Photoinduced Vibrations Drive Ultrafast Structural Distortion in Lead Halide Perovskite.

Autor: Duan HG; Max Planck Institute for the Structure and Dynamics of Matter, Luruper Chaussee 149, Hamburg 22761, Germany.; I. Institut für Theoretische Physik, Universität Hamburg, Jungiusstrasse 9, Hamburg 20355, Germany.; The Hamburg Center for Ultrafast Imaging, Luruper Chaussee 149, Hamburg 22761, Germany., Tiwari V; Max Planck Institute for the Structure and Dynamics of Matter, Luruper Chaussee 149, Hamburg 22761, Germany.; Department of Chemistry, University of Hamburg, Martin-Luther-King Platz 6, Hamburg 20146, Germany., Jha A; Max Planck Institute for the Structure and Dynamics of Matter, Luruper Chaussee 149, Hamburg 22761, Germany., Berdiyorov GR; Qatar Environment and Energy Research Institute, Qatar Foundation, Hamad Bin Khalifa University, P.O. Box 34110, Doha, Qatar., Akimov A; Department of Chemistry, State University of New York at Buffalo, Buffalo New York 14260, United States., Vendrell O; Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229, Heidelberg 69120, Germany., Nayak PK; Department of Physics, University of Oxford, Clarendon Laboratory, Parks Road, Oxford OX1 3PU, United Kingdom.; TIFR Centre for Interdisciplinary Sciences, Tata Institute of Fundamental Research, Hyderabad 500046, India., Snaith HJ; Department of Physics, University of Oxford, Clarendon Laboratory, Parks Road, Oxford OX1 3PU, United Kingdom., Thorwart M; I. Institut für Theoretische Physik, Universität Hamburg, Jungiusstrasse 9, Hamburg 20355, Germany.; The Hamburg Center for Ultrafast Imaging, Luruper Chaussee 149, Hamburg 22761, Germany., Li Z; Max Planck Institute for the Structure and Dynamics of Matter, Luruper Chaussee 149, Hamburg 22761, Germany.; State Key Laboratory for Mesoscopic Physics, School of Physics, Peking University, Beijing 100871, China., Madjet ME; Qatar Environment and Energy Research Institute, Qatar Foundation, Hamad Bin Khalifa University, P.O. Box 34110, Doha, Qatar., Miller RJD; Max Planck Institute for the Structure and Dynamics of Matter, Luruper Chaussee 149, Hamburg 22761, Germany.; The Hamburg Center for Ultrafast Imaging, Luruper Chaussee 149, Hamburg 22761, Germany.; The Departments of Chemistry and Physics, University of Toronto, 80 Saint George Street, Toronto, Ontario M5S 3H6, Canada.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2020 Sep 30; Vol. 142 (39), pp. 16569-16578. Date of Electronic Publication: 2020 Sep 15.
DOI: 10.1021/jacs.0c03970
Abstrakt: The success of organic-inorganic perovskites in optoelectronics is dictated by the complex interplay between various underlying microscopic phenomena. The structural dynamics of organic cations and the inorganic sublattice after photoexcitation are hypothesized to have a direct effect on the material properties, thereby affecting the overall device performance. Here, we use ultrafast heterodyne-detected two-dimensional (2D) electronic spectroscopy to reveal impulsively excited vibrational modes of methylammonium (MA) lead iodide perovskite, which drive the structural distortion after photoexcitation. Vibrational analysis of the measured data allows us to monitor the time-evolved librational motion of the MA cation along with the vibrational coherences of the inorganic sublattice. Wavelet analysis of the observed vibrational coherences reveals the coherent generation of the librational motion of the MA cation within ∼300 fs complemented with the coherent evolution of the inorganic skeletal motion. To rationalize this observation, we employed the configuration interaction singles (CIS), which support our experimental observations of the coherent generation of librational motions in the MA cation and highlight the importance of the anharmonic interaction between the MA cation and the inorganic sublattice. Moreover, our advanced theoretical calculations predict the transfer of the photoinduced vibrational coherence from the MA cation to the inorganic sublattice, leading to reorganization of the lattice to form a polaronic state with a long lifetime. Our study uncovers the interplay of the organic cation and inorganic sublattice during formation of the polaron, which may lead to novel design principles for the next generation of perovskite solar cell materials.
Databáze: MEDLINE