Effect of Charge Localization on the Effective Hyperfine Interaction in Organic Semiconducting Polymers

Geng, Rugang; Subedi, Ram C.; Luong, Hoang M.; Pham, Minh T.; Huang, Weichuan; Li, Xiaoguang; Hong, Kunlun; Shao, Ming; Xiao, Kai; Hornak, Lawrence A.; Nguyen, Tho D.

doi:10.1103/PhysRevLett.120.086602

Title: Effect of Charge Localization on the Effective Hyperfine Interaction in Organic Semiconducting Polymers

Journal Article · 22 February 2018 · Physical Review Letters

DOI: https://doi.org/10.1103/PhysRevLett.120.086602 · OSTI ID:1494885

Geng, Rugang ^[1]; Subedi, Ram C. ^[1]; Luong, Hoang M. ^[1]; Pham, Minh T. ^[1]; Huang, Weichuan ^[2]; Li, Xiaoguang ^[2];

^[3]; Shao, Ming ^[3];

^[3]; Hornak, Lawrence A. ^[4]; Nguyen, Tho D. ^[1]

Univ. of Georgia, Athens, GA (United States). Dept. of Physics and Astronomy
Univ. of Science and Technology of China, Hefei (China). Hefei National Lab. for Physical Sciences at the Microscale, Dept. of Physics, and Collaborative Innovation Center of Advanced Microstructures
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
Univ. of Georgia, Athens, GA (United States). College of Engineering

Hyperfine interaction (HFI), originating from the coupling between spins of charge carriers and nuclei, has been demonstrated to strongly influence the spin dynamics of localized charges in organic semiconductors. Nevertheless, the role of charge localization on the HFI strength in organic thin films has not yet been experimentally investigated. In this study, the statistical relation hypothesis that the effective HFI of holes in regioregular poly(3-hexylthiophene) (P3HT) is proportional to 1/N^0.5 has been examined, where N is the number of the random nuclear spins within the envelope of the hole wave function. First, by studying magnetoconductance in hole-only devices made by isotope-labeled P3HT we verify that HFI is indeed the dominant spin interaction in P3HT. Second, assuming that holes delocalize fully over the P3HT polycrystalline domain, the strength of HFI is experimentally demonstrated to be proportional to 1/N^0.52 in excellent agreement with the statistical relation. Third, the HFI of electrons in P3HT is about 3 times stronger than that of holes due to the stronger localization of the electrons. Finally, the effective HFI in organic light emitting diodes is found to be a superposition of effective electron and hole HFI. Such a statistical relation may be generally applied to other semiconducting polymers. Lastly, this Letter may provide great benefits for organic optoelectronics, chemical reaction kinetics, and magnetoreception in biology.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

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

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1494885

Journal Information:: Physical Review Letters, Vol. 120, Issue 8; ISSN 0031-9007

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 31 works

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References (53)

Chemical compass model of avian magnetoreception Maeda, Kiminori; Henbest, Kevin B.; Cintolesi, Filippo Nature, Vol. 453, Issue 7193 https://doi.org/10.1038/nature06834	journal	April 2008
Indirect Hyperfine Interactions in the Paramagnetic Resonance Spectra of Aromatic Free Radicals McConnell, Harden M. The Journal of Chemical Physics, Vol. 24, Issue 4 https://doi.org/10.1063/1.1742605	journal	April 1956
Enhancement of organic magnetoresistance by electrical conditioning Niedermeier, U.; Vieth, M.; Pätzold, R. Applied Physics Letters, Vol. 92, Issue 19 https://doi.org/10.1063/1.2924765	journal	May 2008
A quantitative interpretation of the magnetic field effect on hyperfine-coupling-induced triplet fromation from radical ion pairs Weller, A.; Nolting, F.; Staerk, H. Chemical Physics Letters, Vol. 96, Issue 1 https://doi.org/10.1016/0009-2614(83)80109-2	journal	March 1983
Conjugated Chromophore Arrays with Unusually Large Hole Polaron Delocalization Lengths Susumu, Kimihiro; Frail, Paul R.; Angiolillo, Paul J. Journal of the American Chemical Society, Vol. 128, Issue 26 https://doi.org/10.1021/ja0614823	journal	July 2006
Polaron spin current transport in organic semiconductors Watanabe, Shun; Ando, Kazuya; Kang, Keehoon Nature Physics, Vol. 10, Issue 4 https://doi.org/10.1038/nphys2901	journal	March 2014
Enhanced room-temperature spin Seebeck effect in a YIG/C ₆₀ /Pt layered heterostructure Das, R.; Kalappattil, V.; Geng, R. AIP Advances, Vol. 8, Issue 5 https://doi.org/10.1063/1.5007233	journal	May 2018
Origin of the different transport properties of electron and hole polarons in an ambipolar polyselenophene-based conjugated polymer Chen, Zhuoying; Bird, Matthew; Lemaur, Vincent Physical Review B, Vol. 84, Issue 11 https://doi.org/10.1103/PhysRevB.84.115211	journal	September 2011
EPR study of positive holes on phenylene vinylene chains: from dimer to polymer Zezin, Aleksei A.; Feldman, Vladimir I.; Warman, John M. Chemical Physics Letters, Vol. 389, Issue 1-3 https://doi.org/10.1016/j.cplett.2004.03.071	journal	May 2004
Environment-assisted quantum control of a solid-state spin via coherent dark states Hansom, Jack; Schulte, Carsten H. H.; Le Gall, Claire Nature Physics, Vol. 10, Issue 10 https://doi.org/10.1038/nphys3077	journal	September 2014
Spintronics goes plastic Sanvito, Stefano Nature Materials, Vol. 6, Issue 11 https://doi.org/10.1038/nmat2050	journal	November 2007
Separating hyperfine from spin-orbit interactions in organic semiconductors by multi-octave magnetic resonance using coplanar waveguide microresonators Joshi, G.; Miller, R.; Ogden, L. Applied Physics Letters, Vol. 109, Issue 10 https://doi.org/10.1063/1.4960158	journal	September 2016
Isotope effect in spin response of π-conjugated polymer films and devices Nguyen, Tho D.; Hukic-Markosian, Golda; Wang, Fujian Nature Materials, Vol. 9, Issue 4 https://doi.org/10.1038/nmat2633	journal	February 2010
Tuning magnetoresistance between positive and negative values in organic semiconductors Hu, Bin; Wu, Yue Nature Materials, Vol. 6, Issue 12 https://doi.org/10.1038/nmat2034	journal	October 2007
Giant magnetoresistance in organic spin-valves Xiong, Z. H.; Wu, Di; Valy Vardeny, Z. Nature, Vol. 427, Issue 6977 https://doi.org/10.1038/nature02325	journal	February 2004
Spin routes in organic semiconductors Dediu, V. Alek; Hueso, Luis E.; Bergenti, Ilaria Nature Materials, Vol. 8, Issue 9 https://doi.org/10.1038/nmat2510	journal	August 2009
Triplet–singlet spin relaxation via nuclei in a double quantum dot Johnson, A. C.; Petta, J. R.; Taylor, J. M. Nature, Vol. 435, Issue 7044 https://doi.org/10.1038/nature03815	journal	June 2005
Pumping spins through polymers Koopmans, Bert Nature Physics, Vol. 10, Issue 4 https://doi.org/10.1038/nphys2928	journal	March 2014
Room-temperature coupling between electrical current and nuclear spins in OLEDs Malissa, H.; Kavand, M.; Waters, D. P. Science, Vol. 345, Issue 6203 https://doi.org/10.1126/science.1255624	journal	September 2014
Optical Pumping of the Electronic and Nuclear Spin of Single Charge-Tunable Quantum Dots Bracker, A.; Stinaff, E.; Gammon, D. Physical Review Letters, Vol. 94, Issue 4 https://doi.org/10.1103/PhysRevLett.94.047402	journal	February 2005
Inverse spin Hall effect from pulsed spin current in organic semiconductors with tunable spin–orbit coupling Sun, Dali; van Schooten, Kipp J.; Kavand, Marzieh Nature Materials, Vol. 15, Issue 8 https://doi.org/10.1038/nmat4618	journal	April 2016
Efficient spin transport through polyaniline Mendes, J. B. S.; Alves Santos, O.; Gomes, J. P. Physical Review B, Vol. 95, Issue 1 https://doi.org/10.1103/PhysRevB.95.014413	journal	January 2017
Unravelling the role of the interface for spin injection into organic semiconductors Barraud, Clément; Seneor, Pierre; Mattana, Richard Nature Physics, Vol. 6, Issue 8 https://doi.org/10.1038/nphys1688	journal	June 2010
Highly efficient inverted organic photovoltaics using solution based titanium oxide as electron selective contact Waldauf, C.; Morana, M.; Denk, P. Applied Physics Letters, Vol. 89, Issue 23 https://doi.org/10.1063/1.2402890	journal	December 2006
Tuning the Performance of Organic Spintronic Devices Using X-Ray Generated Traps Rybicki, J.; Lin, R.; Wang, F. Physical Review Letters, Vol. 109, Issue 7 https://doi.org/10.1103/PhysRevLett.109.076603	journal	August 2012
Room temperature organic spintronics Morley, N. A.; Rao, A.; Dhandapani, D. Journal of Applied Physics, Vol. 103, Issue 7 https://doi.org/10.1063/1.2829245	journal	April 2008
Theory for Spin Diffusion in Disordered Organic Semiconductors Bobbert, P. A.; Wagemans, W.; van Oost, F. W. A. Physical Review Letters, Vol. 102, Issue 15 https://doi.org/10.1103/PhysRevLett.102.156604	journal	April 2009
Bipolaron Mechanism for Organic Magnetoresistance Bobbert, P. A.; Nguyen, T. D.; van Oost, F. W. A. Physical Review Letters, Vol. 99, Issue 21 https://doi.org/10.1103/PhysRevLett.99.216801	journal	November 2007
Magnetic field effects in chemical kinetics and related phenomena Steiner, Ulrich E.; Ulrich, Thomas Chemical Reviews, Vol. 89, Issue 1 https://doi.org/10.1021/cr00091a003	journal	January 1989
Magnetic Field Effects in π -Conjugated Polymer-Fullerene Blends: Evidence for Multiple Components Wang, F. J.; Bässler, Heinz; Valy Vardeny, Z. Physical Review Letters, Vol. 101, Issue 23 https://doi.org/10.1103/PhysRevLett.101.236805	journal	December 2008
Electronic Delocalization in the Radical Cations of Porphyrin Oligomer Molecular Wires Peeks, Martin D.; Tait, Claudia E.; Neuhaus, Patrik Journal of the American Chemical Society, Vol. 139, Issue 30 https://doi.org/10.1021/jacs.7b05386	journal	July 2017
Separating Positive and Negative Magnetoresistance in Organic Semiconductor Devices Bloom, F. L.; Wagemans, W.; Kemerink, M. Physical Review Letters, Vol. 99, Issue 25 https://doi.org/10.1103/PhysRevLett.99.257201	journal	December 2007
Spins in few-electron quantum dots Hanson, R.; Kouwenhoven, L. P.; Petta, J. R. Reviews of Modern Physics, Vol. 79, Issue 4 https://doi.org/10.1103/RevModPhys.79.1217	journal	October 2007
Electronic analog of the electro‐optic modulator Datta, Supriyo; Das, Biswajit Applied Physics Letters, Vol. 56, Issue 7 https://doi.org/10.1063/1.102730	journal	February 1990
A review on organic spintronic materials and devices: I. Magnetic field effect on organic light emitting diodes Geng, Rugang; Daugherty, Timothy Tyler; Do, Kevin Journal of Science: Advanced Materials and Devices, Vol. 1, Issue 2 https://doi.org/10.1016/j.jsamd.2016.05.002	journal	June 2016
Hyperfine interaction and magnetoresistance in organic semiconductors Sheng, Y.; Nguyen, T. D.; Veeraraghavan, G. Physical Review B, Vol. 74, Issue 4 https://doi.org/10.1103/PhysRevB.74.045213	journal	July 2006
Importance of Spin-Orbit Interaction for the Electron Spin Relaxation in Organic Semiconductors Nuccio, L.; Willis, M.; Schulz, L. Physical Review Letters, Vol. 110, Issue 21 https://doi.org/10.1103/PhysRevLett.110.216602	journal	May 2013
Application of regioregular polythiophene in spintronic devices: Effect of interface Majumdar, Sayani; Laiho, R.; Laukkanen, P. Applied Physics Letters, Vol. 89, Issue 12 https://doi.org/10.1063/1.2356463	journal	September 2006
The role of magnetic fields on the transport and efficiency of aluminum tris(8-hydroxyquinoline) based organic light emitting diodes Desai, P.; Shakya, P.; Kreouzis, T. Journal of Applied Physics, Vol. 102, Issue 7 https://doi.org/10.1063/1.2787158	journal	October 2007
The isotopic effects of deuteration on optoelectronic properties of conducting polymers Shao, Ming; Keum, Jong; Chen, Jihua Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4180	journal	January 2014
Effects of Thermal Annealing Upon the Morphology of Polymer-Fullerene Blends Verploegen, Eric; Mondal, Rajib; Bettinger, Christopher J. Advanced Functional Materials, Vol. 20, Issue 20 https://doi.org/10.1002/adfm.201000975	journal	August 2010
Hyperfine-Field-Mediated Spin Beating in Electrostatically Bound Charge Carrier Pairs McCamey, D. R.; van Schooten, K. J.; Baker, W. J. Physical Review Letters, Vol. 104, Issue 1, Article No. 017601 https://doi.org/10.1103/PhysRevLett.104.017601	journal	January 2010
Charge injection and transport in single-layer organic light-emitting diodes Crone, B. K.; Campbell, I. H.; Davids, P. S. Applied Physics Letters, Vol. 73, Issue 21 https://doi.org/10.1063/1.122706	journal	November 1998
Extreme electron polaron spatial delocalization in π-conjugated materials Rawson, Jeff; Angiolillo, Paul J.; Therien, Michael J. Proceedings of the National Academy of Sciences, Vol. 112, Issue 45 https://doi.org/10.1073/pnas.1512318112	journal	October 2015
Molecular spintronics Sanvito, Stefano Chemical Society Reviews, Vol. 40, Issue 6 https://doi.org/10.1039/c1cs15047b	journal	January 2011
Improving efficiency by balancing carrier transport in poly(9,9-dioctylfluorene) light-emitting diodes using tetraphenylporphyrin as a hole-trapping, emissive dopant Campbell, Alasdair J.; Bradley, Donal D. C.; Virgili, Tersilla Applied Physics Letters, Vol. 79, Issue 23 https://doi.org/10.1063/1.1421415	journal	December 2001
Highly-efficient charge separation and polaron delocalization in polymer–fullerene bulk-heterojunctions: a comparative multi-frequency EPR and DFT study Niklas, Jens; Mardis, Kristy L.; Banks, Brian P. Physical Chemistry Chemical Physics, Vol. 15, Issue 24 https://doi.org/10.1039/c3cp51477c	journal	January 2013
Magnetoconductance Response in Unipolar and Bipolar Organic Diodes at Ultrasmall Fields Nguyen, T. D.; Gautam, B. R.; Ehrenfreund, E. Physical Review Letters, Vol. 105, Issue 16 https://doi.org/10.1103/PhysRevLett.105.166804	journal	October 2010
Organic Spin Valves: A Review Devkota, Jagannath; Geng, Rugang; Subedi, Ram Chandra Advanced Functional Materials, Vol. 26, Issue 22 https://doi.org/10.1002/adfm.201504209	journal	March 2016
Environment-assisted quantum control of a solid-state spin via coherent dark states Hansom, J.; Schulte, Chh; Le Gall, Claire Apollo - University of Cambridge Repository https://doi.org/10.17863/cam.40225	text	January 2014
Highly-Efficient Charge Separation and Polaron Delocalization in Polymer-Fullerene Bulk-Heterojunctions: A Comparative Multi-Frequency EPR & DFT Study Niklas, Jens; Mardis, Kristy L.; Banks, Brian P. arXiv https://doi.org/10.48550/arxiv.1305.6434	text	January 2013
Environment-assisted quantum control of a solid-state spin via coherent dark states Hansom, Jack; Schulte, Carsten H. H.; Gall, Claire Le arXiv https://doi.org/10.48550/arxiv.1408.1272	text	January 2014
Separating hyperfine from spin-orbit interactions in organic semiconductors by multi-octave magnetic resonance using coplanar waveguide microresonators Joshi, Gajadhar; Miller, Richards; Ogden, Lillie arXiv https://doi.org/10.48550/arxiv.1603.03807	text	January 2016

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