Light-Induced Transient Lattice Dynamics and Metastable Phase Transition in CH3NH3PbI3 Nanocrystals

Ariel A. Leonard; Benjamin T. Diroll; Nathan C. Flanders; Shobhana Panuganti; Alexandra Brumberg; Matthew S. Kirschner; Shelby A. Cuthriell; Samantha M. Harvey; Nicolas E. Watkins; Jin Yu; Michael R. Wasielewski; Mercouri G. Kanatzidis; William R. Dichtel; Xiaoyi Zhang; Lin X. Chen; Richard D. Schaller

doi:10.1021/acsnano.2c06950

Light-Induced Transient Lattice Dynamics and Metastable Phase Transition in CH₃NH₃PbI₃ Nanocrystals

Ariel A. Leonard, Benjamin T. Diroll, Nathan C. Flanders, Shobhana Panuganti, Alexandra Brumberg, Matthew S. Kirschner, Shelby A. Cuthriell, Samantha M. Harvey, Nicolas E. Watkins, Jin Yu, Michael R. Wasielewski, Mercouri G. Kanatzidis, William R. Dichtel, Xiaoyi Zhang, Lin X. Chen, Richard D. Schaller^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

Methylammonium lead iodide (MAPbI₃) perovskite nanocrystals (NCs) offer desirable optoelectronic properties with prospective utility in photovoltaics, lasers, and light-emitting diodes (LEDs). Structural rearrangements of MAPbI₃ in response to photoexcitation, such as lattice distortions and phase transitions, are of particular interest, as these engender long carrier lifetime and bolster carrier diffusion. Here, we use variable temperature X-ray diffraction (XRD) and synchrotron-based transient X-ray diffraction (TRXRD) to investigate lattice response following ultrafast optical excitation. MAPbI₃ NCs are found to slowly undergo a phase transition from the tetragonal to a pseudocubic phase over the course of 1 ns under 0.02-4.18 mJ/cm² fluence photoexcitation, with apparent nonthermal lattice distortions attributed to polaron formation. Lattice recovery exceeds time scales expected for both carrier recombination and thermal dissipation, indicating meta-stability likely due to the proximal phase transition, with symmetry-breaking along equatorial and axial directions. These findings are relevant for fundamental understanding and applications of structure-function properties.

Original language	English (US)
Pages (from-to)	5306-5315
Number of pages	10
Journal	ACS nano
Volume	17
Issue number	6
DOIs	https://doi.org/10.1021/acsnano.2c06950
State	Published - Mar 28 2023

Keywords

lattice dynamics
metastable state
methylammonium lead iodide
perovskite
photoinduced phase transition
polaron
transient X-ray diffraction

ASJC Scopus subject areas

Engineering(all)
Physics and Astronomy(all)
Materials Science(all)

Access to Document

10.1021/acsnano.2c06950

Cite this

Leonard, A. A., Diroll, B. T., Flanders, N. C., Panuganti, S., Brumberg, A., Kirschner, M. S., Cuthriell, S. A., Harvey, S. M., Watkins, N. E., Yu, J., Wasielewski, M. R., Kanatzidis, M. G., Dichtel, W. R., Zhang, X., Chen, L. X., & Schaller, R. D. (2023). Light-Induced Transient Lattice Dynamics and Metastable Phase Transition in CH₃NH₃PbI₃ Nanocrystals. ACS nano, 17(6), 5306-5315. https://doi.org/10.1021/acsnano.2c06950

@article{2c0fcc401b044374810f8f750b1b513c,

title = "Light-Induced Transient Lattice Dynamics and Metastable Phase Transition in CH3NH3PbI3 Nanocrystals",

abstract = "Methylammonium lead iodide (MAPbI3) perovskite nanocrystals (NCs) offer desirable optoelectronic properties with prospective utility in photovoltaics, lasers, and light-emitting diodes (LEDs). Structural rearrangements of MAPbI3 in response to photoexcitation, such as lattice distortions and phase transitions, are of particular interest, as these engender long carrier lifetime and bolster carrier diffusion. Here, we use variable temperature X-ray diffraction (XRD) and synchrotron-based transient X-ray diffraction (TRXRD) to investigate lattice response following ultrafast optical excitation. MAPbI3 NCs are found to slowly undergo a phase transition from the tetragonal to a pseudocubic phase over the course of 1 ns under 0.02-4.18 mJ/cm2 fluence photoexcitation, with apparent nonthermal lattice distortions attributed to polaron formation. Lattice recovery exceeds time scales expected for both carrier recombination and thermal dissipation, indicating meta-stability likely due to the proximal phase transition, with symmetry-breaking along equatorial and axial directions. These findings are relevant for fundamental understanding and applications of structure-function properties.",

keywords = "lattice dynamics, metastable state, methylammonium lead iodide, perovskite, photoinduced phase transition, polaron, transient X-ray diffraction",

author = "Leonard, {Ariel A.} and Diroll, {Benjamin T.} and Flanders, {Nathan C.} and Shobhana Panuganti and Alexandra Brumberg and Kirschner, {Matthew S.} and Cuthriell, {Shelby A.} and Harvey, {Samantha M.} and Watkins, {Nicolas E.} and Jin Yu and Wasielewski, {Michael R.} and Kanatzidis, {Mercouri G.} and Dichtel, {William R.} and Xiaoyi Zhang and Chen, {Lin X.} and Schaller, {Richard D.}",

note = "Funding Information: The authors acknowledge support from the Ultrafast Initiative of the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, through Argonne National Laboratory under Contract No. DE-AC02-06CH11357. The authors acknowledge support from the National Science Foundation MSN under grant 1808590. This material is based upon work supported by the National Science Foundation Graduate Student Fellowship Program under Grant No. DGE-1842165 (S.P., A.B., S.M.H., and N.E.W.). S.M.H. and M.R.W. were supported by the Office of Science, Office of Basic Energy Sciences, Department of Energy under award DE-FG02-99ER14999. Work performed at the Center for Nanoscale Materials and Advanced Photon Source, both U.S. Department of Energy Office of Science User Facilities, was supported by the U.S. DOE, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. The submitted manuscript was created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02-06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DEO Public Access Plan: http://energy.gov/downloads/doe-public-access-plan . Publisher Copyright: {\textcopyright} 2023 UChicago Argonne, LLC, Operator of Argonne National Laboratory. Published by American Chemical Society.",

year = "2023",

month = mar,

day = "28",

doi = "10.1021/acsnano.2c06950",

language = "English (US)",

volume = "17",

pages = "5306--5315",

journal = "ACS nano",

issn = "1936-0851",

publisher = "American Chemical Society",

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Leonard, AA, Diroll, BT, Flanders, NC, Panuganti, S, Brumberg, A, Kirschner, MS, Cuthriell, SA, Harvey, SM, Watkins, NE, Yu, J, Wasielewski, MR , Kanatzidis, MG , Dichtel, WR, Zhang, X, Chen, LX & Schaller, RD 2023, 'Light-Induced Transient Lattice Dynamics and Metastable Phase Transition in CH₃NH₃PbI₃ Nanocrystals', ACS nano, vol. 17, no. 6, pp. 5306-5315. https://doi.org/10.1021/acsnano.2c06950

TY - JOUR

T1 - Light-Induced Transient Lattice Dynamics and Metastable Phase Transition in CH3NH3PbI3 Nanocrystals

AU - Leonard, Ariel A.

AU - Diroll, Benjamin T.

AU - Flanders, Nathan C.

AU - Panuganti, Shobhana

AU - Brumberg, Alexandra

AU - Kirschner, Matthew S.

AU - Cuthriell, Shelby A.

AU - Harvey, Samantha M.

AU - Watkins, Nicolas E.

AU - Yu, Jin

AU - Wasielewski, Michael R.

AU - Kanatzidis, Mercouri G.

AU - Dichtel, William R.

AU - Zhang, Xiaoyi

AU - Chen, Lin X.

AU - Schaller, Richard D.

N1 - Funding Information: The authors acknowledge support from the Ultrafast Initiative of the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, through Argonne National Laboratory under Contract No. DE-AC02-06CH11357. The authors acknowledge support from the National Science Foundation MSN under grant 1808590. This material is based upon work supported by the National Science Foundation Graduate Student Fellowship Program under Grant No. DGE-1842165 (S.P., A.B., S.M.H., and N.E.W.). S.M.H. and M.R.W. were supported by the Office of Science, Office of Basic Energy Sciences, Department of Energy under award DE-FG02-99ER14999. Work performed at the Center for Nanoscale Materials and Advanced Photon Source, both U.S. Department of Energy Office of Science User Facilities, was supported by the U.S. DOE, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. The submitted manuscript was created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02-06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DEO Public Access Plan: http://energy.gov/downloads/doe-public-access-plan . Publisher Copyright: © 2023 UChicago Argonne, LLC, Operator of Argonne National Laboratory. Published by American Chemical Society.

PY - 2023/3/28

Y1 - 2023/3/28

N2 - Methylammonium lead iodide (MAPbI3) perovskite nanocrystals (NCs) offer desirable optoelectronic properties with prospective utility in photovoltaics, lasers, and light-emitting diodes (LEDs). Structural rearrangements of MAPbI3 in response to photoexcitation, such as lattice distortions and phase transitions, are of particular interest, as these engender long carrier lifetime and bolster carrier diffusion. Here, we use variable temperature X-ray diffraction (XRD) and synchrotron-based transient X-ray diffraction (TRXRD) to investigate lattice response following ultrafast optical excitation. MAPbI3 NCs are found to slowly undergo a phase transition from the tetragonal to a pseudocubic phase over the course of 1 ns under 0.02-4.18 mJ/cm2 fluence photoexcitation, with apparent nonthermal lattice distortions attributed to polaron formation. Lattice recovery exceeds time scales expected for both carrier recombination and thermal dissipation, indicating meta-stability likely due to the proximal phase transition, with symmetry-breaking along equatorial and axial directions. These findings are relevant for fundamental understanding and applications of structure-function properties.

AB - Methylammonium lead iodide (MAPbI3) perovskite nanocrystals (NCs) offer desirable optoelectronic properties with prospective utility in photovoltaics, lasers, and light-emitting diodes (LEDs). Structural rearrangements of MAPbI3 in response to photoexcitation, such as lattice distortions and phase transitions, are of particular interest, as these engender long carrier lifetime and bolster carrier diffusion. Here, we use variable temperature X-ray diffraction (XRD) and synchrotron-based transient X-ray diffraction (TRXRD) to investigate lattice response following ultrafast optical excitation. MAPbI3 NCs are found to slowly undergo a phase transition from the tetragonal to a pseudocubic phase over the course of 1 ns under 0.02-4.18 mJ/cm2 fluence photoexcitation, with apparent nonthermal lattice distortions attributed to polaron formation. Lattice recovery exceeds time scales expected for both carrier recombination and thermal dissipation, indicating meta-stability likely due to the proximal phase transition, with symmetry-breaking along equatorial and axial directions. These findings are relevant for fundamental understanding and applications of structure-function properties.

KW - lattice dynamics

KW - metastable state

KW - methylammonium lead iodide

KW - perovskite

KW - photoinduced phase transition

KW - polaron

KW - transient X-ray diffraction

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U2 - 10.1021/acsnano.2c06950

DO - 10.1021/acsnano.2c06950

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