The Nature of Electron Mobility in Hybrid Perovskite CH3NH3PbI3

Ma, Jie; Wang, Lin-Wang

doi:10.1021/acs.nanolett.7b00832

The Nature of Electron Mobility in Hybrid Perovskite CH₃NH₃PbI₃

Journal Article · Tue May 23 00:00:00 EDT 2017 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.7b00832· OSTI ID:1476502

^[1]; Wang, Lin-Wang ^[2]

Beijing Inst. of Technology (China). School of Physics and Advanced Research Inst. for Multidisciplinary Science; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis and Chemical Sciences Div.; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Div.
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis and Chemical Sciences Div.; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Div.

The peroskovite CH₃NH₃PbI₃ one of the most promising candidates for cheap and high-efficiency solar cells. One of its unique features is the long carrier diffusion length (>100 μm), but its carrier mobility is rather modest. The nature of the mobility is unclear. Here, using nonadiabatic wave function dynamics simulations, we show that the random rotations of the CH₃NH₃cations play an important role in the carrier mobility. Our previous work showed that the electron and hole wave functions were localized and spatially separated due to the random orientations of the CH₃NH₃ cations in the tetragonal phase. We find that the localized carriers are able to conduct random walks due to the electrostatic potential fluctuation caused by the CH₃NH₃ random rotations. The calculated electron mobilities are in the experimentally measured range. We thus conclude that the carrier mobility of CH₃NH₃PbI₃ is likely driven by the dynamic disorder that causes the fluctuation of the electrostatic potential.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences & Biosciences Division (SC-22.1)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1476502

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 6 Vol. 17; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

Temperature-Dependent Charge-Carrier Dynamics in CH ₃ NH ₃ PbI ₃ Perovskite Thin Films Milot, Rebecca L.; Eperon, Giles E.; Snaith, Henry J. Advanced Functional Materials, Vol. 25, Issue 39 https://doi.org/10.1002/adfm.201502340	journal	September 2015
High Charge Carrier Mobilities and Lifetimes in Organolead Trihalide Perovskites Wehrenfennig, Christian; Eperon, Giles E.; Johnston, Michael B. Advanced Materials, Vol. 26, Issue 10 https://doi.org/10.1002/adma.201305172	journal	December 2013
Intrinsic Charge Transport across Phase Transitions in Hybrid Organo-Inorganic Perovskites Yi, Hee Taek; Wu, Xiaoxi; Zhu, Xiaoyang Advanced Materials, Vol. 28, Issue 30 https://doi.org/10.1002/adma.201600011	journal	May 2016
Organic Cations Might Not Be Essential to the Remarkable Properties of Band Edge Carriers in Lead Halide Perovskites Zhu, Haiming; Trinh, M. Tuan; Wang, Jue Advanced Materials, Vol. 29, Issue 1 https://doi.org/10.1002/adma.201603072	journal	October 2016
Self-Regulation Mechanism for Charged Point Defects in Hybrid Halide Perovskites Walsh, Aron; Scanlon, David O.; Chen, Shiyou Angewandte Chemie International Edition, Vol. 54, Issue 6 https://doi.org/10.1002/anie.201409740	journal	December 2014
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
Hybrid Organic–Inorganic Perovskites on the Move Egger, David A.; Rappe, Andrew M.; Kronik, Leeor Accounts of Chemical Research, Vol. 49, Issue 3 https://doi.org/10.1021/acs.accounts.5b00540	journal	February 2016
Methylammonium Rotational Dynamics in Lead Halide Perovskite by Classical Molecular Dynamics: The Role of Temperature Mattoni, A.; Filippetti, A.; Saba, M. I. The Journal of Physical Chemistry C, Vol. 119, Issue 30 https://doi.org/10.1021/acs.jpcc.5b04283	journal	July 2015
Ferroelastic Fingerprints in Methylammonium Lead Iodide Perovskite Hermes, Ilka M.; Bretschneider, Simon A.; Bergmann, Victor W. The Journal of Physical Chemistry C, Vol. 120, Issue 10 https://doi.org/10.1021/acs.jpcc.5b11469	journal	January 2016
Modeling of Thermal Effect on the Electronic Properties of Photovoltaic Perovskite CH₃NH₃PbI₃: The Case of Tetragonal Phase Montero-Alejo, Ana L.; Menéndez-Proupin, E.; Hidalgo-Rojas, D. The Journal of Physical Chemistry C, Vol. 120, Issue 15 https://doi.org/10.1021/acs.jpcc.6b01013	journal	April 2016
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
Real-Time Observation of Organic Cation Reorientation in Methylammonium Lead Iodide Perovskites Bakulin, Artem A.; Selig, Oleg; Bakker, Huib J. The Journal of Physical Chemistry Letters, Vol. 6, Issue 18 https://doi.org/10.1021/acs.jpclett.5b01555	journal	August 2015
Are Mobilities in Hybrid Organic–Inorganic Halide Perovskites Actually “High”? Brenner, Thomas M.; Egger, David A.; Rappe, Andrew M. The Journal of Physical Chemistry Letters, Vol. 6, Issue 23 https://doi.org/10.1021/acs.jpclett.5b02390	journal	November 2015
Charge Carriers in Hybrid Organic–Inorganic Lead Halide Perovskites Might Be Protected as Large Polarons Zhu, X. -Y.; Podzorov, V. The Journal of Physical Chemistry Letters, Vol. 6, Issue 23 https://doi.org/10.1021/acs.jpclett.5b02462	journal	November 2015
Phonon–Electron Scattering Limits Free Charge Mobility in Methylammonium Lead Iodide Perovskites Karakus, Melike; Jensen, Søren A.; D’Angelo, Francesco The Journal of Physical Chemistry Letters, Vol. 6, Issue 24 https://doi.org/10.1021/acs.jpclett.5b02485	journal	December 2015
Terahertz Conductivity within Colloidal CsPbBr ₃ Perovskite Nanocrystals: Remarkably High Carrier Mobilities and Large Diffusion Lengths Yettapu, Gurivi Reddy; Talukdar, Debnath; Sarkar, Sohini Nano Letters, Vol. 16, Issue 8 https://doi.org/10.1021/acs.nanolett.6b01168	journal	July 2016
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
Interplay of Orientational Order and Electronic Structure in Methylammonium Lead Iodide: Implications for Solar Cell Operation Quarti, Claudio; Mosconi, Edoardo; De Angelis, Filippo Chemistry of Materials, Vol. 26, Issue 22 https://doi.org/10.1021/cm5032046	journal	November 2014
Study of Local Structure in Selected Organic–Inorganic Perovskites in the Pm 3̅ m Phase Worhatch, Richard J.; Kim, HyunJeong; Swainson, Ian P. Chemistry of Materials, Vol. 20, Issue 4 https://doi.org/10.1021/cm702668d	journal	February 2008
Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties Stoumpos, Constantinos C.; Malliakas, Christos D.; Kanatzidis, Mercouri G. Inorganic Chemistry, Vol. 52, Issue 15, p. 9019-9038 https://doi.org/10.1021/ic401215x	journal	July 2013
CsSnI₃ : Semiconductor or Metal? High Electrical Conductivity and Strong Near-Infrared Photoluminescence from a Single Material. High Hole Mobility and Phase-Transitions Chung, In; Song, Jung-Hwan; Im, Jino Journal of the American Chemical Society, Vol. 134, Issue 20, p. 8579-8587 https://doi.org/10.1021/ja301539s	journal	May 2012
Organometal Halide Perovskite Solar Cell Materials Rationalized: Ultrafast Charge Generation, High and Microsecond-Long Balanced Mobilities, and Slow Recombination Ponseca, Carlito S.; Savenije, Tom J.; Abdellah, Mohamed Journal of the American Chemical Society, Vol. 136, Issue 14 https://doi.org/10.1021/ja412583t	journal	February 2014
Improved Understanding of the Electronic and Energetic Landscapes of Perovskite Solar Cells: High Local Charge Carrier Mobility, Reduced Recombination, and Extremely Shallow Traps Oga, Hikaru; Saeki, Akinori; Ogomi, Yuhei Journal of the American Chemical Society, Vol. 136, Issue 39 https://doi.org/10.1021/ja506936f	journal	September 2014
Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells Kojima, Akihiro; Teshima, Kenjiro; Shirai, Yasuo Journal of the American Chemical Society, Vol. 131, Issue 17, p. 6050-6051 https://doi.org/10.1021/ja809598r	journal	May 2009
First-Principles Modeling of Mixed Halide Organometal Perovskites for Photovoltaic Applications Mosconi, Edoardo; Amat, Anna; Nazeeruddin, Md. K. The Journal of Physical Chemistry C, Vol. 117, Issue 27 https://doi.org/10.1021/jp4048659	journal	July 2013
Thermal Effects on CH ₃ NH ₃ PbI ₃ Perovskite from Ab Initio Molecular Dynamics Simulations Carignano, Marcelo A.; Kachmar, Ali; Hutter, Jürg The Journal of Physical Chemistry C, Vol. 119, Issue 17 https://doi.org/10.1021/jp510568n	journal	March 2015
Solid-State Mesostructured Perovskite CH ₃ NH ₃ PbI ₃ Solar Cells: Charge Transport, Recombination, and Diffusion Length Zhao, Yixin; Nardes, Alexandre M.; Zhu, Kai The Journal of Physical Chemistry Letters, Vol. 5, Issue 3 https://doi.org/10.1021/jz500003v	journal	January 2014
Thermally Activated Exciton Dissociation and Recombination Control the Carrier Dynamics in Organometal Halide Perovskite Savenije, Tom J.; Ponseca, Carlito S.; Kunneman, Lucas The Journal of Physical Chemistry Letters, Vol. 5, Issue 13 https://doi.org/10.1021/jz500858a	journal	June 2014
Rotation of Methyl Side Groups in Polymers: A Fourier Transform Approach to Quasielastic Neutron Scattering. 1. Homopolymers Arrighi, V.; Higgins, J. S.; Burgess, A. N. Macromolecules, Vol. 28, Issue 8 https://doi.org/10.1021/ma00112a021	journal	April 1995
Atomistic Origins of High-Performance in Hybrid Halide Perovskite Solar Cells Frost, Jarvist M.; Butler, Keith T.; Brivio, Federico Nano Letters, Vol. 14, Issue 5 https://doi.org/10.1021/nl500390f	journal	April 2014
Controllable Self-Induced Passivation of Hybrid Lead Iodide Perovskites toward High Performance Solar Cells Chen, Qi; Zhou, Huanping; Song, Tze-Bin Nano Letters, Vol. 14, Issue 7 https://doi.org/10.1021/nl501838y	journal	June 2014
Nanoscale Charge Localization Induced by Random Orientations of Organic Molecules in Hybrid Perovskite CH ₃ NH ₃ PbI ₃ Ma, Jie; Wang, Lin-Wang Nano Letters, Vol. 15, Issue 1 https://doi.org/10.1021/nl503494y	journal	December 2014
Sequential deposition as a route to high-performance perovskite-sensitized solar cells Burschka, Julian; Pellet, Norman; Moon, Soo-Jin Nature, Vol. 499, Issue 7458, p. 316-319 https://doi.org/10.1038/nature12340	journal	July 2013
Efficient planar heterojunction perovskite solar cells by vapour deposition Liu, Mingzhen; Johnston, Michael B.; Snaith, Henry J. Nature, Vol. 501, Issue 7467, p. 395-398 https://doi.org/10.1038/nature12509	journal	September 2013
Revealing the role of organic cations in hybrid halide perovskite CH3NH3PbI3 Motta, Carlo; El-Mellouhi, Fedwa; Kais, Sabre Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8026	journal	April 2015
The dynamics of methylammonium ions in hybrid organic–inorganic perovskite solar cells Leguy, Aurelien M. A.; Frost, Jarvist Moore; McMahon, Andrew P. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8124	journal	May 2015
Perovskite solar cells with a planar heterojunction structure prepared using room-temperature solution processing techniques Liu, Dianyi; Kelly, Timothy L. Nature Photonics, Vol. 8, Issue 2, p. 133-138 https://doi.org/10.1038/nphoton.2013.342	journal	December 2013
Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9% Kim, Hui-Seon; Lee, Chang-Ryul; Im, Jeong-Hyeok Scientific Reports, Vol. 2, Issue 1 https://doi.org/10.1038/srep00591	journal	August 2012
Intrinsic and Extrinsic Charge Transport in CH3NH3PbI3 Perovskites Predicted from First-Principles Zhao, Tianqi; Shi, Wen; Xi, Jinyang Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep19968	journal	January 2016
Structural and electronic properties of organo-halide lead perovskites: a combined IR-spectroscopy and ab initio molecular dynamics investigation Mosconi, Edoardo; Quarti, Claudio; Ivanovska, Tanja Phys. Chem. Chem. Phys., Vol. 16, Issue 30 https://doi.org/10.1039/C4CP00569D	journal	January 2014
High intrinsic carrier mobility and photon absorption in the perovskite CH ₃ NH ₃ PbI ₃ Wang, Youwei; Zhang, Yubo; Zhang, Peihong Physical Chemistry Chemical Physics, Vol. 17, Issue 17 https://doi.org/10.1039/C5CP00448A	journal	January 2015
Structural and electronic properties of organo-halide hybrid perovskites from ab initio molecular dynamics Quarti, Claudio; Mosconi, Edoardo; De Angelis, Filippo Physical Chemistry Chemical Physics, Vol. 17, Issue 14 https://doi.org/10.1039/C5CP00599J	journal	January 2015
Rotational dynamics of organic cations in the CH ₃ NH ₃ PbI ₃ perovskite Chen, Tianran; Foley, Benjamin J.; Ipek, Bahar Physical Chemistry Chemical Physics, Vol. 17, Issue 46 https://doi.org/10.1039/C5CP05348J	journal	January 2015
6.5% efficient perovskite quantum-dot-sensitized solar cell Im, Jeong-Hyeok; Lee, Chang-Ryul; Lee, Jin-Wook Nanoscale, Vol. 3, Issue 10, p. 4088-4093 https://doi.org/10.1039/c1nr10867k	journal	January 2011
Low-temperature processed meso-superstructured to thin-film perovskite solar cells Ball, James M.; Lee, Michael M.; Hey, Andrew Energy & Environmental Science, Vol. 6, Issue 6 https://doi.org/10.1039/c3ee40810h	journal	January 2013
Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3)PbI3 for solid-state sensitised solar cell applications Baikie, Tom; Fang, Yanan; Kadro, Jeannette M. Journal of Materials Chemistry A, Vol. 1, Issue 18 https://doi.org/10.1039/c3ta10518k	journal	January 2013
Dynamic disorder in methylammoniumtrihalogenoplumbates (II) observed by millimeter‐wave spectroscopy Poglitsch, A.; Weber, D. The Journal of Chemical Physics, Vol. 87, Issue 11, p. 6373-6378 https://doi.org/10.1063/1.453467	journal	December 1987
A simple approach to the Landau–Zener formula Vutha, Amar C. European Journal of Physics, Vol. 31, Issue 2 https://doi.org/10.1088/0143-0807/31/2/016	journal	February 2010
Energetics and dynamics in organic–inorganic halide perovskite photovoltaics and light emitters Sum, Tze Chien; Chen, Shi; Xing, Guichuan Nanotechnology, Vol. 26, Issue 34 https://doi.org/10.1088/0957-4484/26/34/342001	journal	August 2015
Nonadiabatic molecular dynamics simulation for carrier transport in a pentathiophene butyric acid monolayer Ren, Junfeng; Vukmirović, Nenad; Wang, Lin-Wang Physical Review B, Vol. 87, Issue 20 https://doi.org/10.1103/PhysRevB.87.205117	journal	May 2013
Hybrid perovskites for photovoltaics: Insights from first principles Filippetti, A.; Mattoni, A. Physical Review B, Vol. 89, Issue 12 https://doi.org/10.1103/PhysRevB.89.125203	journal	March 2014
Charge-Transport Regime of Crystalline Organic Semiconductors: Diffusion Limited by Thermal Off-Diagonal Electronic Disorder Troisi, Alessandro; Orlandi, Giorgio Physical Review Letters, Vol. 96, Issue 8 https://doi.org/10.1103/PhysRevLett.96.086601	journal	March 2006
Electron transfer reactions in chemistry. Theory and experiment Marcus, Rudolph A. Reviews of Modern Physics, Vol. 65, Issue 3, p. 599-610 https://doi.org/10.1103/RevModPhys.65.599	journal	July 1993
Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites Lee, M. M.; Teuscher, J.; Miyasaka, T. Science, Vol. 338, Issue 6107, p. 643-647 https://doi.org/10.1126/science.1228604	journal	October 2012
Long-Range Balanced Electron- and Hole-Transport Lengths in Organic-Inorganic CH₃NH₃PbI₃ Xing, G.; Mathews, N.; Sun, S. Science, Vol. 342, Issue 6156, p. 344-347 https://doi.org/10.1126/science.1243167	journal	October 2013
Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber Stranks, S. D.; Eperon, G. E.; Grancini, G. Science, Vol. 342, Issue 6156, p. 341-344 https://doi.org/10.1126/science.1243982	journal	October 2013
Interface engineering of highly efficient perovskite solar cells Zhou, H.; Chen, Q.; Li, G. Science, Vol. 345, Issue 6196 https://doi.org/10.1126/science.1254050	journal	July 2014
A hole-conductor-free, fully printable mesoscopic perovskite solar cell with high stability Mei, A.; Li, X.; Liu, L. Science, Vol. 345, Issue 6194, p. 295-298 https://doi.org/10.1126/science.1254763	journal	July 2014
Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals Shi, D.; Adinolfi, V.; Comin, R. Science, Vol. 347, Issue 6221 https://doi.org/10.1126/science.aaa2725	journal	January 2015
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
High-performance photovoltaic perovskite layers fabricated through intramolecular exchange Yang, W. S.; Noh, J. H.; Jeon, N. J. Science, Vol. 348, Issue 6240 https://doi.org/10.1126/science.aaa9272	journal	May 2015
Electrostatic gating of hybrid halide perovskite field-effect transistors: balanced ambipolar transport at room-temperature Mei, Y.; Zhang, C.; Vardeny, Z. V. MRS Communications, Vol. 5, Issue 2 https://doi.org/10.1557/mrc.2015.21	journal	May 2015

Cited By (2)

Vapour-Deposited Cesium Lead Iodide Perovskites: Microsecond Charge Carrier Lifetimes and Enhanced Photovoltaic Performance Hutter, Eline M.; Sutton, Rebecca J.; Chandrashekar, Sanjana ACS Energy Letters, Vol. 2, Issue 8 https://doi.org/10.1021/acsenergylett.7b00591	journal	August 2017
Impact of electron-phonon scattering on optical properties of CH$_3$NH$_3$PbI$_3$ hybrid perovskite material Galvani, Benoit; Suchet, Daniel; Delamarre, Amaury arXiv https://doi.org/10.48550/arxiv.1909.08455	preprint	January 2019

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