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Title: Excited-state vibrational dynamics toward the polaron in methylammonium lead iodide perovskite

Hybrid organic–inorganic perovskites have attractive optoelectronic properties including exceptional solar cell performance. The improved properties of perovskites have been attributed to polaronic effects involving stabilization of localized charge character by structural deformations and polarizations. Here we examine the Pb–I structural dynamics leading to polaron formation in methylammonium lead iodide perovskite by transient absorption, time-domain Raman spectroscopy, and density functional theory. Methylammonium lead iodide perovskite exhibits excited-state coherent nuclear wave packets oscillating at ~20, ~43, and ~75 cm -1 which involve skeletal bending, in-plane bending, and c-axis stretching of the I–Pb–I bonds, respectively. The amplitudes of these wave packet motions report on the magnitude of the excited-state structural changes, in particular, the formation of a bent and elongated octahedral PbI 6 4- geometry. We have predicted the excited-state geometry and structural changes between the neutral and polaron states using a normal-mode projection method, which supports and rationalizes the experimental results. This study reveals the polaron formation via nuclear dynamics that may be important for efficient charge separation.
Authors:
 [1] ;  [2] ;  [3] ;  [4] ;  [4] ; ORCiD logo [5] ;  [6] ;  [7] ; ORCiD logo [2] ; ORCiD logo [4]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Dong-A Univ., Busan (Korea, Republic of). Dept. of Chemistry
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Andrés Bello National Univ., Santiago (Chile). Dept. of Physical Sciences; Univ. of California, Berkeley, CA (United States). Dept. of Physics; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  4. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
  5. Osram Opto Semiconductors GmbH, Regensburg (Germany)
  6. Univ. of California, Berkeley, CA (United States). Dept. of Physics. Kavli Energy NanoSciences Inst.; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  7. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry. Dept. of Materials Science and Engineering. Kavli Energy NanoSciences Inst.; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Publication Date:
Report Number(s):
LA-UR-17-31256
Journal ID: ISSN 2041-1723
Grant/Contract Number:
AC52-06NA25396; AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); LANL Laboratory Directed Research and Development (LDRD) Program; LBNL Laboratory Directed Research and Development (LDRD) Program
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Material Science
OSTI Identifier:
1459840

Park, Myeongkee, Neukirch, Amanda J., Reyes-Lillo, Sebastian E., Lai, Minliang, Ellis, Scott R., Dietze, Daniel, Neaton, Jeffrey B., Yang, Peidong, Tretiak, Sergei, and Mathies, Richard A.. Excited-state vibrational dynamics toward the polaron in methylammonium lead iodide perovskite. United States: N. p., Web. doi:10.1038/s41467-018-04946-7.
Park, Myeongkee, Neukirch, Amanda J., Reyes-Lillo, Sebastian E., Lai, Minliang, Ellis, Scott R., Dietze, Daniel, Neaton, Jeffrey B., Yang, Peidong, Tretiak, Sergei, & Mathies, Richard A.. Excited-state vibrational dynamics toward the polaron in methylammonium lead iodide perovskite. United States. doi:10.1038/s41467-018-04946-7.
Park, Myeongkee, Neukirch, Amanda J., Reyes-Lillo, Sebastian E., Lai, Minliang, Ellis, Scott R., Dietze, Daniel, Neaton, Jeffrey B., Yang, Peidong, Tretiak, Sergei, and Mathies, Richard A.. 2018. "Excited-state vibrational dynamics toward the polaron in methylammonium lead iodide perovskite". United States. doi:10.1038/s41467-018-04946-7. https://www.osti.gov/servlets/purl/1459840.
@article{osti_1459840,
title = {Excited-state vibrational dynamics toward the polaron in methylammonium lead iodide perovskite},
author = {Park, Myeongkee and Neukirch, Amanda J. and Reyes-Lillo, Sebastian E. and Lai, Minliang and Ellis, Scott R. and Dietze, Daniel and Neaton, Jeffrey B. and Yang, Peidong and Tretiak, Sergei and Mathies, Richard A.},
abstractNote = {Hybrid organic–inorganic perovskites have attractive optoelectronic properties including exceptional solar cell performance. The improved properties of perovskites have been attributed to polaronic effects involving stabilization of localized charge character by structural deformations and polarizations. Here we examine the Pb–I structural dynamics leading to polaron formation in methylammonium lead iodide perovskite by transient absorption, time-domain Raman spectroscopy, and density functional theory. Methylammonium lead iodide perovskite exhibits excited-state coherent nuclear wave packets oscillating at ~20, ~43, and ~75 cm-1 which involve skeletal bending, in-plane bending, and c-axis stretching of the I–Pb–I bonds, respectively. The amplitudes of these wave packet motions report on the magnitude of the excited-state structural changes, in particular, the formation of a bent and elongated octahedral PbI64- geometry. We have predicted the excited-state geometry and structural changes between the neutral and polaron states using a normal-mode projection method, which supports and rationalizes the experimental results. This study reveals the polaron formation via nuclear dynamics that may be important for efficient charge separation.},
doi = {10.1038/s41467-018-04946-7},
journal = {Nature Communications},
number = ,
volume = 9,
place = {United States},
year = {2018},
month = {6}
}