Soft Lattice and Defect Covalency Rationalize Tolerance of β‐CsPbI 3 Perovskite Solar Cells to Native Defects

Chu, Weibin; Saidi, Wissam A.; Zhao, Jin; Prezhdo, Oleg V.

doi:10.1002/ange.201915702

Soft Lattice and Defect Covalency Rationalize Tolerance of β‐CsPbI ₃ Perovskite Solar Cells to Native Defects

Journal Article · Tue Feb 18 23:00:00 EST 2020 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.201915702· OSTI ID:1600593

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Departments of Chemistry, and Physics and Astronomy University of Southern California Los Angeles CA 90089 USA
Department of Mechanical Engineering and Materials Science University of Pittsburgh Pittsburgh PA 15261 USA
ICQD/Hefei National Laboratory for Physical Sciences at the Microscale CAS Key Laboratory of Strongly-Coupled Quantum Matter Physics, and Department of Physics University of Science and Technology of China Hefei Anhui 230026 China, Department of Physics and Astronomy University of Pittsburgh Pittsburgh PA 15260 USA, Synergetic Innovation Center of Quantum Information &, Quantum Physics University of Science and Technology of China Hefei Anhui 230026 China

Abstract

Although all‐inorganic metal halide perovskites (MHPs) have shown tremendous improvement, they are still inferior to the hybrid organic–inorganic MHPs in efficiency. Recently, a conceptually new β‐CsPbI ₃ perovskite reached 18.4 % efficiency combined with good thermodynamic stability at ambient conditions. We use ab initio non‐adiabatic molecular dynamics to show that native point defects in β‐CsPbI ₃ are generally benign for nonradiative charge recombination, regardless of whether they introduce shallow or deep trap states. These results indicate that MHPs do not follow the simple models used to explain defect‐mediated charge recombination in the conventional semiconductors. The strong tolerance is due to the softness of the perovskite lattice, which permits separation of electrons and holes upon defect formation, and only allows carriers to couple to the low‐frequency vibrations. Both factors decrease notably the non‐adiabatic coupling and slow down the dissipation of energy to heat.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0014429

OSTI ID:: 1600593

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 16 Vol. 132; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (61)

Unique Properties of Halide Perovskites as Possible Origins of the Superior Solar Cell Performance Yin, Wan-Jian; Shi, Tingting; Yan, Yanfa Advanced Materials, Vol. 26, Issue 27 https://doi.org/10.1002/adma.201306281	journal	May 2014
Predicting the Open-Circuit Voltage of CH ₃ NH ₃ PbI ₃ Perovskite Solar Cells Using Electroluminescence and Photovoltaic Quantum Efficiency Spectra: the Role of Radiative and Non-Radiative Recombination Tress, Wolfgang; Marinova, Nevena; Inganäs, Olle Advanced Energy Materials, Vol. 5, Issue 3 https://doi.org/10.1002/aenm.201400812	journal	September 2014
Intrinsic Thermal Instability of Methylammonium Lead Trihalide Perovskite Conings, Bert; Drijkoningen, Jeroen; Gauquelin, Nicolas Advanced Energy Materials, Vol. 5, Issue 15 https://doi.org/10.1002/aenm.201500477	journal	June 2015
A New Perspective on the Role of A-Site Cations in Perovskite Solar Cells Myung, Chang Woo; Yun, Jeonghun; Lee, Geunsik Advanced Energy Materials, Vol. 8, Issue 14 https://doi.org/10.1002/aenm.201702898	journal	January 2018
Methodologies toward Highly Efficient Perovskite Solar Cells Seok, Sang Il; Grätzel, Michael; Park, Nam-Gyu Small, Vol. 14, Issue 20 https://doi.org/10.1002/smll.201704177	journal	February 2018
Ab initio nonadiabatic molecular dynamics investigations on the excited carriers in condensed matter systems Zheng, Qijing; Chu, Weibin; Zhao, Chuanyu Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 9, Issue 6 https://doi.org/10.1002/wcms.1411	journal	March 2019
General behavior of longitudinal optical phonons in cubic diatomic crystals Baonza, V. G. Solid State Communications, Vol. 130, Issue 6 https://doi.org/10.1016/j.ssc.2004.02.027	journal	May 2004
The Renaissance of Halide Perovskites and Their Evolution as Emerging Semiconductors Stoumpos, Constantinos C.; Kanatzidis, Mercouri G. Accounts of Chemical Research, Vol. 48, Issue 10 https://doi.org/10.1021/acs.accounts.5b00229	journal	September 2015
Structural Stabilities and Electronic Properties of High-Angle Grain Boundaries in Perovskite Cesium Lead Halides Guo, Yaguang; Wang, Qian; Saidi, Wissam A. The Journal of Physical Chemistry C, Vol. 121, Issue 3 https://doi.org/10.1021/acs.jpcc.6b11434	journal	January 2017
Intrinsic Point Defects in Inorganic Cesium Lead Iodide Perovskite CsPbI ₃ Huang, Yang; Yin, Wan-Jian; He, Yao The Journal of Physical Chemistry C, Vol. 122, Issue 2 https://doi.org/10.1021/acs.jpcc.7b10045	journal	January 2018
How Important Is the Organic Part of Lead Halide Perovskite Photovoltaic Cells? Efficient CsPbBr ₃ Cells Kulbak, Michael; Cahen, David; Hodes, Gary The Journal of Physical Chemistry Letters, Vol. 6, Issue 13 https://doi.org/10.1021/acs.jpclett.5b00968	journal	June 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
Cesium Enhances Long-Term Stability of Lead Bromide Perovskite-Based Solar Cells Kulbak, Michael; Gupta, Satyajit; Kedem, Nir The Journal of Physical Chemistry Letters, Vol. 7, Issue 1 https://doi.org/10.1021/acs.jpclett.5b02597	journal	December 2015
High Defect Tolerance in Lead Halide Perovskite CsPbBr ₃ Kang, Jun; Wang, Lin-Wang The Journal of Physical Chemistry Letters, Vol. 8, Issue 2 https://doi.org/10.1021/acs.jpclett.6b02800	journal	January 2017
Segregation of Native Defects to the Grain Boundaries in Methylammonium Lead Iodide Perovskite Shan, Weitao; Saidi, Wissam A. The Journal of Physical Chemistry Letters, Vol. 8, Issue 23 https://doi.org/10.1021/acs.jpclett.7b02727	journal	November 2017
Delocalized Impurity Phonon Induced Electron–Hole Recombination in Doped Semiconductors Zhang, Lili; Zheng, Qijing; Xie, Yu Nano Letters, Vol. 18, Issue 3 https://doi.org/10.1021/acs.nanolett.7b03933	journal	February 2018
Hole Trapping by Iodine Interstitial Defects Decreases Free Carrier Losses in Perovskite Solar Cells: A Time-Domain Ab Initio Study Li, Wei; Liu, Jin; Bai, Fu-Quan ACS Energy Letters, Vol. 2, Issue 6 https://doi.org/10.1021/acsenergylett.7b00183	journal	May 2017
Cubic or Orthorhombic? Revealing the Crystal Structure of Metastable Black-Phase CsPbI ₃ by Theory and Experiment Sutton, Rebecca J.; Filip, Marina R.; Haghighirad, Amir A. ACS Energy Letters, Vol. 3, Issue 8 https://doi.org/10.1021/acsenergylett.8b00672	journal	June 2018
Atomistic Origins of Surface Defects in CH ₃ NH ₃ PbBr ₃ Perovskite and Their Electronic Structures Liu, Yunxia; Palotas, Krisztian; Yuan, Xiao ACS Nano, Vol. 11, Issue 2 https://doi.org/10.1021/acsnano.6b08260	journal	February 2017
Anharmonicity and Disorder in the Black Phases of Cesium Lead Iodide Used for Stable Inorganic Perovskite Solar Cells Marronnier, Arthur; Roma, Guido; Boyer-Richard, Soline ACS Nano, Vol. 12, Issue 4 https://doi.org/10.1021/acsnano.8b00267	journal	March 2018
Surface Defect Dynamics in Organic–Inorganic Hybrid Perovskites: From Mechanism to Interfacial Properties Stecker, Collin; Liu, Kexi; Hieulle, Jeremy ACS Nano, Vol. 13, Issue 10 https://doi.org/10.1021/acsnano.9b06585	journal	September 2019
The PYXAID Program for Non-Adiabatic Molecular Dynamics in Condensed Matter Systems Akimov, Alexey V.; Prezhdo, Oleg V. Journal of Chemical Theory and Computation, Vol. 9, Issue 11 https://doi.org/10.1021/ct400641n	journal	October 2013
Advanced Capabilities of the PYXAID Program: Integration Schemes, Decoherence Effects, Multiexcitonic States, and Field-Matter Interaction Akimov, Alexey V.; Prezhdo, Oleg V. Journal of Chemical Theory and Computation, Vol. 10, Issue 2 https://doi.org/10.1021/ct400934c	journal	January 2014
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
Strong Covalency-Induced Recombination Centers in Perovskite Solar Cell Material CH ₃ NH ₃ PbI ₃ Agiorgousis, Michael L.; Sun, Yi-Yang; Zeng, Hao Journal of the American Chemical Society, Vol. 136, Issue 41 https://doi.org/10.1021/ja5079305	journal	October 2014
Solution-Phase Synthesis of Cesium Lead Halide Perovskite Nanowires Zhang, Dandan; Eaton, Samuel W.; Yu, Yi Journal of the American Chemical Society, Vol. 137, Issue 29 https://doi.org/10.1021/jacs.5b05404	journal	July 2015
Ultrafast Dynamics of Photongenerated Holes at a CH ₃ OH/TiO ₂ Rutile Interface Chu, Weibin; Saidi, Wissam A.; Zheng, Qijing Journal of the American Chemical Society, Vol. 138, Issue 41 https://doi.org/10.1021/jacs.6b08725	journal	October 2016
All-Inorganic Perovskite Solar Cells Liang, Jia; Wang, Caixing; Wang, Yanrong Journal of the American Chemical Society, Vol. 138, Issue 49 https://doi.org/10.1021/jacs.6b10227	journal	November 2016
Thermodynamically Stable Orthorhombic γ-CsPbI ₃ Thin Films for High-Performance Photovoltaics Zhao, Boya; Jin, Shi-Feng; Huang, Sheng Journal of the American Chemical Society, Vol. 140, Issue 37 https://doi.org/10.1021/jacs.8b06050	journal	August 2018
The Role of Intrinsic Defects in Methylammonium Lead Iodide Perovskite Kim, Jongseob; Lee, Sung-Hoon; Lee, Jung Hoon The Journal of Physical Chemistry Letters, Vol. 5, Issue 8 https://doi.org/10.1021/jz500370k	journal	March 2014
The Impact of the Crystallization Processes on the Structural and Optical Properties of Hybrid Perovskite Films for Photovoltaics Grancini, Giulia; Marras, Sergio; Prato, Mirko The Journal of Physical Chemistry Letters, Vol. 5, Issue 21 https://doi.org/10.1021/jz501877h	journal	October 2014
Brief report: The bulk modulus-volume relationship for oxides Anderson, Don L.; Anderson, Orson L. Journal of Geophysical Research, Vol. 75, Issue 17 https://doi.org/10.1029/JB075i017p03494	journal	June 1970
Extended carrier lifetimes and diffusion in hybrid perovskites revealed by Hall effect and photoconductivity measurements Chen, Y.; Yi, H. T.; Wu, X. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12253	journal	August 2016
Acoustic-optical phonon up-conversion and hot-phonon bottleneck in lead-halide perovskites Yang, Jianfeng; Wen, Xiaoming; Xia, Hongze Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14120	journal	January 2017
Overcoming ultraviolet light instability of sensitized TiO2 with meso-superstructured organometal tri-halide perovskite solar cells Leijtens, Tomas; Eperon, Giles E.; Pathak, Sandeep Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3885	journal	December 2013
Defects in perovskite-halides and their effects in solar cells Ball, James M.; Petrozza, Annamaria Nature Energy, Vol. 1, Issue 11 https://doi.org/10.1038/nenergy.2016.149	journal	October 2016
Solvent-controlled growth of inorganic perovskite films in dry environment for efficient and stable solar cells Wang, Pengyang; Zhang, Xingwang; Zhou, Yuqin Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04636-4	journal	June 2018
Ferroelectric large polarons Miyata, Kiyoshi; Zhu, X. -Y. Nature Materials, Vol. 17, Issue 5 https://doi.org/10.1038/s41563-018-0068-7	journal	April 2018
Radiative efficiency of lead iodide based perovskite solar cells Tvingstedt, Kristofer; Malinkiewicz, Olga; Baumann, Andreas Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep06071	journal	August 2014
Thermal degradation of CH ₃ NH ₃ PbI ₃ perovskite into NH ₃ and CH ₃ I gases observed by coupled thermogravimetry–mass spectrometry analysis Juarez-Perez, Emilio J.; Hawash, Zafer; Raga, Sonia R. Energy & Environmental Science, Vol. 9, Issue 11 https://doi.org/10.1039/C6EE02016J	journal	January 2016
Inorganic perovskite solar cells: an emerging member of the photovoltaic community Duan, Jialong; Xu, Hongzhe; Sha, W. E. I. Journal of Materials Chemistry A, Vol. 7, Issue 37 https://doi.org/10.1039/C9TA06674H	journal	January 2019
Decoherence-induced surface hopping Jaeger, Heather M.; Fischer, Sean; Prezhdo, Oleg V. The Journal of Chemical Physics, Vol. 137, Issue 22 https://doi.org/10.1063/1.4757100	journal	December 2012
Unusual defect physics in CH ₃ NH ₃ PbI ₃ perovskite solar cell absorber Yin, Wan-Jian; Shi, Tingting; Yan, Yanfa Applied Physics Letters, Vol. 104, Issue 6 https://doi.org/10.1063/1.4864778	journal	February 2014
Nature of the cubic to tetragonal phase transition in methylammonium lead iodide perovskite Saidi, Wissam A.; Choi, Joshua J. The Journal of Chemical Physics, Vol. 145, Issue 14 https://doi.org/10.1063/1.4964094	journal	October 2016
Pressure-induced phase transformation of CsPbI ₃ by X-ray diffraction and Raman spectroscopy Yuan, Guan; Qin, Shan; Wu, Xiang Phase Transitions, Vol. 91, Issue 1 https://doi.org/10.1080/01411594.2017.1357180	journal	June 2017
Statistics of the Recombinations of Holes and Electrons Shockley, W.; Read, W. T. Physical Review, Vol. 87, Issue 5 https://doi.org/10.1103/PhysRev.87.835	journal	September 1952
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Ab initio molecular dynamics for open-shell transition metals Kresse, G.; Hafner, J. Physical Review B, Vol. 48, Issue 17 https://doi.org/10.1103/PhysRevB.48.13115	journal	November 1993
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Prediction of bulk modulus at high temperatures from longitudinal phonon frequencies: Application to diamond, c − BN , and 3 C − SiC Aguado, F.; Baonza, V. G. Physical Review B, Vol. 73, Issue 2 https://doi.org/10.1103/PhysRevB.73.024111	journal	January 2006
Local Polar Fluctuations in Lead Halide Perovskite Crystals Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z. Physical Review Letters, Vol. 118, Issue 13 https://doi.org/10.1103/PhysRevLett.118.136001	journal	March 2017
Ultrafast THz Probe of Photoinduced Polarons in Lead-Halide Perovskites Cinquanta, Eugenio; Meggiolaro, Daniele; Motti, Silvia G. Physical Review Letters, Vol. 122, Issue 16 https://doi.org/10.1103/PhysRevLett.122.166601	journal	April 2019
Trajectory Surface Hopping in the Time-Dependent Kohn-Sham Approach for Electron-Nuclear Dynamics Craig, Colleen F.; Duncan, Walter R.; Prezhdo, Oleg V. Physical Review Letters, Vol. 95, Issue 16 https://doi.org/10.1103/PhysRevLett.95.163001	journal	October 2005
Large polarons in lead halide perovskites Miyata, Kiyoshi; Meggiolaro, Daniele; Trinh, M. Tuan Science Advances, Vol. 3, Issue 8 https://doi.org/10.1126/sciadv.1701217	journal	August 2017
Low-frequency lattice phonons in halide perovskites explain high defect tolerance toward electron-hole recombination Chu, Weibin; Zheng, Qijing; Prezhdo, Oleg V. Science Advances, Vol. 6, Issue 7 https://doi.org/10.1126/sciadv.aaw7453	journal	February 2020
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
Quantum dot-induced phase stabilization of -CsPbI3 perovskite for high-efficiency photovoltaics Swarnkar, A.; Marshall, A. R.; Sanehira, E. M. Science, Vol. 354, Issue 6308 https://doi.org/10.1126/science.aag2700	journal	October 2016
Thermodynamically stabilized β-CsPbI ₃ –based perovskite solar cells with efficiencies >18% Wang, Yong; Dar, M. Ibrahim; Ono, Luis K. Science, Vol. 365, Issue 6453 https://doi.org/10.1126/science.aav8680	journal	August 2019
Linear Network Model of Gene Regulation for the Yeast Cell Cycle Chang No, Yoon; Seung Kee, Han; Hak Yong, Kim Journal of the Korean Physical Society, Vol. 44, Issue 3 https://doi.org/10.3938/jkps.44.638	journal	March 2004

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