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Title: Chemical nature of ferroelastic twin domains in CH 3NH 3PbI 3 perovskite

Abstract

The extraordinary optoelectronic performance of hybrid organic–inorganic perovskites has resulted in extensive efforts to unravel their properties. Recently, observations of ferroic twin domains in methylammonium lead triiodide drew significant attention as a possible explanation for the current–voltage hysteretic behaviour in these materials. However, the properties of the twin domains, their local chemistry and the chemical impact on optoelectronic performance remain unclear. Here, using multimodal chemical and functional imaging methods, we unveil the mechanical origin of the twin domain contrast observed with piezoresponse force microscopy in methylammonium lead triiodide. By combining experimental results with first principles simulations we reveal an inherent coupling between ferroelastic twin domains and chemical segregation. Furthermore, these results reveal an interplay of ferroic properties and chemical segregation on the optoelectronic performance of hybrid organic–inorganic perovskites, and offer an exploratory path to improving functional devices.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4];  [5]; ORCiD logo [2];  [5];  [5]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2];  [5]; ORCiD logo [2]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Asylum Research an Oxford Instruments Co., Santa Barbara, CA (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Pusan National Univ., Busan (South Korea)
  5. Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1486954
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Materials
Additional Journal Information:
Journal Volume: 17; Journal Issue: 11; Journal ID: ISSN 1476-1122
Publisher:
Springer Nature - Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Liu, Yongtao, Collins, Liam F., Proksch, Roger, Kim, Songkil, Watson, Brianna R., Doughty, Benjamin, Calhoun, Tessa R., Ahmadi, Mahshid, Ievlev, Anton V., Jesse, Stephen, Retterer, Scott T., Belianinov, Alex, Xiao, Kai, Huang, Jingsong, Sumpter, Bobby G., Kalinin, Sergei V., Hu, Bin, and Ovchinnikova, Olga S. Chemical nature of ferroelastic twin domains in CH3NH3PbI3 perovskite. United States: N. p., 2018. Web. doi:10.1038/s41563-018-0152-z.
Liu, Yongtao, Collins, Liam F., Proksch, Roger, Kim, Songkil, Watson, Brianna R., Doughty, Benjamin, Calhoun, Tessa R., Ahmadi, Mahshid, Ievlev, Anton V., Jesse, Stephen, Retterer, Scott T., Belianinov, Alex, Xiao, Kai, Huang, Jingsong, Sumpter, Bobby G., Kalinin, Sergei V., Hu, Bin, & Ovchinnikova, Olga S. Chemical nature of ferroelastic twin domains in CH3NH3PbI3 perovskite. United States. doi:10.1038/s41563-018-0152-z.
Liu, Yongtao, Collins, Liam F., Proksch, Roger, Kim, Songkil, Watson, Brianna R., Doughty, Benjamin, Calhoun, Tessa R., Ahmadi, Mahshid, Ievlev, Anton V., Jesse, Stephen, Retterer, Scott T., Belianinov, Alex, Xiao, Kai, Huang, Jingsong, Sumpter, Bobby G., Kalinin, Sergei V., Hu, Bin, and Ovchinnikova, Olga S. Mon . "Chemical nature of ferroelastic twin domains in CH3NH3PbI3 perovskite". United States. doi:10.1038/s41563-018-0152-z. https://www.osti.gov/servlets/purl/1486954.
@article{osti_1486954,
title = {Chemical nature of ferroelastic twin domains in CH3NH3PbI3 perovskite},
author = {Liu, Yongtao and Collins, Liam F. and Proksch, Roger and Kim, Songkil and Watson, Brianna R. and Doughty, Benjamin and Calhoun, Tessa R. and Ahmadi, Mahshid and Ievlev, Anton V. and Jesse, Stephen and Retterer, Scott T. and Belianinov, Alex and Xiao, Kai and Huang, Jingsong and Sumpter, Bobby G. and Kalinin, Sergei V. and Hu, Bin and Ovchinnikova, Olga S.},
abstractNote = {The extraordinary optoelectronic performance of hybrid organic–inorganic perovskites has resulted in extensive efforts to unravel their properties. Recently, observations of ferroic twin domains in methylammonium lead triiodide drew significant attention as a possible explanation for the current–voltage hysteretic behaviour in these materials. However, the properties of the twin domains, their local chemistry and the chemical impact on optoelectronic performance remain unclear. Here, using multimodal chemical and functional imaging methods, we unveil the mechanical origin of the twin domain contrast observed with piezoresponse force microscopy in methylammonium lead triiodide. By combining experimental results with first principles simulations we reveal an inherent coupling between ferroelastic twin domains and chemical segregation. Furthermore, these results reveal an interplay of ferroic properties and chemical segregation on the optoelectronic performance of hybrid organic–inorganic perovskites, and offer an exploratory path to improving functional devices.},
doi = {10.1038/s41563-018-0152-z},
journal = {Nature Materials},
issn = {1476-1122},
number = 11,
volume = 17,
place = {United States},
year = {2018},
month = {8}
}

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Works referenced in this record:

Mapping nanoscale elasticity and dissipation using dual frequency contact resonance AFM
journal, August 2011


Norm-conserving and ultrasoft pseudopotentials for first-row and transition elements
journal, October 1994


Domain Walls Conductivity in Hybrid Organometallic Perovskites and Their Essential Role in CH3NH3PbI3 Solar Cell High Performance
journal, June 2015

  • Rashkeev, Sergey N.; El-Mellouhi, Fedwa; Kais, Sabre
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep11467

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


Quantitative measurements of electromechanical response with a combined optical beam and interferometric atomic force microscope
journal, June 2015

  • Labuda, Aleksander; Proksch, Roger
  • Applied Physics Letters, Vol. 106, Issue 25
  • DOI: 10.1063/1.4922210

Ferroelectric Domain Wall Induced Band Gap Reduction and Charge Separation in Organometal Halide Perovskites
journal, February 2015

  • Liu, Shi; Zheng, Fan; Koocher, Nathan Z.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 4
  • DOI: 10.1021/jz502666j

Breaking the limits of structural and mechanical imaging of the heterogeneous structure of coal macerals
journal, October 2014


Interfacial Modification of Perovskite Solar Cells Using an Ultrathin MAI Layer Leads to Enhanced Energy Level Alignment, Efficiencies, and Reproducibility
journal, August 2017

  • Hawash, Zafer; Raga, Sonia R.; Son, Dae-Yong
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 17
  • DOI: 10.1021/acs.jpclett.7b01508

Revealing the role of organic cations in hybrid halide perovskite CH3NH3PbI3
journal, April 2015

  • Motta, Carlo; El-Mellouhi, Fedwa; Kais, Sabre
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8026

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Photoinduced enhancement of a triboelectric nanogenerator based on an organolead halide perovskite
journal, January 2016

  • Su, Li; Zhao, Zhenxuan; Li, Huayang
  • Journal of Materials Chemistry C, Vol. 4, Issue 43
  • DOI: 10.1039/C6TC03513B

Enhancement of Ferroelectricity in Strained BaTiO3 Thin Films
journal, November 2004


Electron-hole diffusion lengths > 175 μm in solution-grown CH 3 NH 3 PbI 3 single crystals
journal, January 2015


Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties
journal, July 2013

  • Stoumpos, Constantinos C.; Malliakas, Christos D.; Kanatzidis, Mercouri G.
  • Inorganic Chemistry, Vol. 52, Issue 15, p. 9019-9038
  • DOI: 10.1021/ic401215x

Ferroelectric or non-ferroelectric: Why so many materials exhibit “ferroelectricity” on the nanoscale
journal, June 2017

  • Vasudevan, Rama K.; Balke, Nina; Maksymovych, Peter
  • Applied Physics Reviews, Vol. 4, Issue 2
  • DOI: 10.1063/1.4979015

Scanning Electron Microscopy and Transmission Electron Microscopy Study of Ferroelectric Domains in Doped BaTiO3
journal, August 1986


Mesoscopic structures in ferroelastic crystals: needle twins and right-angled domains
journal, October 1996


High thermoelectric performance BiSbTe alloy with unique low-dimensional structure
journal, June 2009

  • Xie, Wenjie; Tang, Xinfeng; Yan, Yonggao
  • Journal of Applied Physics, Vol. 105, Issue 11
  • DOI: 10.1063/1.3143104

Exploring Local Electrostatic Effects with Scanning Probe Microscopy: Implications for Piezoresponse Force Microscopy and Triboelectricity
journal, October 2014

  • Balke, Nina; Maksymovych, Petro; Jesse, Stephen
  • ACS Nano, Vol. 8, Issue 10
  • DOI: 10.1021/nn505176a

Hybrid rice: achievement, challenges and opportunity
journal, September 2017


Elucidation of Perovskite Film Micro-Orientations Using Two-Photon Total Internal Reflectance Fluorescence Microscopy
journal, July 2015

  • Watson, Brianna R.; Yang, Bin; Xiao, Kai
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 16
  • DOI: 10.1021/acs.jpclett.5b01474

The band excitation method in scanning probe microscopy for rapid mapping of energy dissipation on the nanoscale
journal, September 2007


Ab Initio Study of Interaction of Water, Hydroxyl Radicals, and Hydroxide Ions with CH 3 NH 3 PbI 3 and CH 3 NH 3 PbBr 3 Surfaces
journal, September 2015

  • Zhang, Linghai; Sit, Patrick H. -L.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 39
  • DOI: 10.1021/acs.jpcc.5b07000

Exploring Anomalous Polarization Dynamics in Organometallic Halide Perovskites
journal, January 2018

  • Ahmadi, Mahshid; Collins, Liam; Puretzky, Alexander
  • Advanced Materials, Vol. 30, Issue 11
  • DOI: 10.1002/adma.201705298

Intrinsic Halide Segregation at Nanometer Scale Determines the High Efficiency of Mixed Cation/Mixed Halide Perovskite Solar Cells
journal, December 2016

  • Gratia, Paul; Grancini, Giulia; Audinot, Jean-Nicolas
  • Journal of the American Chemical Society, Vol. 138, Issue 49
  • DOI: 10.1021/jacs.6b10049

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


High-Gain and Low-Driving-Voltage Photodetectors Based on Organolead Triiodide Perovskites
journal, January 2015


Birefringence above T c in single crystals of barium titanate
journal, March 2008


Sequential deposition as a route to high-performance perovskite-sensitized solar cells
journal, July 2013

  • Burschka, Julian; Pellet, Norman; Moon, Soo-Jin
  • Nature, Vol. 499, Issue 7458, p. 316-319
  • DOI: 10.1038/nature12340

Infrared Spectroscopic Study of Vibrational Modes in Methylammonium Lead Halide Perovskites
journal, July 2015

  • Glaser, Tobias; Müller, Christian; Sendner, Michael
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 15
  • DOI: 10.1021/acs.jpclett.5b01309

Exploring the Electronic Band Structure of Organometal Halide Perovskite via Photoluminescence Anisotropy of Individual Nanocrystals
journal, August 2016


Ferroelastic Fingerprints in Methylammonium Lead Iodide Perovskite
journal, January 2016

  • Hermes, Ilka M.; Bretschneider, Simon A.; Bergmann, Victor W.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 10
  • DOI: 10.1021/acs.jpcc.5b11469

Ferroelastic Domain Structure and Switching in Epitaxial Ferroelectric thin Films
journal, August 2006


Resonance enhancement in piezoresponse force microscopy: Mapping electromechanical activity, contact stiffness, and Q factor
journal, July 2006

  • Jesse, Stephen; Mirman, Boris; Kalinin, Sergei V.
  • Applied Physics Letters, Vol. 89, Issue 2
  • DOI: 10.1063/1.2221496

Band Excitation in Scanning Probe Microscopy: Recognition and Functional Imaging
journal, April 2014


Domain formation and elastic long-range interaction in ferroelectric perovskites
journal, September 1994


Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990


The Many Faces of Mixed Ion Perovskites: Unraveling and Understanding the Crystallization Process
journal, November 2017


Enhanced Photovoltaic Properties Induced by Ferroelectric Domain Structures in Organometallic Halide Perovskites
journal, May 2017

  • Bi, Fuzhen; Markov, Stanislav; Wang, Rulin
  • The Journal of Physical Chemistry C, Vol. 121, Issue 21
  • DOI: 10.1021/acs.jpcc.7b03091

Ferroelectric domains in methylammonium lead iodide perovskite thin-films
journal, January 2017

  • Röhm, Holger; Leonhard, Tobias; Hoffmann, Michael J.
  • Energy & Environmental Science, Vol. 10, Issue 4
  • DOI: 10.1039/C7EE00420F

Direct observation of intrinsic twin domains in tetragonal CH3NH3PbI3
journal, February 2017

  • Rothmann, Mathias Uller; Li, Wei; Zhu, Ye
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14547

CH 3 NH 3 PbI 3 perovskites: Ferroelasticity revealed
journal, April 2017


Determination of the True Lateral Grain Size in Organic–Inorganic Halide Perovskite Thin Films
journal, April 2017

  • MacDonald, Gordon A.; Heveran, Chelsea M.; Yang, Mengjin
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 39
  • DOI: 10.1021/acsami.7b11434

Solution-processed hybrid perovskite photodetectors with high detectivity
journal, November 2014

  • Dou, Letian; Yang, Yang (Micheal); You, Jingbi
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms6404

Ferroic domains regulate photocurrent in single-crystalline CH3NH3PbI3 films self-grown on FTO/TiO2 substrate
journal, June 2018


    Works referencing / citing this record:

    A new ferroelastic hybrid material with a large spontaneous strain: (Me 3 NOH) 2 [ZnCl 4 ]
    journal, January 2019

    • Yuan, Wei; Zeng, Ying; Tan, Ya-Yin
    • Chemical Communications, Vol. 55, Issue 61
    • DOI: 10.1039/c9cc03862k

    High-temperature ferroelastic phase transition in a perovskite-like complex: [Et 4 N] 2 [PbBr 3 ] 2
    journal, January 2019

    • Huang, Yuan; Yang, Jie; Li, Zi-jian
    • RSC Advances, Vol. 9, Issue 18
    • DOI: 10.1039/c9ra00804g

    Ferroelectric Properties of Perovskite Thin Films and Their Implications for Solar Energy Conversion
    journal, February 2019

    • Röhm, Holger; Leonhard, Tobias; Schulz, Alexander D.
    • Advanced Materials, Vol. 31, Issue 26
    • DOI: 10.1002/adma.201806661

    Heterogeneity at multiple length scales in halide perovskite semiconductors
    journal, July 2019

    • Tennyson, Elizabeth M.; Doherty, Tiarnan A. S.; Stranks, Samuel D.
    • Nature Reviews Materials, Vol. 4, Issue 9
    • DOI: 10.1038/s41578-019-0125-0

    Experimental reconstruction of the contact resonance shape factor for quantification and amplification of bias-induced strain in atomic force microscopy
    journal, April 2019

    • Killgore, Jason P.; Deolia, Akshay; Robins, Lawrence
    • Applied Physics Letters, Vol. 114, Issue 13
    • DOI: 10.1063/1.5091803

    Ferroelectric Properties of Perovskite Thin Films and Their Implications for Solar Energy Conversion
    journal, February 2019

    • Röhm, Holger; Leonhard, Tobias; Schulz, Alexander D.
    • Advanced Materials, Vol. 31, Issue 26
    • DOI: 10.1002/adma.201806661

    Heterogeneity at multiple length scales in halide perovskite semiconductors
    journal, July 2019

    • Tennyson, Elizabeth M.; Doherty, Tiarnan A. S.; Stranks, Samuel D.
    • Nature Reviews Materials, Vol. 4, Issue 9
    • DOI: 10.1038/s41578-019-0125-0

    A new ferroelastic hybrid material with a large spontaneous strain: (Me 3 NOH) 2 [ZnCl 4 ]
    journal, January 2019

    • Yuan, Wei; Zeng, Ying; Tan, Ya-Yin
    • Chemical Communications, Vol. 55, Issue 61
    • DOI: 10.1039/c9cc03862k

    High-temperature ferroelastic phase transition in a perovskite-like complex: [Et 4 N] 2 [PbBr 3 ] 2
    journal, January 2019

    • Huang, Yuan; Yang, Jie; Li, Zi-jian
    • RSC Advances, Vol. 9, Issue 18
    • DOI: 10.1039/c9ra00804g

    Experimental reconstruction of the contact resonance shape factor for quantification and amplification of bias-induced strain in atomic force microscopy
    journal, April 2019

    • Killgore, Jason P.; Deolia, Akshay; Robins, Lawrence
    • Applied Physics Letters, Vol. 114, Issue 13
    • DOI: 10.1063/1.5091803