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

Myeongkee Park, Amanda J. Neukirch, Sebastian E. Reyes-Lillo, Minliang Lai, Scott R. Ellis, Daniel Dietze, Jeffrey B. Neaton, Peidong Yang, Sergei Tretiak, Richard A. Mathies

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38 Citations (Scopus)

Abstract

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 PbI6 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.

Original languageEnglish
Article number2525
JournalNature Communications
Volume9
Issue number1
DOIs
Publication statusPublished - 1 Dec 2018

ASJC Scopus subject areas

  • Chemistry(all)
  • Biochemistry, Genetics and Molecular Biology(all)
  • Physics and Astronomy(all)

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    Park, M., Neukirch, A. J., Reyes-Lillo, S. E., Lai, M., Ellis, S. R., Dietze, D., Neaton, J. B., Yang, P., Tretiak, S., & Mathies, R. A. (2018). Excited-state vibrational dynamics toward the polaron in methylammonium lead iodide perovskite. Nature Communications, 9(1), [2525]. https://doi.org/10.1038/s41467-018-04946-7