Probing long-range carrier-pair spin–spin interactions in a conjugated polymer by detuning of electrically detected spin beating

van Schooten, Kipp J.; Baird, Douglas L.; Limes, Mark E.; Lupton, John M.; Boehme, Christoph

doi:10.1038/ncomms7688

Title: Probing long-range carrier-pair spin–spin interactions in a conjugated polymer by detuning of electrically detected spin beating

Journal Article · Tue Apr 14 00:00:00 EDT 2015 · Nature Communications

DOI:https://doi.org/10.1038/ncomms7688· OSTI ID:1454251

van Schooten, Kipp J. ^[1]; Baird, Douglas L. ^[1]; Limes, Mark E. ^[1]; Lupton, John M. ^[2]; Boehme, Christoph ^[1]

Univ. of Utah, Salt Lake City, UT (United States). Dept. of Physics and Astronomy
Univ. of Utah, Salt Lake City, UT (United States). Dept. of Physics and Astronomy; Univ. of Regensburg, Regensburg (Germany). Inst. of Experimental and Applied Physics

Here, weakly coupled electron spin pairs that experience weak spin–orbit interaction can control electronic transitions in molecular and solid-state systems. Known to determine radical pair reactions, they have been invoked to explain phenomena ranging from avian magnetoreception to spin-dependent charge-carrier recombination and transport. Spin pairs exhibit persistent spin coherence, allowing minute magnetic fields to perturb spin precession and thus recombination rates and photoreaction yields, giving rise to a range of magneto-optoelectronic effects in devices. Little is known, however, about interparticle magnetic interactions within such pairs. Here we present pulsed electrically detected electron spin resonance experiments on poly(styrene-sulfonate)-doped poly(3,4-ethylenedioxythiophene) (PEDOT:PSS) devices, which show how interparticle spin–spin interactions (magnetic-dipolar and spin-exchange) between charge-carrier spin pairs can be probed through the detuning of spin-Rabi oscillations. The deviation from uncoupled precession frequencies quantifies both the exchange (<30 neV) and dipolar (23.5±1.5 neV) interaction energies responsible for the pair’s zero-field splitting, implying quantum mechanical entanglement of charge-carrier spins over distances of 2.1±0.1 nm.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Univ. of Utah, Salt Lake City, UT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

Grant/Contract Number:: SC0000909

OSTI ID:: 1454251

Journal Information:: Nature Communications, Vol. 6, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 34 works

Citation information provided by
Web of Science

References (59)

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
Numerical study of spin-dependent transition rates within pairs of dipolar and exchange coupled spins with $s = \frac{1}{2}$ during magnetic resonant excitation Limes, M. E.; Wang, J.; Baker, W. J. Physical Review B, Vol. 87, Issue 16 https://doi.org/10.1103/PhysRevB.87.165204	journal	April 2013
Analytical study of spin-dependent transition rates within pairs of dipolar and strongly exchange coupled spins with $s$ $=$ $\frac{1}{2}$ during magnetic resonant excitation Glenn, R.; Limes, M. E.; Saam, B. Physical Review B, Vol. 87, Issue 16 https://doi.org/10.1103/PhysRevB.87.165205	journal	April 2013
Measurement of the magnetic interaction between two bound electrons of two separate ions Kotler, Shlomi; Akerman, Nitzan; Navon, Nir Nature, Vol. 510, Issue 7505 https://doi.org/10.1038/nature13403	journal	June 2014
Site-specific electronic structure of an oligo-ethylenedioxythiophene derivative probed by resonant photoemission Osikowicz, W.; Friedlein, R.; Jong, M. P. de New Journal of Physics, Vol. 7 https://doi.org/10.1088/1367-2630/7/1/104	journal	January 2005
Challenges for organic spintronics Boehme, Christoph; Lupton, John M. Nature Nanotechnology, Vol. 8, Issue 9 https://doi.org/10.1038/nnano.2013.177	journal	September 2013
Robust absolute magnetometry with organic thin-film devices Baker, W. J.; Ambal, K.; Waters, D. P. Nature Communications, Vol. 3, Issue 1 https://doi.org/10.1038/ncomms1895	journal	January 2012
Formation cross-sections of singlet and triplet excitons in π-conjugated polymers Wohlgenannt, M.; Tandon, Kunj; Mazumdar, S. Nature, Vol. 409, Issue 6819 https://doi.org/10.1038/35054025	journal	January 2001
Spin Rabi flopping in the photocurrent of a polymer light-emitting diode McCamey, D. R.; Seipel, H. A.; Paik, S. -Y. Nature Materials, Vol. 7, Issue 9 https://doi.org/10.1038/nmat2252	journal	August 2008
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
Sustained Quantum Coherence and Entanglement in the Avian Compass Gauger, Erik M.; Rieper, Elisabeth; Morton, John J. L. Physical Review Letters, Vol. 106, Issue 4 https://doi.org/10.1103/PhysRevLett.106.040503	journal	January 2011
Extremely strong room-temperature transient photocurrent-detected magnetic resonance in organic devices Chen, Ying; Liu, Rui; Cai, Min Physical Review B, Vol. 86, Issue 23 https://doi.org/10.1103/PhysRevB.86.235442	journal	December 2012
Time domain measurement of spin-dependent recombination Boehme, Christoph; Lips, Klaus Applied Physics Letters, Vol. 79, Issue 26 https://doi.org/10.1063/1.1428623	journal	December 2001
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
Spin-dependent electronic processes and long-lived spin coherence of deep-level trap sites in CdS nanocrystals van Schooten, K. J.; Huang, J.; Talapin, D. V. Physical Review B, Vol. 87, Issue 12 https://doi.org/10.1103/PhysRevB.87.125412	journal	March 2013
Transport properties of poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) Aleshin, A. N.; Williams, S. R.; Heeger, A. J. Synthetic Metals, Vol. 94, Issue 2, p. 173-177 https://doi.org/10.1016/S0379-6779(97)04167-2	journal	April 1998
A Model for Photoreceptor-Based Magnetoreception in Birds Ritz, Thorsten; Adem, Salih; Schulten, Klaus Biophysical Journal, Vol. 78, Issue 2 https://doi.org/10.1016/S0006-3495(00)76629-X	journal	February 2000
Effect of exchange coupling on coherently controlled spin-dependent transition rates Gliesche, A.; Michel, C.; Rajevac, V. Physical Review B, Vol. 77, Issue 24 https://doi.org/10.1103/PhysRevB.77.245206	journal	June 2008
Noise-induced quantum coherence drives photo-carrier generation dynamics at polymeric semiconductor heterojunctions Bittner, Eric R.; Silva, Carlos Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4119	journal	January 2014
Electronic Spin Storage in an Electrically Readable Nuclear Spin Memory with a Lifetime >100 Seconds McCamey, D. R.; Van Tol, J.; Morley, G. W. Science, Vol. 330, Issue 6011 https://doi.org/10.1126/science.1197931	journal	December 2010
PELDOR at S- and X-Band Frequencies and the Separation of Exchange Coupling from Dipolar Coupling Weber, Axel; Schiemann, Olav; Bode, Bela Journal of Magnetic Resonance, Vol. 157, Issue 2 https://doi.org/10.1006/jmre.2002.2596	journal	August 2002
Organic magnetoresistance near saturation: Mesoscopic effects in small devices Roundy, R. C.; Vardeny, Z. V.; Raikh, M. E. Physical Review B, Vol. 88, Issue 7 https://doi.org/10.1103/PhysRevB.88.075207	journal	August 2013
Cryptochrome mediates light-dependent magnetosensitivity in Drosophila Gegear, Robert J.; Casselman, Amy; Waddell, Scott Nature, Vol. 454, Issue 7207 https://doi.org/10.1038/nature07183	journal	July 2008
Electrically detected double electron–electron resonance: exchange interaction of P donors and P defects at the Si/SiO interface Suckert, Max; Hoehne, Felix; Dreher, Lukas Molecular Physics, Vol. 111, Issue 18-19 https://doi.org/10.1080/00268976.2013.816796	journal	May 2013
Analytical description of spin-Rabi oscillation controlled electronic transitions rates between weakly coupled pairs of paramagnetic states with $S = \frac{1}{2}$ Glenn, R.; Baker, W. J.; Boehme, C. Physical Review B, Vol. 87, Issue 15 https://doi.org/10.1103/PhysRevB.87.155208	journal	April 2013
Role of Exchange and Dipolar Interactions in the Radical Pair Model of the Avian Magnetic Compass Efimova, Olga; Hore, P. J. Biophysical Journal, Vol. 94, Issue 5 https://doi.org/10.1529/biophysj.107.119362	journal	March 2008
Modulation frequency dependence of continuous-wave optically/electrically detected magnetic resonance Lee, Sang-Yun; Paik, Seoyoung; McCamey, Dane R. Physical Review B, Vol. 86, Issue 11 https://doi.org/10.1103/PhysRevB.86.115204	journal	September 2012
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
Resonance effects indicate a radical-pair mechanism for avian magnetic compass Ritz, Thorsten; Thalau, Peter; Phillips, John B. Nature, Vol. 429, Issue 6988 https://doi.org/10.1038/nature02534	journal	May 2004
Spin-dependent dynamics of polaron pairs in organic semiconductors McCamey, D. R.; Lee, S. -Y.; Paik, S. -Y. Physical Review B, Vol. 82, Issue 12 https://doi.org/10.1103/PhysRevB.82.125206	journal	September 2010
Low-Field Optically Detected EPR Spectroscopy of Transient Photoinduced Radical Pairs Rodgers, Christopher T.; Henbest, Kevin B.; Kukura, Philipp The Journal of Physical Chemistry A, Vol. 109, Issue 23 https://doi.org/10.1021/jp050765z	journal	June 2005
Readout and control of a single nuclear spin with a metastable electron spin ancilla Lee, Sang-Yun; Widmann, Matthias; Rendler, Torsten Nature Nanotechnology, Vol. 8, Issue 7 https://doi.org/10.1038/nnano.2013.104	journal	June 2013
Effects of spin-spin interactions on magnetoresistance in disordered organic semiconductors Harmon, N. J.; Flatté, M. E. Physical Review B, Vol. 85, Issue 24 https://doi.org/10.1103/PhysRevB.85.245213	journal	June 2012
Coherent Spin Manipulation in Molecular Semiconductors: Getting a Handle on Organic Spintronics Lupton, John M.; McCamey, Dane R.; Boehme, Christoph ChemPhysChem, Vol. 11, Issue 14 https://doi.org/10.1002/cphc.201000186	journal	July 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
EDMR of MEH-PPV LEDs Silva, G. B.; Santos, L. F.; Faria, R. M. Physica B: Condensed Matter, Vol. 308-310 https://doi.org/10.1016/S0921-4526(01)00859-6	journal	December 2001
Nuclear-Spin Quantum Memory Poised to Take the Lead Boehme, C.; McCamey, D. R. Science, Vol. 336, Issue 6086 https://doi.org/10.1126/science.1223439	journal	June 2012
Electrical properties of isolated poly(3,4-ethylenedioxythiophene) nanowires prepared by template synthesis Long, Y. Z.; Duvail, J. L.; Chen, Z. J. Polymers for Advanced Technologies, Vol. 20, Issue 6 https://doi.org/10.1002/pat.1379	journal	June 2009
Ultrahigh Magnetoresistance at Room Temperature in Molecular Wires Mahato, R. N.; Lulf, H.; Siekman, M. H. Science, Vol. 341, Issue 6143 https://doi.org/10.1126/science.1237242	journal	July 2013
Semi-metallic polymers Bubnova, Olga; Khan, Zia Ullah; Wang, Hui Nature Materials, Vol. 13, Issue 2 https://doi.org/10.1038/nmat3824	journal	December 2013
Electrically detected crystal orientation dependent spin-Rabi beat oscillation of c-Si(111)/SiO $_{2}$ interface states Paik, Seoyoung; Lee, Sang-Yun; McCamey, Dane R. Physical Review B, Vol. 84, Issue 23 https://doi.org/10.1103/PhysRevB.84.235305	journal	December 2011
Magnetic Field Dependence of the Geminate Recombination of Radical Ion Pairs in Polar Solvents Schulten, K.; Staerk, H.; Weller, A. Zeitschrift für Physikalische Chemie, Vol. 101, Issue 1-6 https://doi.org/10.1524/zpch.1976.101.1-6.371	journal	September 1976
Theory of time-domain measurement of spin-dependent recombination with pulsed electrically detected magnetic resonance Boehme, Christoph; Lips, Klaus Physical Review B, Vol. 68, Issue 24 https://doi.org/10.1103/PhysRevB.68.245105	journal	December 2003
Tuning Hyperfine Fields in Conjugated Polymers for Coherent Organic Spintronics Lee, Sang-Yun; Paik, Seo-Young; McCamey, Dane R. Journal of the American Chemical Society, Vol. 133, Issue 7 https://doi.org/10.1021/ja108352d	journal	February 2011
Transport and recombination through weakly coupled localized spin pairs in semiconductors during coherent spin excitation Rajevac, V.; Boehme, C.; Michel, C. Physical Review B, Vol. 74, Issue 24 https://doi.org/10.1103/PhysRevB.74.245206	journal	December 2006
Quantum biology Lambert, Neill; Chen, Yueh-Nan; Cheng, Yuan-Chung Nature Physics, Vol. 9, Issue 1 https://doi.org/10.1038/nphys2474	journal	December 2012
Pulsed electrically detected magnetic resonance in organic semiconductors: Pulsed electrically detected magnetic resonance in organic semiconductors Boehme, C.; McCamey, D. R.; van Schooten, K. J. physica status solidi (b), Vol. 246, Issue 11-12 https://doi.org/10.1002/pssb.200982357	journal	November 2009
Influence of disorder on electrically and optically detected electron spin nutation Michel, C.; Gliesche, A.; Baranovskii, S. D. Physical Review B, Vol. 79, Issue 5 https://doi.org/10.1103/PhysRevB.79.052201	journal	February 2009
Disruption of Mediator rescues the stunted growth of a lignin-deficient Arabidopsis mutant Bonawitz, Nicholas D.; Kim, Jeong Im; Tobimatsu, Yuki Nature, Vol. 509, Issue 7500, p. 376-380 https://doi.org/10.1038/nature13084	journal	March 2014
Anisotropic hopping conduction in spin-coated PEDOT:PSS thin films Nardes, A. M.; Kemerink, M.; Janssen, R. A. J. Physical Review B, Vol. 76, Issue 8 https://doi.org/10.1103/physrevb.76.085208	journal	August 2007
Microscopic modeling of magnetic-field effects on charge transport in organic semiconductors Schellekens, A. J.; Wagemans, W.; Kersten, S. P. Physical Review B, Vol. 84, Issue 7 https://doi.org/10.1103/physrevb.84.075204	journal	August 2011
Differentiation between polaron-pair and triplet-exciton polaron spin-dependent mechanisms in organic light-emitting diodes by coherent spin beating Baker, W. J.; McCamey, D. R.; van Schooten, K. J. Physical Review B, Vol. 84, Issue 16 https://doi.org/10.1103/physrevb.84.165205	journal	October 2011
Bipolaron Formation in Organic Solar Cells Observed by Pulsed Electrically Detected Magnetic Resonance Behrends, J.; Schnegg, A.; Lips, K. Physical Review Letters, Vol. 105, Issue 17 https://doi.org/10.1103/physrevlett.105.176601	journal	October 2010
Slow Hopping and Spin Dephasing of Coulombically Bound Polaron Pairs in an Organic Semiconductor at Room Temperature Baker, W. J.; Keevers, T. L.; Lupton, J. M. Physical Review Letters, Vol. 108, Issue 26 https://doi.org/10.1103/physrevlett.108.267601	journal	June 2012
Quantum Information Storage for over 180 s Using Donor Spins in a 28Si "Semiconductor Vacuum" Steger, M.; Saeedi, K.; Thewalt, M. L. W. Science, Vol. 336, Issue 6086 https://doi.org/10.1126/science.1217635	journal	June 2012
Sustained Quantum Coherence and Entanglement in the Avian Compass Gauger, Erik; Rieper, Elisabeth; Morton, John J. L. arXiv https://doi.org/10.48550/arxiv.0906.3725	text	January 2009
Readout and control of a single nuclear spin with a meta-stable electron spin ancilla Lee, Sang-Yun; Widmann, Matthias; Rendler, Torsten arXiv https://doi.org/10.48550/arxiv.1302.4608	text	January 2013
Robust absolute magnetometry with organic thin-film devices Baker, W. J.; Ambal, K.; Waters, D. P. Universität Regensburg https://doi.org/10.5283/epub.26688	text	January 2012
Spin-dependent electronic processes and long-lived spin coherence of deep-level trap sites in CdS nanocrystals van Schooten, K. J.; Huang, J.; Talapin, D. V. Universität Regensburg https://doi.org/10.5283/epub.27937	text	January 2013

Cited By (15)

Tuning the effective spin-orbit coupling in molecular semiconductors Schott, Sam; McNellis, Erik R.; Nielsen, Christian B. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15200	journal	May 2017
OLEDs as models for bird magnetoception: detecting electron spin resonance in geomagnetic fields Grünbaum, Tobias; Milster, Sebastian; Kraus, Hermann Faraday Discussions, Vol. 221 https://doi.org/10.1039/c9fd00047j	journal	January 2020
Perdeuteration of poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene] (d-MEH-PPV): control of microscopic charge-carrier spin–spin coupling and of magnetic-field effects in optoelectronic devices Stoltzfus, Dani M.; Joshi, Gajadhar; Popli, Henna Journal of Materials Chemistry C, Vol. 8, Issue 8 https://doi.org/10.1039/c9tc05322k	journal	January 2020
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
Morphology effects on spin-dependent transport and recombination in polyfluorene thin films Miller, Richards; van Schooten, K. J.; Malissa, H. Physical Review B, Vol. 94, Issue 21 https://doi.org/10.1103/physrevb.94.214202	journal	December 2016
Spin dynamics and spin-dependent recombination of a polaron pair under a strong ac drive Malla, Rajesh K.; Raikh, M. E. Physical Review B, Vol. 96, Issue 8 https://doi.org/10.1103/physrevb.96.085311	journal	August 2017
Tuning effective hyperfine fields in PEDOT:PSS thin films by doping Teferi, M. Y.; Ogle, J.; Joshi, G. Physical Review B, Vol. 98, Issue 24 https://doi.org/10.1103/physrevb.98.241201	journal	December 2018
Tuning the effective spin-orbit coupling in molecular semiconductors Schott, Sam; McNellis, Er; Nielsen, Cb Apollo - University of Cambridge Repository https://doi.org/10.17863/cam.9556	text	January 2017
OLEDs as models for bird magnetoception: detecting electron spin resonance in geomagnetic fields Grünbaum, Tobias; Milster, Sebastian; Kraus, Hermann Universität Regensburg https://doi.org/10.5283/epub.41348	text	January 2019
Perdeuteration of poly[2-methoxy-5-(2'- ethylhexyloxy)-1,4-phenylenevinylene] (d-MEH-PPV): control of microscopic charge-carrier spin–spin coupling and of magnetic-field effects in optoelectronic devices Stoltzfus, Dani M.; Joshi, Gajadhar; Popli, Henna Universität Regensburg https://doi.org/10.5283/epub.41666	text	January 2020
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
Spin dynamics and spin-dependent recombination of a polaron pair under a strong ac drive Malla, R. K.; Raikh, M. E. arXiv https://doi.org/10.48550/arxiv.1704.00392	text	January 2017
Tuning effective hyperfine fields in PEDOT:PSS thin films by doping Teferi, M. Y.; Ogle, J.; Joshi, G. arXiv https://doi.org/10.48550/arxiv.1804.05139	text	January 2018
OLEDs as models for bird magnetoception: detecting electron spin resonance in geomagnetic fields Grünbaum, Tobias; Milster, Sebastian; Kraus, Hermann arXiv https://doi.org/10.48550/arxiv.1906.03090	text	January 2019
Tuning the effective spin-orbit coupling in molecular semiconductors Schott, Sam; McNellis, Erik R.; Nielsen, Christian B. arXiv https://doi.org/10.48550/arxiv.1704.01371	text	January 2017

Similar Records

OLEDs as models for bird magnetoception: detecting electron spin resonance in geomagnetic fields

Journal Article · Wed Sep 25 00:00:00 EDT 2019 · Faraday Discussions · OSTI ID:1454251

Grünbaum, Tobias; Milster, Sebastian; Kraus, Hermann; +6 more

Renewal: Coherent control of spin states in organic electronics – discovery and investigation of complex room-temperature magnetic quantum excitations

Technical Report · Wed May 31 00:00:00 EDT 2023 · OSTI ID:1454251

Boehme, Christoph; Lupton, John

Morphology effects on spin-dependent transport and recombination in polyfluorene thin films

Journal Article · Mon Dec 05 00:00:00 EST 2016 · Physical Review B · OSTI ID:1454251

Miller, Richards; van Schooten, K. J.; Malissa, H.; +4 more

Related Subjects

36 MATERIALS SCIENCE

Title: Probing long-range carrier-pair spin–spin interactions in a conjugated polymer by detuning of electrically detected spin beating

Citation Formats

References (59)

Cited By (15)

Similar Records

Related Subjects