skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

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 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.

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:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); LANL Laboratory Directed Research and Development (LDRD) Program; LBNL Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1459840
Alternate Identifier(s):
OSTI ID: 1506380
Report Number(s):
LA-UR-17-31256
Journal ID: ISSN 2041-1723; TRN: US1901813
Grant/Contract Number:  
AC52-06NA25396; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Material Science

Citation Formats

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., 2018. 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. https://doi.org/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. https://doi.org/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},
url = {https://www.osti.gov/biblio/1459840}, journal = {Nature Communications},
issn = {2041-1723},
number = ,
volume = 9,
place = {United States},
year = {Thu Jun 28 00:00:00 EDT 2018},
month = {Thu Jun 28 00:00:00 EDT 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 106 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1: Transient excited state absorption spectrum shown in the 830–940 nm region of MAPbI3 perovskite excited by a ~40 fs FWHM pulse at 560 nm. a Contour plot of excited state absorption band centered at ~855 nm. b–d Time profiles measured at 840–855 (blue), 860–875 (green), and 885–900 nmmore » (red) fit to the sum of two exponentials with the indicated constants. The residual profiles are also shown revealing underlying oscillations especially in the 840−855 and 885−900 nm regions« less

Save / Share:

Works referenced in this record:

Charge Carriers in Hybrid Organic–Inorganic Lead Halide Perovskites Might Be Protected as Large Polarons
journal, November 2015


Generalized Gradient Approximation Made Simple
journal, October 1996


Ionic transport in hybrid lead iodide perovskite solar cells
journal, June 2015


Coulomb Screening and Coherent Phonon in Methylammonium Lead Iodide Perovskites
journal, August 2016


Density functional theory + U modeling of polarons in organohalide lead perovskites
journal, December 2016


Projector augmented-wave method
journal, December 1994


Long-Lived Photoinduced Polarons in Organohalide Perovskites
journal, June 2017


Femtosecond Stimulated Raman Exposes the Role of Vibrational Coherence in Condensed-Phase Photoreactivity
journal, March 2016


Advances and Promises of Layered Halide Hybrid Perovskite Semiconductors
journal, October 2016


Iodide management in formamidinium-lead-halide–based perovskite layers for efficient solar cells
journal, June 2017


Impact of microstructure on the electron–hole interaction in lead halide perovskites
journal, January 2017


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


High-performance photovoltaic perovskite layers fabricated through intramolecular exchange
journal, May 2015


Solar cell efficiency tables (version 50)
journal, June 2017

  • Green, Martin A.; Hishikawa, Yoshihiro; Warta, Wilhelm
  • Progress in Photovoltaics: Research and Applications, Vol. 25, Issue 7
  • https://doi.org/10.1002/pip.2909

A coherent picture of vision
journal, November 2015


Femtosecond Stimulated Raman Spectroscopy
journal, March 2016


Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells
journal, July 2014


Structural Study on Cubic–Tetragonal Transition of CH 3 NH 3 PbI 3
journal, July 2002


Wave packet theory of dynamic absorption spectra in femtosecond pump–probe experiments
journal, April 1990


Microscopic Analysis of Inherent Void Passivation in Perovskite Solar Cells
journal, June 2017


Screening in crystalline liquids protects energetic carriers in hybrid perovskites
journal, September 2016


Optical study on intrinsic exciton states in high-quality CH 3 NH 3 PbBr 3 single crystals
journal, August 2017


Interplay of Orientational Order and Electronic Structure in Methylammonium Lead Iodide: Implications for Solar Cell Operation
journal, November 2014


Low Frequency Resonant Impulsive Raman Modes Reveal Inversion Mechanism for Azobenzene
journal, November 2013


High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells
journal, July 2016


Polaron Stabilization by Cooperative Lattice Distortion and Cation Rotations in Hybrid Perovskite Materials
journal, May 2016


Resonance Raman Investigation of the Interaction between Aromatic Dithiocarbamate Ligands and CdSe Quantum Dots
journal, March 2017


Resonance Raman Spectroscopy and Electron–Phonon Coupling in Zinc Selenide Quantum Dots
journal, December 2016


Effect of Cation Rotation on Charge Dynamics in Hybrid Lead Halide Perovskites
journal, July 2016


Grain boundaries in CdTe thin film solar cells: a review
journal, July 2016


Large polarons in lead halide perovskites
journal, August 2017


Charge-carrier dynamics in vapour-deposited films of the organolead halide perovskite CH 3 NH 3 PbI 3−x Cl x
journal, January 2014


Special points for Brillouin-zone integrations
journal, June 1976


Critical Role of Methylammonium Librational Motion in Methylammonium Lead Iodide (CH 3 NH 3 PbI 3 ) Perovskite Photochemistry
journal, June 2017


Methodologies for high efficiency perovskite solar cells
journal, June 2016


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model
journal, March 1998


Coherent and Homogeneous Intramolecular Charge-Transfer Dynamics of 1- tert -Butyl-6-cyano-1,2,3,4-tetrahydroquinoline (NTC6), a Rigid Analogue of DMABN
journal, July 2014


Structural, optical, and electrical properties of phase-controlled cesium lead iodide nanowires
journal, February 2017


Persistent Energetic Electrons in Methylammonium Lead Iodide Perovskite Thin Films
journal, November 2016


Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber
journal, October 2013


Mapping GFP structure evolution during proton transfer with femtosecond Raman spectroscopy
journal, November 2009


Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3)PbI3 for solid-state sensitised solar cell applications
journal, January 2013


Facet-dependent photovoltaic efficiency variations in single grains of hybrid halide perovskite
journal, July 2016


Terahertz Emission from Hybrid Perovskites Driven by Ultrafast Charge Separation and Strong Electron-Phonon Coupling
journal, January 2018


Deep level trapped defect analysis in CH 3 NH 3 PbI 3 perovskite solar cells by deep level transient spectroscopy
journal, January 2017


Virtual Issue on Metal-Halide Perovskite Nanocrystals—A Bright Future for Optoelectronics
journal, October 2017


Recent advances in perovskite solar cells: efficiency, stability and lead-free perovskite
journal, January 2017


Tailoring of Electron-Collecting Oxide Nanoparticulate Layer for Flexible Perovskite Solar Cells
journal, May 2016


Beneficial Effects of PbI 2 Incorporated in Organo-Lead Halide Perovskite Solar Cells
journal, December 2015


Evidence for conical intersection dynamics mediating ultrafast singlet exciton fission
journal, March 2015


Real-Time Observation of Organic Cation Reorientation in Methylammonium Lead Iodide Perovskites
journal, August 2015


Femtosecond stimulated Raman spectroscopy
journal, December 2010


Evidence for conical intersection dynamics mediating ultrafast singlet exciton fission
text, January 2015


Femtosecond Stimulated Raman Spectroscopy
journal, April 2016


Terahertz Emission from Hybrid Perovskites Driven by Ultrafast Charge Separation and Strong Electron-Phonon Coupling
journal, January 2018


Femtosecond Stimulated Raman Spectroscopy
journal, March 2016


Solar cell efficiency tables (version 50)
journal, June 2017

  • Green, Martin A.; Hishikawa, Yoshihiro; Warta, Wilhelm
  • Progress in Photovoltaics: Research and Applications, Vol. 25, Issue 7
  • https://doi.org/10.1002/pip.2909

Structural, optical, and electrical properties of phase-controlled cesium lead iodide nanowires
journal, February 2017


Femtosecond Stimulated Raman Exposes the Role of Vibrational Coherence in Condensed-Phase Photoreactivity
journal, March 2016


Virtual Issue on Metal-Halide Perovskite Nanocrystals—A Bright Future for Optoelectronics
journal, October 2017


Effect of Cation Rotation on Charge Dynamics in Hybrid Lead Halide Perovskites
journal, July 2016


Resonance Raman Spectroscopy and Electron–Phonon Coupling in Zinc Selenide Quantum Dots
journal, December 2016


Resonance Raman Investigation of the Interaction between Aromatic Dithiocarbamate Ligands and CdSe Quantum Dots
journal, March 2017


Charge Carriers in Hybrid Organic–Inorganic Lead Halide Perovskites Might Be Protected as Large Polarons
journal, November 2015


Tailoring of Electron-Collecting Oxide Nanoparticulate Layer for Flexible Perovskite Solar Cells
journal, May 2016


Long-Lived Photoinduced Polarons in Organohalide Perovskites
journal, June 2017


Polaron Stabilization by Cooperative Lattice Distortion and Cation Rotations in Hybrid Perovskite Materials
journal, May 2016


Critical Role of Methylammonium Librational Motion in Methylammonium Lead Iodide (CH 3 NH 3 PbI 3 ) Perovskite Photochemistry
journal, June 2017


Microscopic Analysis of Inherent Void Passivation in Perovskite Solar Cells
journal, June 2017


Advances and Promises of Layered Halide Hybrid Perovskite Semiconductors
journal, October 2016


Interplay of Orientational Order and Electronic Structure in Methylammonium Lead Iodide: Implications for Solar Cell Operation
journal, November 2014


Coherent and Homogeneous Intramolecular Charge-Transfer Dynamics of 1- tert -Butyl-6-cyano-1,2,3,4-tetrahydroquinoline (NTC6), a Rigid Analogue of DMABN
journal, July 2014


Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model
journal, March 1998


Mapping GFP structure evolution during proton transfer with femtosecond Raman spectroscopy
journal, November 2009


High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells
journal, July 2016


A coherent picture of vision
journal, November 2015


Ionic transport in hybrid lead iodide perovskite solar cells
journal, June 2015


Facet-dependent photovoltaic efficiency variations in single grains of hybrid halide perovskite
journal, July 2016


Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells
journal, July 2014


Evidence for conical intersection dynamics mediating ultrafast singlet exciton fission
journal, March 2015


Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3)PbI3 for solid-state sensitised solar cell applications
journal, January 2013


Wave packet theory of dynamic absorption spectra in femtosecond pump–probe experiments
journal, April 1990


Density functional theory + U modeling of polarons in organohalide lead perovskites
journal, December 2016


Large polarons in lead halide perovskites
journal, August 2017


Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber
journal, October 2013


Methodologies for high efficiency perovskite solar cells
journal, June 2016


Works referencing / citing this record:

Illumination‐Induced Halide Segregation in Gradient Bandgap Mixed‐Halide Perovskite Nanoplatelets
journal, October 2018


Polarons in Metal Halide Perovskites
journal, April 2020


Modeling the Ultrafast Response of Two‐Magnon Raman Excitations in Antiferromagnets on the Femtosecond Timescale
journal, October 2019


Evaluation of Polaron Transport in Solids from First‐principles
journal, January 2020


Two-dimensional electronic spectroscopy reveals liquid-like lineshape dynamics in CsPbI3 perovskite nanocrystals
journal, October 2019


Phonon coherences reveal the polaronic character of excitons in two-dimensional lead halide perovskites
journal, January 2019


Refractive index change dominates the transient absorption response of metal halide perovskite thin films in the near infrared
journal, January 2019


Thermochromism of bromotellurates( iv ): experimental insights
journal, January 2019


White light emission in low-dimensional perovskites
journal, January 2019


Ultrafast THz Probe of Photoinduced Polarons in Lead-Halide Perovskites
journal, April 2019


Phonon coherences reveal the polaronic character of excitons in two-dimensional lead halide perovskites
conference, January 2019


Ultrafast THz probe of photo-induced polarons in lead-halide perovskites
text, January 2018


Characterization of the Ammonium Bending Vibrations in Two-Dimensional Hybrid Lead-Halide Perovskites from Raman Spectroscopy and First-Principles Calculations
journal, January 2021


Static and Dynamic Disorder in Triple-Cation Hybrid Perovskites
journal, July 2018


Cation Dynamics in Hybrid Halide Perovskites
preprint, January 2020


Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.