Origin of long lifetime of band-edge charge carriers in organic–inorganic lead iodide perovskites

Chen, Tianran; Chen, Wei-Liang; Foley, Benjamin J.; Lee, Jooseop; Ruff, Jacob P.  C.; Ko, J. Y.  Peter; Brown, Craig M.; Harriger, Leland W.; Zhang, Depei; Park, Changwon; Yoon, Mina; Chang, Yu-Ming; Choi, Joshua J.; Lee, Seung-Hun

doi:10.1073/pnas.1704421114

Title: Origin of long lifetime of band-edge charge carriers in organic–inorganic lead iodide perovskites

Journal Article · 03 July 2017 · Proceedings of the National Academy of Sciences of the United States of America

DOI: https://doi.org/10.1073/pnas.1704421114 · OSTI ID:1498113

Chen, Tianran ^[1]; Chen, Wei-Liang ^[2]; Foley, Benjamin J. ^[3]; Lee, Jooseop ^[4]; Ruff, Jacob P. C. ^[4]; Ko, J. Y. Peter ^[4]; Brown, Craig M. ^[5]; Harriger, Leland W. ^[5]; Zhang, Depei ^[1]; Park, Changwon ^[6]; Yoon, Mina ^[6]; Chang, Yu-Ming ^[2]; Choi, Joshua J. ^[3]; Lee, Seung-Hun ^[1]

Univ. of Virginia, Charlottesville, VA (United States). Dept. of Physics
National Taiwan Univ., Taipei (Taiwan). Center for Condensed Matter Sceinces
Univ. of Virginia, Charlottesville, VA (United States). Dept. of Chemical Engineering
Cornell Univ., Ithaca, NY (United States). Cornell High Energy Synchrotron Source (CHESS)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)

Long carrier lifetime is what makes hybrid organic–inorganic perovskites high-performance photovoltaic materials. Several microscopic mechanisms behind the unusually long carrier lifetime have been proposed, such as formation of large polarons, Rashba effect, ferroelectric domains, and photon recycling. Here, we show that the screening of band-edge charge carriers by rotation of organic cation molecules can be a major contribution to the prolonged carrier lifetime. Our results reveal that the band-edge carrier lifetime increases when the system enters from a phase with lower rotational entropy to another phase with higher entropy. These results imply that the recombination of the photoexcited electrons and holes is suppressed by the screening, leading to the formation of polarons and thereby extending the lifetime. Furthermore, searching for organic–inorganic perovskites with high rotational entropy over a wide range of temperature may be a key to achieve superior solar cell performance.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0016144; AC02-05CH11231

OSTI ID:: 1498113

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Vol. 114, Issue 29; ISSN 0027-8424

Publisher:: National Academy of Sciences, Washington, DC (United States)Copyright Statement

Country of Publication:: United States

Language:: English

References (43)

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
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
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
Molecular ferroelectric contributions to anomalous hysteresis in hybrid perovskite solar cells Frost, Jarvist M.; Butler, Keith T.; Walsh, Aron APL Materials, Vol. 2, Issue 8 https://doi.org/10.1063/1.4890246	journal	August 2014
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
Hybrid organic—inorganic perovskites: low-cost semiconductors with intriguing charge-transport properties Brenner, Thomas M.; Egger, David A.; Kronik, Leeor Nature Reviews Materials, Vol. 1, Issue 1 https://doi.org/10.1038/natrevmats.2015.7	journal	January 2016
Temperature dependent energy levels of methylammonium lead iodide perovskite Foley, Benjamin J.; Marlowe, Daniel L.; Sun, Keye Applied Physics Letters, Vol. 106, Issue 24 https://doi.org/10.1063/1.4922804	journal	June 2015
Local polar fluctuations in lead halide perovskite crystals Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z. arXiv https://doi.org/10.48550/arxiv.1604.08107	text	January 2016
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
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
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
Ferroelectric Domain Wall Induced Band Gap Reduction and Charge Separation in Organometal Halide Perovskites Liu, Shi; Zheng, Fan; Koocher, Nathan Z. The Journal of Physical Chemistry Letters, Vol. 6, Issue 4 https://doi.org/10.1021/jz502666j	journal	February 2015
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
Direct-indirect character of the bandgap in methylammonium lead iodide perovskite. Hutter, Em; Gélvez-Rueda, Mc; Osherov, A. Apollo - University of Cambridge Repository https://doi.org/10.17863/cam.12468	text	January 2017
Direct Observation of Ferroelectric Domains in Solution-Processed CH ₃ NH ₃ PbI ₃ Perovskite Thin Films Kutes, Yasemin; Ye, Linghan; Zhou, Yuanyuan The Journal of Physical Chemistry Letters, Vol. 5, Issue 19 https://doi.org/10.1021/jz501697b	journal	September 2014
High-resolution X-ray luminescence extension imaging Ou, Xiangyu; Qin, Xian; Huang, Bolong Nature, Vol. 590, Issue 7846 https://doi.org/10.1038/s41586-021-03251-6	journal	February 2021
Screening in crystalline liquids protects energetic carriers in hybrid perovskites Zhu, H.; Miyata, K.; Fu, Y. Science, Vol. 353, Issue 6306 https://doi.org/10.1126/science.aaf9570	journal	September 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
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
Entropy-driven structural transition and kinetic trapping in formamidinium lead iodide perovskite Chen, Tianran; Foley, Benjamin J.; Park, Changwon Science Advances, Vol. 2, Issue 10 https://doi.org/10.1126/sciadv.1601650	journal	October 2016
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
Complete structure and cation orientation in the perovskite photovoltaic methylammonium lead iodide between 100 and 352 K Weller, Mark T.; Weber, Oliver J.; Henry, Paul F. Chemical Communications, Vol. 51, Issue 20 https://doi.org/10.1039/C4CC09944C	journal	January 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
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
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
Steric engineering of metal-halide perovskites with tunable optical band gaps Filip, Marina R.; Eperon, Giles E.; Snaith, Henry J. arXiv https://doi.org/10.48550/arxiv.1409.6478	text	January 2014
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
All-Vacuum-Deposited Stoichiometrically Balanced Inorganic Cesium Lead Halide Perovskite Solar Cells with Stabilized Efficiency Exceeding 11% Chen, Chien-Yu; Lin, Hung-Yu; Chiang, Kai-Ming Advanced Materials, Vol. 29, Issue 12 https://doi.org/10.1002/adma.201605290	journal	January 2017
Bandgap-Tunable Cesium Lead Halide Perovskites with High Thermal Stability for Efficient Solar Cells Sutton, Rebecca J.; Eperon, Giles E.; Miranda, Laura Advanced Energy Materials, Vol. 6, Issue 8 https://doi.org/10.1002/aenm.201502458	journal	February 2016
Cesium-containing triple cation perovskite solar cells: improved stability, reproducibility and high efficiency Saliba, Michael; Matsui, Taisuke; Seo, Ji-Youn Energy & Environmental Science, Vol. 9, Issue 6 https://doi.org/10.1039/C5EE03874J	journal	January 2016
Potassium Incorporation for Enhanced Performance and Stability of Fully Inorganic Cesium Lead Halide Perovskite Solar Cells Nam, Jae Keun; Chai, Sung Uk; Cha, Wonhee Nano Letters, Vol. 17, Issue 3 https://doi.org/10.1021/acs.nanolett.7b00050	journal	February 2017
Tetragonal CH ₃ NH ₃ PbI ₃ is ferroelectric Rakita, Yevgeny; Bar-Elli, Omri; Meirzadeh, Elena Proceedings of the National Academy of Sciences, Vol. 114, Issue 28 https://doi.org/10.1073/pnas.1702429114	journal	June 2017
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
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets Chen, Ruyi; Cui, Qirui; Liao, Liyang Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23414-3	journal	May 2021
Photon recycling in lead iodide perovskite solar cells Pazos-Outon, L. M.; Szumilo, M.; Lamboll, R. Science, Vol. 351, Issue 6280 https://doi.org/10.1126/science.aaf1168	journal	March 2016
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
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
Classical Electrodynamics, 3rd ed . Jackson, J. D.; Fox, Ronald F. American Journal of Physics, Vol. 67, Issue 9 https://doi.org/10.1119/1.19136	journal	September 1999
Electron–phonon coupling in hybrid lead halide perovskites Wright, Adam D.; Verdi, Carla; Milot, Rebecca L. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11755	journal	May 2016
Compositional engineering of perovskite materials for high-performance solar cells Jeon, Nam Joong; Noh, Jun Hong; Yang, Woon Seok Nature, Vol. 517, Issue 7535 https://doi.org/10.1038/nature14133	journal	January 2015
Steric engineering of metal-halide perovskites with tunable optical band gaps Filip, Marina R.; Eperon, Giles E.; Snaith, Henry J. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6757	journal	December 2014
Cubic Perovskite Structure of Black Formamidinium Lead Iodide, α-[HC(NH ₂ ) ₂ ]PbI ₃ , at 298 K Weller, Mark T.; Weber, Oliver J.; Frost, Jarvist M. The Journal of Physical Chemistry Letters, Vol. 6, Issue 16 https://doi.org/10.1021/acs.jpclett.5b01432	journal	July 2015
Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 Perovskites for Solar Cell Applications Umari, Paolo; Mosconi, Edoardo; De Angelis, Filippo Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep04467	journal	March 2014

Cited By (20)

Diagrammatic Monte Carlo Approach to Angular Momentum in Quantum Many-Particle Systems Bighin, G.; Tscherbul, T. V.; Lemeshko, M. Physical Review Letters, Vol. 121, Issue 16 https://doi.org/10.1103/physrevlett.121.165301	journal	October 2018
Unraveling exciton-phonon coupling in individual FAPbI(3) nanocrystals emitting near-infrared single photons Fu, Ming; Tamarat, Philippe; Trebbia, Jean-Baptiste ETH Zurich https://doi.org/10.3929/ethz-b-000285895	text	January 2018
Kopplung von hoch- und niederfrequenten Schwingungsmoden in organisch-anorganischen Perowskiten Grechko, Maksim; Bretschneider, Simon A.; Vietze, Laura Angewandte Chemie, Vol. 130, Issue 41 https://doi.org/10.1002/ange.201806676	journal	September 2018
Hybrid light emitting diodes based on stable, high brightness all-inorganic CsPbI ₃ perovskite nanocrystals and InGaN Zhang, Chengxi; Turyanska, Lyudmila; Cao, Haicheng Nanoscale, Vol. 11, Issue 28 https://doi.org/10.1039/c9nr03707a	journal	January 2019
First‐Principles Simulation of Carrier Recombination Mechanisms in Halide Perovskites Zhang, Xie; Shen, Jimmy‐Xuan; Van de Walle, Chris G. Advanced Energy Materials, Vol. 10, Issue 13 https://doi.org/10.1002/aenm.201902830	journal	April 2020
Diagrammatic Monte Carlo approach to angular momentum in quantum many-particle systems Bighin, G.; Tscherbul, T. V.; Lemeshko, M. arXiv https://doi.org/10.48550/arxiv.1803.07990	text	January 2018
Ferroelectric and Piezoelectric Effects on the Optical Process in Advanced Materials and Devices Zhang, Yang; Jie, Wenjing; Chen, Ping Advanced Materials, Vol. 30, Issue 34 https://doi.org/10.1002/adma.201707007	journal	June 2018
Unraveling exciton–phonon coupling in individual FAPbI3 nanocrystals emitting near-infrared single photons Fu, Ming; Tamarat, Philippe; Trebbia, Jean-Baptiste Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05876-0	journal	August 2018
Properties of Excitons and Photogenerated Charge Carriers in Metal Halide Perovskites Jiang, Ying; Wang, Xiao; Pan, Anlian Advanced Materials, Vol. 31, Issue 47 https://doi.org/10.1002/adma.201806671	journal	September 2018
Communicating Two States in Perovskite Revealed by Time-Resolved Photoluminescence Spectroscopy Chen, Yanwen; Wang, Tianmeng; Li, Zhipeng Scientific Reports, Vol. 8, Issue 1 https://doi.org/10.1038/s41598-018-34645-8	journal	November 2018
Halide-Perovskite Resonant Nanophotonics Makarov, Sergey; Furasova, Aleksandra; Tiguntseva, Ekaterina arXiv https://doi.org/10.48550/arxiv.1806.08917	preprint	January 2018
Structural fluctuations cause spin-split states in tetragonal (CH ₃ NH ₃ )PbI ₃ as evidenced by the circular photogalvanic effect Niesner, Daniel; Hauck, Martin; Shrestha, Shreetu Proceedings of the National Academy of Sciences, Vol. 115, Issue 38 https://doi.org/10.1073/pnas.1805422115	journal	September 2018
Catalyst‐Free and Morphology‐Controlled Growth of 2D Perovskite Nanowires for Polarized Light Detection Ghoshal, Debjit; Wang, Tianmeng; Tsai, Hsin‐Zon Advanced Optical Materials, Vol. 7, Issue 15 https://doi.org/10.1002/adom.201900039	journal	May 2019
Crystal structures and rotational dynamics of a two-dimensional metal halide perovskite (OA) ₂ PbI ₄ Hu, Xiao; Zhang, Depei; Chen, Tianran The Journal of Chemical Physics, Vol. 152, Issue 1 https://doi.org/10.1063/1.5131667	journal	January 2020
Halide-Perovskite Resonant Nanophotonics Makarov, Sergey; Furasova, Aleksandra; Tiguntseva, Ekaterina Advanced Optical Materials, Vol. 7, Issue 1 https://doi.org/10.1002/adom.201800784	journal	August 2018
Vibrational Coupling between Organic and Inorganic Sublattices of Hybrid Perovskites Grechko, Maksim; Bretschneider, Simon A.; Vietze, Laura Angewandte Chemie International Edition, Vol. 57, Issue 41 https://doi.org/10.1002/anie.201806676	journal	September 2018
Rationalizing the Molecular Design of Hole‐Selective Contacts to Improve Charge Extraction in Perovskite Solar Cells Wang, Qiong; Mosconi, Edoardo; Wolff, Christian Advanced Energy Materials, Vol. 9, Issue 28 https://doi.org/10.1002/aenm.201900990	journal	June 2019
Communicating Two States in Perovskite Revealed by Time-Resolved Photoluminescence Spectroscopy Chen, Yanwen; Wang, Tianmeng; Li, Zhipeng arXiv https://doi.org/10.48550/arxiv.1811.00704	preprint	January 2018
Spintronics of Hybrid Organic–Inorganic Perovskites: Miraculous Basis of Integrated Optoelectronic Devices Liao, Kun; Hu, Xiaoyong; Cheng, Yinke Advanced Optical Materials, Vol. 7, Issue 15 https://doi.org/10.1002/adom.201900350	journal	June 2019
Real-Time Observation of Order-Disorder Transformation of Organic Cations Induced Phase Transition and Anomalous Photoluminescence in Hybrid Perovskites Yang, Bin; Ming, Wenmei; Du, Mao-Hua Advanced Materials, Vol. 30, Issue 22 https://doi.org/10.1002/adma.201705801	journal	April 2018

Figures / Tables (6)

Similar Records

Organic molecular dynamics and charge-carrier lifetime in lead iodide perovskite MAPbl₃

Journal Article · 2022 · Proceedings of the National Academy of Sciences of the United States of America · OSTI ID:1841315

Koda, Akihiro; Okabe, Hirotaka; Hiraishi, Masatoshi; +4 more

Simultaneous band-gap narrowing and carrier-lifetime prolongation of organic–inorganic trihalide perovskites

Journal Article · 2016 · Proceedings of the National Academy of Sciences of the United States of America · OSTI ID:1296606

Kong, Lingping; Liu, Gang; Gong, Jue; +12 more

Simultaneous band-gap narrowing and carrier-lifetime prolongation of organic–inorganic trihalide perovskites

Journal Article · 2016 · Proceedings of the National Academy of Sciences of the United States of America · OSTI ID:1354526