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

Abstract

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 tomore » other semiconducting polymers. Lastly, this Letter may provide great benefits for organic optoelectronics, chemical reaction kinetics, and magnetoreception in biology.« less

Authors:
 [1];  [1];  [1];  [1];  [2];  [2]; ORCiD logo [3];  [3]; ORCiD logo [3];  [4];  [1]
  1. Univ. of Georgia, Athens, GA (United States). Dept. of Physics and Astronomy
  2. 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
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  4. Univ. of Georgia, Athens, GA (United States). College of Engineering
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1494885
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Letters
Additional Journal Information:
Journal Volume: 120; Journal Issue: 8; Journal ID: ISSN 0031-9007
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Geng, Rugang, Subedi, Ram C., Luong, Hoang M., Pham, Minh T., Huang, Weichuan, Li, Xiaoguang, Hong, Kunlun, Shao, Ming, Xiao, Kai, Hornak, Lawrence A., and Nguyen, Tho D. Effect of Charge Localization on the Effective Hyperfine Interaction in Organic Semiconducting Polymers. United States: N. p., 2018. Web. doi:10.1103/PhysRevLett.120.086602.
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. Effect of Charge Localization on the Effective Hyperfine Interaction in Organic Semiconducting Polymers. United States. doi:10.1103/PhysRevLett.120.086602.
Geng, Rugang, Subedi, Ram C., Luong, Hoang M., Pham, Minh T., Huang, Weichuan, Li, Xiaoguang, Hong, Kunlun, Shao, Ming, Xiao, Kai, Hornak, Lawrence A., and Nguyen, Tho D. Thu . "Effect of Charge Localization on the Effective Hyperfine Interaction in Organic Semiconducting Polymers". United States. doi:10.1103/PhysRevLett.120.086602. https://www.osti.gov/servlets/purl/1494885.
@article{osti_1494885,
title = {Effect of Charge Localization on the Effective Hyperfine Interaction in Organic Semiconducting Polymers},
author = {Geng, Rugang and Subedi, Ram C. and Luong, Hoang M. and Pham, Minh T. and Huang, Weichuan and Li, Xiaoguang and Hong, Kunlun and Shao, Ming and Xiao, Kai and Hornak, Lawrence A. and Nguyen, Tho D.},
abstractNote = {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/N0.5 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/N0.52 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.},
doi = {10.1103/PhysRevLett.120.086602},
journal = {Physical Review Letters},
number = 8,
volume = 120,
place = {United States},
year = {2018},
month = {2}
}

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Figures / Tables:

Figure 1 Figure 1: (a) Raman spectra of isotope-labeled P3HT. The insets show the chemical structures of hydrogenated P3HT and full-deuterated P3HT. (b) Photoluminescence of the isotopes at a low temperature of 10 K. (c) IV characteristics and (d) MC (with 0.5 G resolution) of the isotopebased hole-only devices at 10 K.

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Works referenced in this record:

Chemical compass model of avian magnetoreception
journal, April 2008

  • Maeda, Kiminori; Henbest, Kevin B.; Cintolesi, Filippo
  • Nature, Vol. 453, Issue 7193
  • DOI: 10.1038/nature06834

Indirect Hyperfine Interactions in the Paramagnetic Resonance Spectra of Aromatic Free Radicals
journal, April 1956

  • McConnell, Harden M.
  • The Journal of Chemical Physics, Vol. 24, Issue 4
  • DOI: 10.1063/1.1742605

Enhancement of organic magnetoresistance by electrical conditioning
journal, May 2008

  • Niedermeier, U.; Vieth, M.; Pätzold, R.
  • Applied Physics Letters, Vol. 92, Issue 19
  • DOI: 10.1063/1.2924765

A quantitative interpretation of the magnetic field effect on hyperfine-coupling-induced triplet fromation from radical ion pairs
journal, March 1983


Conjugated Chromophore Arrays with Unusually Large Hole Polaron Delocalization Lengths
journal, July 2006

  • Susumu, Kimihiro; Frail, Paul R.; Angiolillo, Paul J.
  • Journal of the American Chemical Society, Vol. 128, Issue 26
  • DOI: 10.1021/ja0614823

Polaron spin current transport in organic semiconductors
journal, March 2014

  • Watanabe, Shun; Ando, Kazuya; Kang, Keehoon
  • Nature Physics, Vol. 10, Issue 4
  • DOI: 10.1038/nphys2901

Enhanced room-temperature spin Seebeck effect in a YIG/C 60 /Pt layered heterostructure
journal, May 2018

  • Das, R.; Kalappattil, V.; Geng, R.
  • AIP Advances, Vol. 8, Issue 5
  • DOI: 10.1063/1.5007233

Origin of the different transport properties of electron and hole polarons in an ambipolar polyselenophene-based conjugated polymer
journal, September 2011


EPR study of positive holes on phenylene vinylene chains: from dimer to polymer
journal, May 2004


Environment-assisted quantum control of a solid-state spin via coherent dark states
journal, September 2014

  • Hansom, Jack; Schulte, Carsten H. H.; Le Gall, Claire
  • Nature Physics, Vol. 10, Issue 10
  • DOI: 10.1038/nphys3077

Spintronics goes plastic
journal, November 2007


Isotope effect in spin response of π-conjugated polymer films and devices
journal, February 2010

  • Nguyen, Tho D.; Hukic-Markosian, Golda; Wang, Fujian
  • Nature Materials, Vol. 9, Issue 4
  • DOI: 10.1038/nmat2633

Tuning magnetoresistance between positive and negative values in organic semiconductors
journal, October 2007


Giant magnetoresistance in organic spin-valves
journal, February 2004


Spin routes in organic semiconductors
journal, August 2009

  • Dediu, V. Alek; Hueso, Luis E.; Bergenti, Ilaria
  • Nature Materials, Vol. 8, Issue 9
  • DOI: 10.1038/nmat2510

Triplet–singlet spin relaxation via nuclei in a double quantum dot
journal, June 2005

  • Johnson, A. C.; Petta, J. R.; Taylor, J. M.
  • Nature, Vol. 435, Issue 7044
  • DOI: 10.1038/nature03815

Pumping spins through polymers
journal, March 2014


Room-temperature coupling between electrical current and nuclear spins in OLEDs
journal, September 2014


Optical Pumping of the Electronic and Nuclear Spin of Single Charge-Tunable Quantum Dots
journal, February 2005


Inverse spin Hall effect from pulsed spin current in organic semiconductors with tunable spin–orbit coupling
journal, April 2016

  • Sun, Dali; van Schooten, Kipp J.; Kavand, Marzieh
  • Nature Materials, Vol. 15, Issue 8
  • DOI: 10.1038/nmat4618

Efficient spin transport through polyaniline
journal, January 2017


Unravelling the role of the interface for spin injection into organic semiconductors
journal, June 2010

  • Barraud, Clément; Seneor, Pierre; Mattana, Richard
  • Nature Physics, Vol. 6, Issue 8
  • DOI: 10.1038/nphys1688

Highly efficient inverted organic photovoltaics using solution based titanium oxide as electron selective contact
journal, December 2006

  • Waldauf, C.; Morana, M.; Denk, P.
  • Applied Physics Letters, Vol. 89, Issue 23
  • DOI: 10.1063/1.2402890

Tuning the Performance of Organic Spintronic Devices Using X-Ray Generated Traps
journal, August 2012


Room temperature organic spintronics
journal, April 2008

  • Morley, N. A.; Rao, A.; Dhandapani, D.
  • Journal of Applied Physics, Vol. 103, Issue 7
  • DOI: 10.1063/1.2829245

Theory for Spin Diffusion in Disordered Organic Semiconductors
journal, April 2009


Bipolaron Mechanism for Organic Magnetoresistance
journal, November 2007


Magnetic field effects in chemical kinetics and related phenomena
journal, January 1989

  • Steiner, Ulrich E.; Ulrich, Thomas
  • Chemical Reviews, Vol. 89, Issue 1
  • DOI: 10.1021/cr00091a003

Magnetic Field Effects in π -Conjugated Polymer-Fullerene Blends: Evidence for Multiple Components
journal, December 2008


Electronic Delocalization in the Radical Cations of Porphyrin Oligomer Molecular Wires
journal, July 2017

  • Peeks, Martin D.; Tait, Claudia E.; Neuhaus, Patrik
  • Journal of the American Chemical Society, Vol. 139, Issue 30
  • DOI: 10.1021/jacs.7b05386

Separating Positive and Negative Magnetoresistance in Organic Semiconductor Devices
journal, December 2007


Spins in few-electron quantum dots
journal, October 2007


Electronic analog of the electro‐optic modulator
journal, February 1990

  • Datta, Supriyo; Das, Biswajit
  • Applied Physics Letters, Vol. 56, Issue 7
  • DOI: 10.1063/1.102730

A review on organic spintronic materials and devices: I. Magnetic field effect on organic light emitting diodes
journal, June 2016

  • Geng, Rugang; Daugherty, Timothy Tyler; Do, Kevin
  • Journal of Science: Advanced Materials and Devices, Vol. 1, Issue 2
  • DOI: 10.1016/j.jsamd.2016.05.002

Hyperfine interaction and magnetoresistance in organic semiconductors
journal, July 2006


Importance of Spin-Orbit Interaction for the Electron Spin Relaxation in Organic Semiconductors
journal, May 2013


Application of regioregular polythiophene in spintronic devices: Effect of interface
journal, September 2006

  • Majumdar, Sayani; Laiho, R.; Laukkanen, P.
  • Applied Physics Letters, Vol. 89, Issue 12
  • DOI: 10.1063/1.2356463

The role of magnetic fields on the transport and efficiency of aluminum tris(8-hydroxyquinoline) based organic light emitting diodes
journal, October 2007

  • Desai, P.; Shakya, P.; Kreouzis, T.
  • Journal of Applied Physics, Vol. 102, Issue 7
  • DOI: 10.1063/1.2787158

The isotopic effects of deuteration on optoelectronic properties of conducting polymers
journal, January 2014

  • Shao, Ming; Keum, Jong; Chen, Jihua
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4180

Effects of Thermal Annealing Upon the Morphology of Polymer-Fullerene Blends
journal, August 2010

  • Verploegen, Eric; Mondal, Rajib; Bettinger, Christopher J.
  • Advanced Functional Materials, Vol. 20, Issue 20
  • DOI: 10.1002/adfm.201000975

Hyperfine-Field-Mediated Spin Beating in Electrostatically Bound Charge Carrier Pairs
journal, January 2010

  • McCamey, D. R.; van Schooten, K. J.; Baker, W. J.
  • Physical Review Letters, Vol. 104, Issue 1, Article No. 017601
  • DOI: 10.1103/PhysRevLett.104.017601

Charge injection and transport in single-layer organic light-emitting diodes
journal, November 1998

  • Crone, B. K.; Campbell, I. H.; Davids, P. S.
  • Applied Physics Letters, Vol. 73, Issue 21
  • DOI: 10.1063/1.122706

Extreme electron polaron spatial delocalization in π-conjugated materials
journal, October 2015

  • Rawson, Jeff; Angiolillo, Paul J.; Therien, Michael J.
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 45
  • DOI: 10.1073/pnas.1512318112

Molecular spintronics
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
journal, December 2001

  • Campbell, Alasdair J.; Bradley, Donal D. C.; Virgili, Tersilla
  • Applied Physics Letters, Vol. 79, Issue 23
  • DOI: 10.1063/1.1421415

Highly-efficient charge separation and polaron delocalization in polymer–fullerene bulk-heterojunctions: a comparative multi-frequency EPR and DFT study
journal, January 2013

  • Niklas, Jens; Mardis, Kristy L.; Banks, Brian P.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 24
  • DOI: 10.1039/c3cp51477c

Magnetoconductance Response in Unipolar and Bipolar Organic Diodes at Ultrasmall Fields
journal, October 2010


Organic Spin Valves: A Review
journal, March 2016

  • Devkota, Jagannath; Geng, Rugang; Subedi, Ram Chandra
  • Advanced Functional Materials, Vol. 26, Issue 22
  • DOI: 10.1002/adfm.201504209

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