Real-Time Observation of Organic Cation Reorientation in Methylammonium Lead Iodide Perovskites

Artem A. Bakulin, Oleg Selig, Huib J. Bakker, Yves L.A. Rezus, Christian Müller, Tobias Glaser, Robert Lovrincic, Zhenhua Sun, Zhuoying Chen, Aron Walsh, Jarvist M. Frost, Thomas L.C. Jansen

Research output: Contribution to journalArticle

196 Citations (Scopus)

Abstract

The introduction of a mobile and polarized organic moiety as a cation in 3D lead-iodide perovskites brings fascinating optoelectronic properties to these materials. The extent and the time scales of the orientational mobility of the organic cation and the molecular mechanism behind its motion remain unclear, with different experimental and computational approaches providing very different qualitative and quantitative description of the molecular dynamics. Here we use ultrafast 2D vibrational spectroscopy of methylammonium (MA) lead iodide to directly resolve the rotation of the organic cations within the MAPbI3 lattice. Our results reveal two characteristic time constants of motion. Using ab initio molecular dynamics simulations, we identify these as a fast (∼300 fs) "wobbling-in-a-cone" motion around the crystal axis and a relatively slow (∼3 ps) jump-like reorientation of the molecular dipole with respect to the iodide lattice. The observed dynamics are essential for understanding the electronic properties of perovskite materials.

Original languageEnglish
Pages (from-to)3663-3669
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume6
Issue number18
DOIs
Publication statusPublished - 2015 Sep 2

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Iodides
perovskites
iodides
retraining
Cations
Lead
Positive ions
cations
Molecular dynamics
molecular dynamics
Vibrational spectroscopy
Electronic properties
Optoelectronic devices
Perovskite
time constant
Cones
cones
dipoles
Crystals
Computer simulation

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Physical and Theoretical Chemistry

Cite this

Bakulin, A. A., Selig, O., Bakker, H. J., Rezus, Y. L. A., Müller, C., Glaser, T., ... Jansen, T. L. C. (2015). Real-Time Observation of Organic Cation Reorientation in Methylammonium Lead Iodide Perovskites. Journal of Physical Chemistry Letters, 6(18), 3663-3669. https://doi.org/10.1021/acs.jpclett.5b01555
Bakulin, Artem A. ; Selig, Oleg ; Bakker, Huib J. ; Rezus, Yves L.A. ; Müller, Christian ; Glaser, Tobias ; Lovrincic, Robert ; Sun, Zhenhua ; Chen, Zhuoying ; Walsh, Aron ; Frost, Jarvist M. ; Jansen, Thomas L.C. / Real-Time Observation of Organic Cation Reorientation in Methylammonium Lead Iodide Perovskites. In: Journal of Physical Chemistry Letters. 2015 ; Vol. 6, No. 18. pp. 3663-3669.
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Bakulin, AA, Selig, O, Bakker, HJ, Rezus, YLA, Müller, C, Glaser, T, Lovrincic, R, Sun, Z, Chen, Z, Walsh, A, Frost, JM & Jansen, TLC 2015, 'Real-Time Observation of Organic Cation Reorientation in Methylammonium Lead Iodide Perovskites', Journal of Physical Chemistry Letters, vol. 6, no. 18, pp. 3663-3669. https://doi.org/10.1021/acs.jpclett.5b01555

Real-Time Observation of Organic Cation Reorientation in Methylammonium Lead Iodide Perovskites. / Bakulin, Artem A.; Selig, Oleg; Bakker, Huib J.; Rezus, Yves L.A.; Müller, Christian; Glaser, Tobias; Lovrincic, Robert; Sun, Zhenhua; Chen, Zhuoying; Walsh, Aron; Frost, Jarvist M.; Jansen, Thomas L.C.

In: Journal of Physical Chemistry Letters, Vol. 6, No. 18, 02.09.2015, p. 3663-3669.

Research output: Contribution to journalArticle

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AU - Bakulin, Artem A.

AU - Selig, Oleg

AU - Bakker, Huib J.

AU - Rezus, Yves L.A.

AU - Müller, Christian

AU - Glaser, Tobias

AU - Lovrincic, Robert

AU - Sun, Zhenhua

AU - Chen, Zhuoying

AU - Walsh, Aron

AU - Frost, Jarvist M.

AU - Jansen, Thomas L.C.

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AB - The introduction of a mobile and polarized organic moiety as a cation in 3D lead-iodide perovskites brings fascinating optoelectronic properties to these materials. The extent and the time scales of the orientational mobility of the organic cation and the molecular mechanism behind its motion remain unclear, with different experimental and computational approaches providing very different qualitative and quantitative description of the molecular dynamics. Here we use ultrafast 2D vibrational spectroscopy of methylammonium (MA) lead iodide to directly resolve the rotation of the organic cations within the MAPbI3 lattice. Our results reveal two characteristic time constants of motion. Using ab initio molecular dynamics simulations, we identify these as a fast (∼300 fs) "wobbling-in-a-cone" motion around the crystal axis and a relatively slow (∼3 ps) jump-like reorientation of the molecular dipole with respect to the iodide lattice. The observed dynamics are essential for understanding the electronic properties of perovskite materials.

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