Quantifying Photoinduced Polaronic Distortions in Inorganic Lead Halide Perovskite Nanocrystals
Abstract
The development of next-generation perovskitebased optoelectronic devices relies critically on the understanding of the interaction between charge carriers and the polar lattice in out-of-equilibrium conditions. While it has become increasingly evident for CsPbBr3 perovskites that the Pb–Br framework flexibility plays a key role in their light-activated functionality, the corresponding local structural rearrangement has not yet been unambiguously identified. In this work, we demonstrate that the photoinduced lattice changes in the system are due to a specific polaronic distortion, associated with the activation of a longitudinal optical phonon mode at 18 meV by electron–phonon coupling, and we quantify the associated structural changes with atomic-level precision. Key to this achievement is the combination of timeresolved and temperature-dependent studies at Br K and Pb L3 X-ray absorption edges with refined ab initio simulations, which fully account for the screened core-hole final state effects on the X-ray absorption spectra. From the temporal kinetics, we show that carrier recombination reversibly unlocks the structural deformation at both Br and Pb sites. The comparison with the temperaturedependent XAS results rules out thermal effects as the primary source of distortion of the Pb–Br bonding motif during photoexcitation. Our work provides a comprehensive description of the CsPbBr3 perovskites’ photophysics,more »
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[3];
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- Laboratory of Ultrafast Spectroscopy (LSU) and Lausanne Centre for Ultrafast Science (LACUS), École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland
- Laboratory for Neutron Scattering and Imaging, Paul Scherrer Institute, CH-5232 Villigen-PSI, Switzerland, National Centre for Computational Design and Discovery of Novel Materials (MARVEL), École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland
- Laboratory of Ultrafast Spectroscopy (LSU) and Lausanne Centre for Ultrafast Science (LACUS), École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland, LabCri, Universidade Federal de Minas Gerais, 31270-901 Belo Horizonte, Brazil
- Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S. Cass Avenue, Lemont, Illinois 60439, United States
- Advanced Photon Source, Argonne National Laboratory, 9700 S. Cass Avenue, Lemont, Illinois 60439, United States
- Paul Scherrer Institute (PSI), 5232 Villigen, Switzerland
- Institute of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir Prelog Weg 1, CH-8093 Zürich, Switzerland, Laboratory for Thin Films and Photovoltaics, Empa-Swiss Federal Laboratories for Materials Science and Technology, CH-8600 Dübendorf, Switzerland
- Publication Date:
- Research Org.:
- Univ. of Pavia (Italy); Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
- OSTI Identifier:
- 1785609
- Alternate Identifier(s):
- OSTI ID: 1798295; OSTI ID: 1831738
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Published Article
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Name: Journal of the American Chemical Society Journal Volume: 143 Journal Issue: 24; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Phonons; Lattices; Energy; Electrical conductivity; Perovskites
Citation Formats
Cannelli, Oliviero, Colonna, Nicola, Puppin, Michele, Rossi, Thomas C., Kinschel, Dominik, Leroy, Ludmila M. D., Löffler, Janina, Budarz, James M., March, Anne Marie, Doumy, Gilles, Al Haddad, Andre, Tu, Ming-Feng, Kumagai, Yoshiaki, Walko, Donald, Smolentsev, Grigory, Krieg, Franziska, Boehme, Simon C., Kovalenko, Maksym V., Chergui, Majed, and Mancini, Giulia F. Quantifying Photoinduced Polaronic Distortions in Inorganic Lead Halide Perovskite Nanocrystals. United States: N. p., 2021.
Web. doi:10.1021/jacs.1c02403.
Cannelli, Oliviero, Colonna, Nicola, Puppin, Michele, Rossi, Thomas C., Kinschel, Dominik, Leroy, Ludmila M. D., Löffler, Janina, Budarz, James M., March, Anne Marie, Doumy, Gilles, Al Haddad, Andre, Tu, Ming-Feng, Kumagai, Yoshiaki, Walko, Donald, Smolentsev, Grigory, Krieg, Franziska, Boehme, Simon C., Kovalenko, Maksym V., Chergui, Majed, & Mancini, Giulia F. Quantifying Photoinduced Polaronic Distortions in Inorganic Lead Halide Perovskite Nanocrystals. United States. https://doi.org/10.1021/jacs.1c02403
Cannelli, Oliviero, Colonna, Nicola, Puppin, Michele, Rossi, Thomas C., Kinschel, Dominik, Leroy, Ludmila M. D., Löffler, Janina, Budarz, James M., March, Anne Marie, Doumy, Gilles, Al Haddad, Andre, Tu, Ming-Feng, Kumagai, Yoshiaki, Walko, Donald, Smolentsev, Grigory, Krieg, Franziska, Boehme, Simon C., Kovalenko, Maksym V., Chergui, Majed, and Mancini, Giulia F. Wed .
"Quantifying Photoinduced Polaronic Distortions in Inorganic Lead Halide Perovskite Nanocrystals". United States. https://doi.org/10.1021/jacs.1c02403.
@article{osti_1785609,
title = {Quantifying Photoinduced Polaronic Distortions in Inorganic Lead Halide Perovskite Nanocrystals},
author = {Cannelli, Oliviero and Colonna, Nicola and Puppin, Michele and Rossi, Thomas C. and Kinschel, Dominik and Leroy, Ludmila M. D. and Löffler, Janina and Budarz, James M. and March, Anne Marie and Doumy, Gilles and Al Haddad, Andre and Tu, Ming-Feng and Kumagai, Yoshiaki and Walko, Donald and Smolentsev, Grigory and Krieg, Franziska and Boehme, Simon C. and Kovalenko, Maksym V. and Chergui, Majed and Mancini, Giulia F.},
abstractNote = {The development of next-generation perovskitebased optoelectronic devices relies critically on the understanding of the interaction between charge carriers and the polar lattice in out-of-equilibrium conditions. While it has become increasingly evident for CsPbBr3 perovskites that the Pb–Br framework flexibility plays a key role in their light-activated functionality, the corresponding local structural rearrangement has not yet been unambiguously identified. In this work, we demonstrate that the photoinduced lattice changes in the system are due to a specific polaronic distortion, associated with the activation of a longitudinal optical phonon mode at 18 meV by electron–phonon coupling, and we quantify the associated structural changes with atomic-level precision. Key to this achievement is the combination of timeresolved and temperature-dependent studies at Br K and Pb L3 X-ray absorption edges with refined ab initio simulations, which fully account for the screened core-hole final state effects on the X-ray absorption spectra. From the temporal kinetics, we show that carrier recombination reversibly unlocks the structural deformation at both Br and Pb sites. The comparison with the temperaturedependent XAS results rules out thermal effects as the primary source of distortion of the Pb–Br bonding motif during photoexcitation. Our work provides a comprehensive description of the CsPbBr3 perovskites’ photophysics, offering novel insights on the light-induced response of the system and its exceptional optoelectronic properties.},
doi = {10.1021/jacs.1c02403},
journal = {Journal of the American Chemical Society},
number = 24,
volume = 143,
place = {United States},
year = {Wed Jun 02 00:00:00 EDT 2021},
month = {Wed Jun 02 00:00:00 EDT 2021}
}
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