Quantifying Photoinduced Polaronic Distortions in Inorganic Lead Halide Perovskite Nanocrystals.

Autor: Cannelli O; Laboratory of Ultrafast Spectroscopy (LSU) and Lausanne Centre for Ultrafast Science (LACUS), École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland., Colonna N; 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., Puppin M; Laboratory of Ultrafast Spectroscopy (LSU) and Lausanne Centre for Ultrafast Science (LACUS), École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland., Rossi TC; Laboratory of Ultrafast Spectroscopy (LSU) and Lausanne Centre for Ultrafast Science (LACUS), École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland., Kinschel D; Laboratory of Ultrafast Spectroscopy (LSU) and Lausanne Centre for Ultrafast Science (LACUS), École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland., Leroy LMD; 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., Löffler J; Laboratory of Ultrafast Spectroscopy (LSU) and Lausanne Centre for Ultrafast Science (LACUS), École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland., Budarz JM; Laboratory of Ultrafast Spectroscopy (LSU) and Lausanne Centre for Ultrafast Science (LACUS), École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland., March AM; Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S. Cass Avenue, Lemont, Illinois 60439, United States., Doumy G; Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S. Cass Avenue, Lemont, Illinois 60439, United States., Al Haddad A; Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S. Cass Avenue, Lemont, Illinois 60439, United States., Tu MF; Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S. Cass Avenue, Lemont, Illinois 60439, United States., Kumagai Y; Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S. Cass Avenue, Lemont, Illinois 60439, United States., Walko D; Advanced Photon Source, Argonne National Laboratory, 9700 S. Cass Avenue, Lemont, Illinois 60439, United States., Smolentsev G; Paul Scherrer Institute (PSI), 5232 Villigen, Switzerland., Krieg F; 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., Boehme SC; 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., Kovalenko MV; 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., Chergui M; Laboratory of Ultrafast Spectroscopy (LSU) and Lausanne Centre for Ultrafast Science (LACUS), École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland., Mancini GF; Laboratory of Ultrafast Spectroscopy (LSU) and Lausanne Centre for Ultrafast Science (LACUS), École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2021 Jun 23; Vol. 143 (24), pp. 9048-9059. Date of Electronic Publication: 2021 Jun 02.
DOI: 10.1021/jacs.1c02403
Abstrakt: 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 CsPbBr 3 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 L 3 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 CsPbBr 3 perovskites' photophysics, offering novel insights on the light-induced response of the system and its exceptional optoelectronic properties.
Databáze: MEDLINE
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