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Title: Long-lived polarization memory in the electronic states of lead-halide perovskites from local structural dynamics

Abstract

Anharmonic crystal lattice dynamics have been observed in lead halide perovskites on picosecond timescales. Here, we report that the soft nature of the perovskite crystal lattice gives rise to dynamic fluctuations in the electronic properties of excited states. We use linear polarization selective transient absorption spectroscopy to study the charge carrier relaxation dynamics in lead-halide perovskite films and nanocrystals. We find that photo-excited charge carriers maintain an initial polarization anisotropy for several picoseconds, independent of crystallite size and composition, and well beyond the reported timescales of carrier scattering. First-principles calculations find intrinsic anisotropies in the transition dipole moment, which depend on the orientation of light polarization and the polar distortion of the local crystal lattice. Lattice dynamics are imprinted in the optical transitions and anisotropies arise on the time-scales of structural motion. The strong coupling between electronic states and structural dynamics requires a unique interpretation of recombination and transport mechanisms.

Authors:
 [1]; ORCiD logo [2];  [1];  [1];  [3];  [1];  [4]; ORCiD logo [1];  [4]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Cambridge, Cambridge (United Kingdom)
  2. Univ. of Pennsylvania, Philadelphia, PA (United States)
  3. Victoria Univ. of Wellington, Wellington (New Zealand)
  4. Soochow Univ., Suzhou (People's Republic of China)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); Engineering and Physical Sciences Research Council (EPSRC)
OSTI Identifier:
1559795
Grant/Contract Number:  
AC02-05CH11231; EP/G037221/1; EP/L015978/1; N00014-17-1-2574; UF130278; RG140472
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Rivett, Jasmine P. H., Tan, Liang Z., Price, Michael B., Bourelle, Sean A., Davis, Nathaniel J. L. K., Xiao, James, Zou, Yatao, Middleton, Rox, Sun, Baoquan, Rappe, Andrew M., Credgington, Dan, and Deschler, Felix. Long-lived polarization memory in the electronic states of lead-halide perovskites from local structural dynamics. United States: N. p., 2018. Web. doi:10.1038/s41467-018-06009-3.
Rivett, Jasmine P. H., Tan, Liang Z., Price, Michael B., Bourelle, Sean A., Davis, Nathaniel J. L. K., Xiao, James, Zou, Yatao, Middleton, Rox, Sun, Baoquan, Rappe, Andrew M., Credgington, Dan, & Deschler, Felix. Long-lived polarization memory in the electronic states of lead-halide perovskites from local structural dynamics. United States. doi:10.1038/s41467-018-06009-3.
Rivett, Jasmine P. H., Tan, Liang Z., Price, Michael B., Bourelle, Sean A., Davis, Nathaniel J. L. K., Xiao, James, Zou, Yatao, Middleton, Rox, Sun, Baoquan, Rappe, Andrew M., Credgington, Dan, and Deschler, Felix. Thu . "Long-lived polarization memory in the electronic states of lead-halide perovskites from local structural dynamics". United States. doi:10.1038/s41467-018-06009-3. https://www.osti.gov/servlets/purl/1559795.
@article{osti_1559795,
title = {Long-lived polarization memory in the electronic states of lead-halide perovskites from local structural dynamics},
author = {Rivett, Jasmine P. H. and Tan, Liang Z. and Price, Michael B. and Bourelle, Sean A. and Davis, Nathaniel J. L. K. and Xiao, James and Zou, Yatao and Middleton, Rox and Sun, Baoquan and Rappe, Andrew M. and Credgington, Dan and Deschler, Felix},
abstractNote = {Anharmonic crystal lattice dynamics have been observed in lead halide perovskites on picosecond timescales. Here, we report that the soft nature of the perovskite crystal lattice gives rise to dynamic fluctuations in the electronic properties of excited states. We use linear polarization selective transient absorption spectroscopy to study the charge carrier relaxation dynamics in lead-halide perovskite films and nanocrystals. We find that photo-excited charge carriers maintain an initial polarization anisotropy for several picoseconds, independent of crystallite size and composition, and well beyond the reported timescales of carrier scattering. First-principles calculations find intrinsic anisotropies in the transition dipole moment, which depend on the orientation of light polarization and the polar distortion of the local crystal lattice. Lattice dynamics are imprinted in the optical transitions and anisotropies arise on the time-scales of structural motion. The strong coupling between electronic states and structural dynamics requires a unique interpretation of recombination and transport mechanisms.},
doi = {10.1038/s41467-018-06009-3},
journal = {Nature Communications},
issn = {2041-1723},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {8}
}

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Cited by: 8 works
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Works referenced in this record:

Hot-carrier cooling and photoinduced refractive index changes in organic–inorganic lead halide perovskites
journal, September 2015

  • Price, Michael B.; Butkus, Justinas; Jellicoe, Tom C.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9420

Local Polar Fluctuations in Lead Halide Perovskite Crystals
journal, March 2017


Carrier-phonon interactions in hybrid halide perovskites probed with ultrafast anisotropy studies
conference, September 2016

  • Rivett, Jasmine P. H.; Richter, Johannes M.; Price, Michael B.
  • SPIE Nanoscience + Engineering, SPIE Proceedings
  • DOI: 10.1117/12.2238906

Polar Fluctuations in Metal Halide Perovskites Uncovered by Acoustic Phonon Anomalies
journal, September 2017


Rashba Effect in a Single Colloidal CsPbBr 3 Perovskite Nanocrystal Detected by Magneto-Optical Measurements
journal, July 2017


k ‐space carrier dynamics in GaAs
journal, April 1992

  • Portella, M. T.; Bigot, J. ‐Y.; Schoenlein, R. W.
  • Applied Physics Letters, Vol. 60, Issue 17
  • DOI: 10.1063/1.107083

Large polarons in lead halide perovskites
journal, August 2017

  • Miyata, Kiyoshi; Meggiolaro, Daniele; Trinh, M. Tuan
  • Science Advances, Vol. 3, Issue 8
  • DOI: 10.1126/sciadv.1701217

Inkjet printing of single-crystal films
journal, July 2011

  • Minemawari, Hiromi; Yamada, Toshikazu; Matsui, Hiroyuki
  • Nature, Vol. 475, Issue 7356, p. 364-367
  • DOI: 10.1038/nature10313

Rashba and Dresselhaus Couplings in Halide Perovskites: Accomplishments and Opportunities for Spintronics and Spin–Orbitronics
journal, July 2017


Ultrafast carrier thermalization in lead iodide perovskite probed with two-dimensional electronic spectroscopy
journal, August 2017

  • Richter, Johannes M.; Branchi, Federico; Valduga de Almeida Camargo, Franco
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/s41467-017-00546-z

Enhancing photoluminescence yields in lead halide perovskites by photon recycling and light out-coupling
journal, December 2016

  • Richter, Johannes M.; Abdi-Jalebi, Mojtaba; Sadhanala, Aditya
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms13941

Switchable S = 1/2 and J = 1/2 Rashba bands in ferroelectric halide perovskites
journal, April 2014

  • Kim, M.; Im, J.; Freeman, A. J.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 19
  • DOI: 10.1073/pnas.1405780111

Methylammonium Rotational Dynamics in Lead Halide Perovskite by Classical Molecular Dynamics: The Role of Temperature
journal, July 2015

  • Mattoni, A.; Filippetti, A.; Saba, M. I.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 30
  • DOI: 10.1021/acs.jpcc.5b04283

Organic Cation Rotation and Immobilization in Pure and Mixed Methylammonium Lead-Halide Perovskites
journal, March 2017

  • Selig, Oleg; Sadhanala, Aditya; Müller, Christian
  • Journal of the American Chemical Society, Vol. 139, Issue 11
  • DOI: 10.1021/jacs.6b12239

GIGANTEA is a co-chaperone which facilitates maturation of ZEITLUPE in the Arabidopsis circadian clock
journal, February 2017


Structural and electronic properties of organo-halide hybrid perovskites from ab initio molecular dynamics
journal, January 2015

  • Quarti, Claudio; Mosconi, Edoardo; De Angelis, Filippo
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 14
  • DOI: 10.1039/C5CP00599J

Overcoming the electroluminescence efficiency limitations of perovskite light-emitting diodes
journal, December 2015


Polarized Optical Reflection Spectra of the Highly Anisotropic Organic Semiconductor TEA(TCNQ)2
journal, April 1974


Size-Dependent Valence and Conduction Band-Edge Energies of Semiconductor Nanocrystals
journal, June 2011

  • Jasieniak, Jacek; Califano, Marco; Watkins, Scott E.
  • ACS Nano, Vol. 5, Issue 7
  • DOI: 10.1021/nn201681s

Rashba Spin–Orbit Coupling Enhanced Carrier Lifetime in CH 3 NH 3 PbI 3
journal, November 2015


Morphological Control for High Performance, Solution-Processed Planar Heterojunction Perovskite Solar Cells
journal, September 2013

  • Eperon, Giles E.; Burlakov, Victor M.; Docampo, Pablo
  • Advanced Functional Materials, Vol. 24, Issue 1, p. 151-157
  • DOI: 10.1002/adfm.201302090

Direct Observation of Dynamic Symmetry Breaking above Room Temperature in Methylammonium Lead Iodide Perovskite
journal, October 2016


Hybrid Perovskites for Photovoltaics: Charge-Carrier Recombination, Diffusion, and Radiative Efficiencies
journal, December 2015


Dynamical Origin of the Rashba Effect in Organohalide Lead Perovskites: A Key to Suppressed Carrier Recombination in Perovskite Solar Cells?
journal, April 2016

  • Etienne, Thibaud; Mosconi, Edoardo; De Angelis, Filippo
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 9
  • DOI: 10.1021/acs.jpclett.6b00564

Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites
journal, October 2012


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


Exciton versus Free Carrier Photogeneration in Organometal Trihalide Perovskites Probed by Broadband Ultrafast Polarization Memory Dynamics
journal, March 2015


Importance of Spin–Orbit Coupling in Hybrid Organic/Inorganic Perovskites for Photovoltaic Applications
journal, August 2013

  • Even, Jacky; Pedesseau, Laurent; Jancu, Jean-Marc
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 17
  • DOI: 10.1021/jz401532q

High Charge Carrier Mobilities and Lifetimes in Organolead Trihalide Perovskites
journal, December 2013

  • Wehrenfennig, Christian; Eperon, Giles E.; Johnston, Michael B.
  • Advanced Materials, Vol. 26, Issue 10
  • DOI: 10.1002/adma.201305172

R/G/B/Natural White Light Thin Colloidal Quantum Dot-Based Light-Emitting Devices
journal, August 2014


Low electron-polar optical phonon scattering as a fundamental aspect of carrier mobility in methylammonium lead halide CH 3 NH 3 PbI 3 perovskites
journal, January 2016

  • Filippetti, A.; Mattoni, A.; Caddeo, C.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 22
  • DOI: 10.1039/C6CP01402J

Polarization selective spectroscopy experiments: methodology and pitfalls
journal, January 2005

  • Tan, Howe-Siang; Piletic, Ivan R.; Fayer, M. D.
  • Journal of the Optical Society of America B, Vol. 22, Issue 9
  • DOI: 10.1364/JOSAB.22.002009

Bandgap Engineering of Lead-Free Double Perovskite Cs 2 AgBiBr 6 through Trivalent Metal Alloying
journal, June 2017

  • Du, Ke-zhao; Meng, Weiwei; Wang, Xiaoming
  • Angewandte Chemie International Edition, Vol. 56, Issue 28
  • DOI: 10.1002/anie.201703970

Femtosecond Orientational Relaxation of Photoexcited Carriers in GaAs
journal, July 1984


Giant Rashba Splitting in CH 3 NH 3 PbBr 3 Organic-Inorganic Perovskite
journal, September 2016


Observation of a hot-phonon bottleneck in lead-iodide perovskites
journal, October 2015


Bandgap Engineering of Lead-Free Double Perovskite Cs 2 AgBiBr 6 through Trivalent Metal Alloying
journal, June 2017


Large polarons in lead halide perovskites
text, January 2017

  • Miyata, Kiyoshi; Trinh, M. Tuan; Joshi, Prakriti Pradhan
  • Columbia University
  • DOI: 10.7916/d89s32wc

    Works referencing / citing this record:

    Morphological Control for High Performance, Solution-Processed Planar Heterojunction Perovskite Solar Cells
    journal, September 2013

    • Eperon, Giles E.; Burlakov, Victor M.; Docampo, Pablo
    • Advanced Functional Materials, Vol. 24, Issue 1, p. 151-157
    • DOI: 10.1002/adfm.201302090

    High Charge Carrier Mobilities and Lifetimes in Organolead Trihalide Perovskites
    journal, December 2013

    • Wehrenfennig, Christian; Eperon, Giles E.; Johnston, Michael B.
    • Advanced Materials, Vol. 26, Issue 10
    • DOI: 10.1002/adma.201305172

    R/G/B/Natural White Light Thin Colloidal Quantum Dot-Based Light-Emitting Devices
    journal, August 2014


    Bandgap Engineering of Lead-Free Double Perovskite Cs 2 AgBiBr 6 through Trivalent Metal Alloying
    journal, June 2017

    • Du, Ke-zhao; Meng, Weiwei; Wang, Xiaoming
    • Angewandte Chemie International Edition, Vol. 56, Issue 28
    • DOI: 10.1002/anie.201703970

    Polarized Optical Reflection Spectra of the Highly Anisotropic Organic Semiconductor TEA(TCNQ)2
    journal, April 1974


    Hybrid Perovskites for Photovoltaics: Charge-Carrier Recombination, Diffusion, and Radiative Efficiencies
    journal, December 2015


    Methylammonium Rotational Dynamics in Lead Halide Perovskite by Classical Molecular Dynamics: The Role of Temperature
    journal, July 2015

    • Mattoni, A.; Filippetti, A.; Saba, M. I.
    • The Journal of Physical Chemistry C, Vol. 119, Issue 30
    • DOI: 10.1021/acs.jpcc.5b04283

    Dynamical Origin of the Rashba Effect in Organohalide Lead Perovskites: A Key to Suppressed Carrier Recombination in Perovskite Solar Cells?
    journal, April 2016

    • Etienne, Thibaud; Mosconi, Edoardo; De Angelis, Filippo
    • The Journal of Physical Chemistry Letters, Vol. 7, Issue 9
    • DOI: 10.1021/acs.jpclett.6b00564

    Rashba and Dresselhaus Couplings in Halide Perovskites: Accomplishments and Opportunities for Spintronics and Spin–Orbitronics
    journal, July 2017


    Rashba Spin–Orbit Coupling Enhanced Carrier Lifetime in CH 3 NH 3 PbI 3
    journal, November 2015


    Rashba Effect in a Single Colloidal CsPbBr 3 Perovskite Nanocrystal Detected by Magneto-Optical Measurements
    journal, July 2017


    Direct Observation of Dynamic Symmetry Breaking above Room Temperature in Methylammonium Lead Iodide Perovskite
    journal, October 2016


    Polar Fluctuations in Metal Halide Perovskites Uncovered by Acoustic Phonon Anomalies
    journal, September 2017


    Organic Cation Rotation and Immobilization in Pure and Mixed Methylammonium Lead-Halide Perovskites
    journal, March 2017

    • Selig, Oleg; Sadhanala, Aditya; Müller, Christian
    • Journal of the American Chemical Society, Vol. 139, Issue 11
    • DOI: 10.1021/jacs.6b12239

    Importance of Spin–Orbit Coupling in Hybrid Organic/Inorganic Perovskites for Photovoltaic Applications
    journal, August 2013

    • Even, Jacky; Pedesseau, Laurent; Jancu, Jean-Marc
    • The Journal of Physical Chemistry Letters, Vol. 4, Issue 17
    • DOI: 10.1021/jz401532q

    Size-Dependent Valence and Conduction Band-Edge Energies of Semiconductor Nanocrystals
    journal, June 2011

    • Jasieniak, Jacek; Califano, Marco; Watkins, Scott E.
    • ACS Nano, Vol. 5, Issue 7
    • DOI: 10.1021/nn201681s

    Inkjet printing of single-crystal films
    journal, July 2011

    • Minemawari, Hiromi; Yamada, Toshikazu; Matsui, Hiroyuki
    • Nature, Vol. 475, Issue 7356, p. 364-367
    • DOI: 10.1038/nature10313

    Enhancing photoluminescence yields in lead halide perovskites by photon recycling and light out-coupling
    journal, December 2016

    • Richter, Johannes M.; Abdi-Jalebi, Mojtaba; Sadhanala, Aditya
    • Nature Communications, Vol. 7, Issue 1
    • DOI: 10.1038/ncomms13941

    Observation of a hot-phonon bottleneck in lead-iodide perovskites
    journal, October 2015


    GIGANTEA is a co-chaperone which facilitates maturation of ZEITLUPE in the Arabidopsis circadian clock
    journal, February 2017


    Structural and electronic properties of organo-halide hybrid perovskites from ab initio molecular dynamics
    journal, January 2015

    • Quarti, Claudio; Mosconi, Edoardo; De Angelis, Filippo
    • Physical Chemistry Chemical Physics, Vol. 17, Issue 14
    • DOI: 10.1039/c5cp00599j

    Low electron-polar optical phonon scattering as a fundamental aspect of carrier mobility in methylammonium lead halide CH 3 NH 3 PbI 3 perovskites
    journal, January 2016

    • Filippetti, A.; Mattoni, A.; Caddeo, C.
    • Physical Chemistry Chemical Physics, Vol. 18, Issue 22
    • DOI: 10.1039/c6cp01402j

    k ‐space carrier dynamics in GaAs
    journal, April 1992

    • Portella, M. T.; Bigot, J. ‐Y.; Schoenlein, R. W.
    • Applied Physics Letters, Vol. 60, Issue 17
    • DOI: 10.1063/1.107083

    Switchable S = 1/2 and J = 1/2 Rashba bands in ferroelectric halide perovskites
    journal, April 2014

    • Kim, M.; Im, J.; Freeman, A. J.
    • Proceedings of the National Academy of Sciences, Vol. 111, Issue 19
    • DOI: 10.1073/pnas.1405780111

    Exciton versus Free Carrier Photogeneration in Organometal Trihalide Perovskites Probed by Broadband Ultrafast Polarization Memory Dynamics
    journal, March 2015


    Giant Rashba Splitting in CH 3 NH 3 PbBr 3 Organic-Inorganic Perovskite
    journal, September 2016


    Local Polar Fluctuations in Lead Halide Perovskite Crystals
    journal, March 2017


    Femtosecond Orientational Relaxation of Photoexcited Carriers in GaAs
    journal, July 1984


    Large polarons in lead halide perovskites
    journal, August 2017

    • Miyata, Kiyoshi; Meggiolaro, Daniele; Trinh, M. Tuan
    • Science Advances, Vol. 3, Issue 8
    • DOI: 10.1126/sciadv.1701217

    Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites
    journal, October 2012


    Overcoming the electroluminescence efficiency limitations of perovskite light-emitting diodes
    journal, December 2015


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


    Polarization selective spectroscopy experiments: methodology and pitfalls
    journal, January 2005

    • Tan, Howe-Siang; Piletic, Ivan R.; Fayer, M. D.
    • Journal of the Optical Society of America B, Vol. 22, Issue 9
    • DOI: 10.1364/josab.22.002009