Quantifying Photoinduced Polaronic Distortions in Inorganic Lead Halide Perovskite Nanocrystals
The development of next-generation perovskite-based 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 time-resolved 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 temperature-dependent 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.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2021 |
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| Erschienen: |
2021 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:143 |
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| Enthalten in: |
Journal of the American Chemical Society - 143(2021), 24 vom: 23. Juni, Seite 9048-9059 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Cannelli, Oliviero [VerfasserIn] |
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| Links: |
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| Anmerkungen: |
Date Revised 02.04.2024 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/jacs.1c02403 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| 520 | |a The development of next-generation perovskite-based 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 time-resolved 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 temperature-dependent 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 | ||
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| 700 | 1 | |a Puppin, Michele |e verfasserin |4 aut | |
| 700 | 1 | |a Rossi, Thomas C |e verfasserin |4 aut | |
| 700 | 1 | |a Kinschel, Dominik |e verfasserin |4 aut | |
| 700 | 1 | |a Leroy, Ludmila M D |e verfasserin |4 aut | |
| 700 | 1 | |a Löffler, Janina |e verfasserin |4 aut | |
| 700 | 1 | |a Budarz, James M |e verfasserin |4 aut | |
| 700 | 1 | |a March, Anne Marie |e verfasserin |4 aut | |
| 700 | 1 | |a Doumy, Gilles |e verfasserin |4 aut | |
| 700 | 1 | |a Al Haddad, Andre |e verfasserin |4 aut | |
| 700 | 1 | |a Tu, Ming-Feng |e verfasserin |4 aut | |
| 700 | 1 | |a Kumagai, Yoshiaki |e verfasserin |4 aut | |
| 700 | 1 | |a Walko, Donald |e verfasserin |4 aut | |
| 700 | 1 | |a Smolentsev, Grigory |e verfasserin |4 aut | |
| 700 | 1 | |a Krieg, Franziska |e verfasserin |4 aut | |
| 700 | 1 | |a Boehme, Simon C |e verfasserin |4 aut | |
| 700 | 1 | |a Kovalenko, Maksym V |e verfasserin |4 aut | |
| 700 | 1 | |a Chergui, Majed |e verfasserin |4 aut | |
| 700 | 1 | |a Mancini, Giulia F |e verfasserin |4 aut | |
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