlett.40.1472	journal	May 1978
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
Organic and solution-processed tandem solar cells with 17.3% efficiency Meng, Lingxian; Zhang, Yamin; Wan, Xiangjian Science, Vol. 361, Issue 6407 https://doi.org/10.1126/science.aat2612	journal	August 2018
Ultrafast Long-Range Charge Separation in Organic Semiconductor Photovoltaic Diodes Gelinas, Simon; Rao, Akshay; Kumar, Abhishek 19th International Conference on Ultrafast Phenomena https://doi.org/10.1364/up.2014.07.mon.c.7	conference	January 2014
Direct observation of ultrafast long-range charge separation at polymer:fullerene heterojunctions Provencher, Françoise; Bérubé, Nicolas; Parker, Anthony W. arXiv https://doi.org/10.48550/arxiv.1310.8331	text	January 2013
Entropy and disorder enable charge separation in organic solar cells Hood, Samantha N.; Kassal, Ivan arXiv https://doi.org/10.48550/arxiv.1603.06304	text	January 2016

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Title: Energetics and Escape of Interchain-Delocalized Ion Pairs in Nonpolar Media

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