Origin of Rashba Spin-Orbit Coupling in 2D and 3D Lead Iodide Perovskites

Pham, Minh T.; Amerling, Eric; Luong, Hoang M.; Pham, Huy T.; Larsen, George K.; Whittaker-Brooks, Luisa; Nguyen, Tho D.

doi:10.1038/s41598-020-61768-8

Origin of Rashba Spin-Orbit Coupling in 2D and 3D Lead Iodide Perovskites

Journal Article · Wed Mar 18 00:00:00 EDT 2020 · Scientific Reports

DOI:https://doi.org/10.1038/s41598-020-61768-8· OSTI ID:1628976

Pham, Minh T. ^[1]; Amerling, Eric ^[2]; Luong, Hoang M. ^[3]; Pham, Huy T. ^[4]; Larsen, George K. ^[5]; Whittaker-Brooks, Luisa ^[2]; Nguyen, Tho D. ^[3]

Univ. of Georgia, Athens, GA (United States). Dept. of Physics & Astronomy; DOE/OSTI
Univ. of Utah, Salt Lake City, UT (United States). Dept. of Chemistry
Univ. of Georgia, Athens, GA (United States). Dept. of Physics & Astronomy
Phenikaa Univ., Hanoi (Vietnam). Dept. of Materials Science and Engineering
Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL). National Security Directorate

isaWhittaker-Brooks2 & Tho D. Nguyen1* We studied spin dynamics of charge carriers in the superlattice-like Ruddlesden-Popper hybrid lead iodide perovskite semiconductors, 2D (BA)2(MA)Pb2I7 (with MA= CH3NH3, and BA= CH3(CH2)3NH3), and 3D MAPbI3 using the magnetic field effect (MFE) on conductivity and electroluminescence in their light emitting diodes (LEDs) at cryogenic temperatures. The semiconductors with distinct structural/ bulk inversion symmetry breaking, when combined with colossal intrinsic spin–orbit coupling (SOC), theoretically give rise to giant Rashba-type SOC. We found that the magneto-conductance (MC) magnitude increases monotonically with the emission intensity and saturates at ≈0.05% and 0.11% for the MAPbI3 and (BA)2(MA)Pb2I7, respectively. The magneto-electroluminescence (MEL) response with similar line shapes as the MC response has a significantly larger magnitude, and essentially stays constant at ≈0.22% and ≈0.20% for MAPbI3 and (BA)2(MA)Pb2I7, respectively. The sign and magnitude of the MC and MEL responses can be quantitatively explained in the framework of the Δg-based excitonic model using rate equations. Remarkably, the width of the MEL response in those materials linearly increases with increasing the applied electric field, where the Rashba coefficient in (BA)2(MA) Pb2I7 is estimated to be about 7 times larger than that in MAPbI3. Our studies might have significant impact on future development of electrically-controlled spin logic devices via Rashba-like effects

View Accepted Manuscript (DOE)

Research Organization:: Savannah River Site (SRS), Aiken, SC (United States)

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

Grant/Contract Number:: AC09-08SR22470

OSTI ID:: 1628976

Journal Information:: Scientific Reports, Journal Name: Scientific Reports Journal Issue: 1 Vol. 10; ISSN 2045-2322

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (54)

Charge Transport in Organic Semiconductors Coropceanu, Veaceslav; Cornil, Jerome; da Silva Filho, Demetrio A. ChemInform, Vol. 38, Issue 29 https://doi.org/10.1002/chin.200729266	journal	July 2007
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
Anomalous room temperature magnetoresistance in organic semiconductors Prigodin, V. N.; Bergeson, J. D.; Lincoln, D. M. Synthetic Metals, Vol. 156, Issue 9-10 https://doi.org/10.1016/j.synthmet.2006.04.010	journal	May 2006
Ruddlesden–Popper Hybrid Lead Iodide Perovskite 2D Homologous Semiconductors Stoumpos, Constantinos C.; Cao, Duyen H.; Clark, Daniel J. Chemistry of Materials, Vol. 28, Issue 8, p. 2852-2867 https://doi.org/10.1021/acs.chemmater.6b00847	journal	April 2016
Exciton and Free Charge Dynamics of Methylammonium Lead Iodide Perovskites Are Different in the Tetragonal and Orthorhombic Phases Wang, He; Whittaker-Brooks, Luisa; Fleming, Graham R. The Journal of Physical Chemistry C, Vol. 119, Issue 34 https://doi.org/10.1021/acs.jpcc.5b04403	journal	August 2015
Estimation of the Rashba Strength from Second Harmonic Generation in 2D and 3D Hybrid Organic–Inorganic Perovskites Yu, Zhi-Gang The Journal of Physical Chemistry C, Vol. 122, Issue 51 https://doi.org/10.1021/acs.jpcc.8b09601	journal	November 2018
Ferroelectricity of CH ₃ NH ₃ PbI ₃ Perovskite Fan, Zhen; Xiao, Juanxiu; Sun, Kuan The Journal of Physical Chemistry Letters, Vol. 6, Issue 7 https://doi.org/10.1021/acs.jpclett.5b00389	journal	March 2015
Dynamical Origin of the Rashba Effect in Organohalide Lead Perovskites: A Key to Suppressed Carrier Recombination in Perovskite Solar Cells? Etienne, Thibaud; Mosconi, Edoardo; De Angelis, Filippo The Journal of Physical Chemistry Letters, Vol. 7, Issue 9 https://doi.org/10.1021/acs.jpclett.6b00564	journal	April 2016
Rashba Spin–Orbit Coupling Enhanced Carrier Lifetime in CH ₃ NH ₃ PbI ₃ Zheng, Fan; Tan, Liang Z.; Liu, Shi Nano Letters, Vol. 15, Issue 12 https://doi.org/10.1021/acs.nanolett.5b01854	journal	November 2015
Perovskites for Solar Thermoelectric Applications: A First Principle Study of CH ₃ NH ₃ AI ₃ (A = Pb and Sn) He, Yuping; Galli, Giulia Chemistry of Materials, Vol. 26, Issue 18 https://doi.org/10.1021/cm5026766	journal	August 2014
Importance of Spin–Orbit Coupling in Hybrid Organic/Inorganic Perovskites for Photovoltaic Applications Even, Jacky; Pedesseau, Laurent; Jancu, Jean-Marc The Journal of Physical Chemistry Letters, Vol. 4, Issue 17 https://doi.org/10.1021/jz401532q	journal	August 2013
Gate control of the electron spin-diffusion length in semiconductor quantum wells Wang, G.; Liu, B. L.; Balocchi, A. Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3372	journal	September 2013
Short-lived charge-transfer excitons in organic photovoltaic cells studied by high-field magneto-photocurrent Devir-Wolfman, Ayeleth H.; Khachatryan, Bagrat; Gautam, Bhoj R. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5529	journal	July 2014
Scaling law for excitons in 2D perovskite quantum wells Blancon, J. -C.; Stier, A. V.; Tsai, H. Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04659-x	journal	June 2018
Carrier tunneling and device characteristics in polymer light‐emitting diodes Parker, I. D. Journal of Applied Physics, Vol. 75, Issue 3 https://doi.org/10.1063/1.356350	journal	February 1994
Large magnetoelectric effect in organic ferroelectric copolymer-based multiferroic tunnel junctions Subedi, Ram Chandra; Geng, Rugang; Luong, Hoang Mai Applied Physics Letters, Vol. 110, Issue 5 https://doi.org/10.1063/1.4974490	journal	January 2017
Oscillatory effects and the magnetic susceptibility of carriers in inversion layers Bychkov, Yu A.; Rashba, E. I. Journal of Physics C: Solid State Physics, Vol. 17, Issue 33 https://doi.org/10.1088/0022-3719/17/33/015	journal	November 1984
Quantum nanostructures in strongly spin-orbit coupled two-dimensional systems Rashba, Emmanuel I. Physical Review B, Vol. 86, Issue 12 https://doi.org/10.1103/physrevb.86.125319	journal	September 2012
Effect of Charge Localization on the Effective Hyperfine Interaction in Organic Semiconducting Polymers Geng, Rugang; Subedi, Ram C.; Luong, Hoang M. Physical Review Letters, Vol. 120, Issue 8 https://doi.org/10.1103/physrevlett.120.086602	journal	February 2018
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
Control of Spin Precession in a Spin-Injected Field Effect Transistor Koo, H. C.; Kwon, J. H.; Eom, J. Science, Vol. 325, Issue 5947 https://doi.org/10.1126/science.1173667	journal	September 2009
Direct Measurement of the Exciton Binding Energy and Effective Masses for Charge carriers in an Organic-Inorganic Tri-halide Perovskite Miyata, Atsuhiko; Mitioglu, Anatolie; Plochocka, Paulina arXiv https://doi.org/10.48550/arxiv.1504.07025	text	January 2015
New Perspectives for Rashba Spin-Orbit Coupling Manchon, A.; Koo, H. C.; Nitta, J. arXiv https://doi.org/10.48550/arxiv.1507.02408	text	January 2015
Magneto-Optical Studies on Spin-Dependent Charge Recombination and Dissociation in Perovskite Solar Cells Hsiao, Yu-Che; Wu, Ting; Li, Mingxing Advanced Materials, Vol. 27, Issue 18 https://doi.org/10.1002/adma.201405946	journal	April 2015
Dielectric study of CH3NH3PbX3 (X = Cl, Br, I) Onoda-Yamamuro, Noriko; Matsuo, Takasuke; Suga, Hiroshi Journal of Physics and Chemistry of Solids, Vol. 53, Issue 7 https://doi.org/10.1016/0022-3697(92)90121-S	journal	July 1992
Perovskite solar cells: an emerging photovoltaic technology Park, Nam-Gyu Materials Today, Vol. 18, Issue 2 https://doi.org/10.1016/j.mattod.2014.07.007	journal	March 2015
Rashba Band Splitting in Organohalide Lead Perovskites: Bulk and Surface Effects Mosconi, Edoardo; Etienne, Thibaud; De Angelis, Filippo The Journal of Physical Chemistry Letters, Vol. 8, Issue 10 https://doi.org/10.1021/acs.jpclett.7b00328	journal	May 2017
Rashba and Dresselhaus Couplings in Halide Perovskites: Accomplishments and Opportunities for Spintronics and Spin–Orbitronics Kepenekian, Mikaël; Even, Jacky The Journal of Physical Chemistry Letters, Vol. 8, Issue 14 https://doi.org/10.1021/acs.jpclett.7b01015	journal	July 2017
Charge-Carrier Mobilities in Metal Halide Perovskites: Fundamental Mechanisms and Limits Herz, Laura M. ACS Energy Letters, Vol. 2, Issue 7 https://doi.org/10.1021/acsenergylett.7b00276	journal	June 2017
Rashba and Dresselhaus Effects in Hybrid Organic–Inorganic Perovskites: From Basics to Devices Kepenekian, Mikaël; Robles, Roberto; Katan, Claudine ACS Nano, Vol. 9, Issue 12 https://doi.org/10.1021/acsnano.5b04409	journal	September 2015
Charge Transport in Organic Semiconductors Coropceanu, Veaceslav; Cornil, Jérôme; da Silva Filho, Demetrio A. Chemical Reviews, Vol. 107, Issue 4 https://doi.org/10.1021/cr050140x	journal	April 2007
Magnetic field effects in hybrid perovskite devices Zhang, C.; Sun, D.; Sheng, C-X. Nature Physics, Vol. 11, Issue 5 https://doi.org/10.1038/Nphys3277	journal	March 2015
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
New perspectives for Rashba spin–orbit coupling Manchon, A.; Koo, H. C.; Nitta, J. Nature Materials, Vol. 14, Issue 9 https://doi.org/10.1038/nmat4360	journal	August 2015
Direct–indirect character of the bandgap in methylammonium lead iodide perovskite Hutter, Eline M.; Gélvez-Rueda, María C.; Osherov, Anna Nature Materials, Vol. 16, Issue 1 https://doi.org/10.1038/nmat4765	journal	October 2016
Electro-optics of perovskite solar cells Lin, Qianqian; Armin, Ardalan; Nagiri, Ravi Chandra Raju Nature Photonics, Vol. 9, Issue 2 https://doi.org/10.1038/nphoton.2014.284	journal	December 2014
Direct measurement of the exciton binding energy and effective masses for charge carriers in organic–inorganic tri-halide perovskites Miyata, Atsuhiko; Mitioglu, Anatolie; Plochocka, Paulina Nature Physics, Vol. 11, Issue 7 https://doi.org/10.1038/nphys3357	journal	June 2015
Highly gate-tuneable Rashba spin-orbit interaction in a gate-all-around InAs nanowire metal-oxide-semiconductor field-effect transistor Takase, K.; Ashikawa, Y.; Zhang, G. Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-01080-0	journal	April 2017
Magnetically tunable organic semiconductors with superparamagnetic nanoparticles Geng, Rugang; Luong, Hoang Mai; Pham, Minh Thien Materials Horizons, Vol. 6, Issue 9 https://doi.org/10.1039/C9MH00265K	journal	January 2019
Research Update: Relativistic origin of slow electron-hole recombination in hybrid halide perovskite solar cells Azarhoosh, Pooya; McKechnie, Scott; Frost, Jarvist M. APL Materials, Vol. 4, Issue 9 https://doi.org/10.1063/1.4955028	journal	September 2016
Large magnetoresistance in nonmagnetic π -conjugated semiconductor thin film devices Mermer, Ö.; Veeraraghavan, G.; Francis, T. L. Physical Review B, Vol. 72, Issue 20 https://doi.org/10.1103/PhysRevB.72.205202	journal	November 2005
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
Effect of spin-orbit coupling on magnetoresistance in organic semiconductors Sheng, Y.; Nguyen, T. D.; Veeraraghavan, G. Physical Review B, Vol. 75, Issue 3 https://doi.org/10.1103/PhysRevB.75.035202	journal	January 2007
Quantum nanostructures in strongly spin-orbit coupled two-dimensional systems Rashba, Emmanuel I. Physical Review B, Vol. 86, Issue 12 https://doi.org/10.1103/PhysRevB.86.125319	journal	September 2012
Traps and trions as origin of magnetoresistance in organic semiconductors Cox, M.; Janssen, P.; Zhu, F. Physical Review B, Vol. 88, Issue 3 https://doi.org/10.1103/PhysRevB.88.035202	journal	July 2013
Giant Rashba Splitting in CH 3 NH 3 PbBr 3 Organic-Inorganic Perovskite Niesner, Daniel; Wilhelm, Max; Levchuk, Ievgen Physical Review Letters, Vol. 117, Issue 12 https://doi.org/10.1103/PhysRevLett.117.126401	journal	September 2016
Effect of Charge Localization on the Effective Hyperfine Interaction in Organic Semiconducting Polymers Geng, Rugang; Subedi, Ram C.; Luong, Hoang M. Physical Review Letters, Vol. 120, Issue 8 https://doi.org/10.1103/PhysRevLett.120.086602	journal	February 2018
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
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
Efficient triplet exciton generation in hybrid perovskites (Conference Presentation) Gundogdu, Kenan Ultrafast Nonlinear Imaging and Spectroscopy V https://doi.org/10.1117/12.2273967	conference	October 2017
Giant Rashba splitting in 2D organic-inorganic halide perovskites measured by transient spectroscopies Zhai, Yaxin; Baniya, Sangita; Zhang, Chuang Science Advances, Vol. 3, Issue 7 https://doi.org/10.1126/sciadv.1700704	journal	July 2017
Electron-hole diffusion lengths > 175 μm in solution-grown CH ₃ NH ₃ PbI ₃ single crystals Dong, Qingfeng; Fang, Yanjun; Shao, Yuchuan Science, Vol. 347, Issue 6225 https://doi.org/10.1126/science.aaa5760	journal	January 2015
Iodide management in formamidinium-lead-halide–based perovskite layers for efficient solar cells Yang, Woon Seok; Park, Byung-Wook; Jung, Eui Hyuk Science, Vol. 356, Issue 6345 https://doi.org/10.1126/science.aan2301	journal	June 2017
Relativistic origin of slow electron-hole recombination in hybrid halide Perovskite solar cells Jarvist M. Frost, Aron Walsh King's College London https://doi.org/10.18742/rdm01-34	collection	January 2016

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