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Title: Intrinsic anion diffusivity in lead halide perovskites is facilitated by a soft lattice

Abstract

Facile ionic transport in lead halide perovskites plays a critical role in device performance. Understanding the microscopic origins of high ionic conductivities has been complicated by indirect measurements and sample microstructural heterogeneities. Here, we report the direct visualization of halide anion interdiffusion in CsPbCl 3 –CsPbBr 3 single crystalline perovskite nanowire heterojunctions using wide-field and confocal photoluminescence measurements. The combination of nanoscale imaging techniques with these single crystalline materials allows us to measure intrinsic anionic lattice diffusivities, free from complications of microscale inhomogeneity. Halide diffusivities were found to be between 10 −13 and ∼10 −12 cm 2 /second at about 100 °C, which are several orders of magnitudes lower than those reported in polycrystalline thin films. Spatially resolved photoluminescence lifetimes and surface potential measurements provide evidence of the central role of halide vacancies in facilitating ionic diffusion. Vacancy formation free energies computed from molecular simulation are small due to the easily deformable perovskite lattice, accounting for the high equilibrium vacancy concentration. Furthermore, molecular simulations suggest that ionic motion is facilitated by low-frequency lattice modes, resulting in low activation barriers for vacancy-mediated transport. This work elucidates the intrinsic solid-state ion diffusion mechanisms in this class of semisoft materials and offers guidelinesmore » for engineering materials with long-term stability in functional devices.« less

Authors:
; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1480900
Alternate Identifier(s):
OSTI ID: 1542340
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 115 Journal Issue: 47; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; halide perovskite nanowire; anion diffusivity; nanoscale imaging; molecular simulation; soft lattice

Citation Formats

Lai, Minliang, Obliger, Amael, Lu, Dylan, Kley, Christopher S., Bischak, Connor G., Kong, Qiao, Lei, Teng, Dou, Letian, Ginsberg, Naomi S., Limmer, David T., and Yang, Peidong. Intrinsic anion diffusivity in lead halide perovskites is facilitated by a soft lattice. United States: N. p., 2018. Web. doi:10.1073/pnas.1812718115.
Lai, Minliang, Obliger, Amael, Lu, Dylan, Kley, Christopher S., Bischak, Connor G., Kong, Qiao, Lei, Teng, Dou, Letian, Ginsberg, Naomi S., Limmer, David T., & Yang, Peidong. Intrinsic anion diffusivity in lead halide perovskites is facilitated by a soft lattice. United States. doi:10.1073/pnas.1812718115.
Lai, Minliang, Obliger, Amael, Lu, Dylan, Kley, Christopher S., Bischak, Connor G., Kong, Qiao, Lei, Teng, Dou, Letian, Ginsberg, Naomi S., Limmer, David T., and Yang, Peidong. Mon . "Intrinsic anion diffusivity in lead halide perovskites is facilitated by a soft lattice". United States. doi:10.1073/pnas.1812718115.
@article{osti_1480900,
title = {Intrinsic anion diffusivity in lead halide perovskites is facilitated by a soft lattice},
author = {Lai, Minliang and Obliger, Amael and Lu, Dylan and Kley, Christopher S. and Bischak, Connor G. and Kong, Qiao and Lei, Teng and Dou, Letian and Ginsberg, Naomi S. and Limmer, David T. and Yang, Peidong},
abstractNote = {Facile ionic transport in lead halide perovskites plays a critical role in device performance. Understanding the microscopic origins of high ionic conductivities has been complicated by indirect measurements and sample microstructural heterogeneities. Here, we report the direct visualization of halide anion interdiffusion in CsPbCl 3 –CsPbBr 3 single crystalline perovskite nanowire heterojunctions using wide-field and confocal photoluminescence measurements. The combination of nanoscale imaging techniques with these single crystalline materials allows us to measure intrinsic anionic lattice diffusivities, free from complications of microscale inhomogeneity. Halide diffusivities were found to be between 10 −13 and ∼10 −12 cm 2 /second at about 100 °C, which are several orders of magnitudes lower than those reported in polycrystalline thin films. Spatially resolved photoluminescence lifetimes and surface potential measurements provide evidence of the central role of halide vacancies in facilitating ionic diffusion. Vacancy formation free energies computed from molecular simulation are small due to the easily deformable perovskite lattice, accounting for the high equilibrium vacancy concentration. Furthermore, molecular simulations suggest that ionic motion is facilitated by low-frequency lattice modes, resulting in low activation barriers for vacancy-mediated transport. This work elucidates the intrinsic solid-state ion diffusion mechanisms in this class of semisoft materials and offers guidelines for engineering materials with long-term stability in functional devices.},
doi = {10.1073/pnas.1812718115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 47,
volume = 115,
place = {United States},
year = {2018},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1073/pnas.1812718115

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Cited by: 13 works
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Works referenced in this record:

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

  • Eames, Christopher; Frost, Jarvist M.; Barnes, Piers R. F.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8497

Synthesis of Composition Tunable and Highly Luminescent Cesium Lead Halide Nanowires through Anion-Exchange Reactions
journal, June 2016

  • Zhang, Dandan; Yang, Yiming; Bekenstein, Yehonadav
  • Journal of the American Chemical Society, Vol. 138, Issue 23
  • DOI: 10.1021/jacs.6b03134

Modeling ion exchange in glass with concentration‐dependent diffusion coefficients and mobilities
journal, June 1996

  • Lupascu, Alexandru
  • Optical Engineering, Vol. 35, Issue 6
  • DOI: 10.1117/1.600727

Hysteresis, Stability, and Ion Migration in Lead Halide Perovskite Photovoltaics
journal, May 2016

  • Miyano, Kenjiro; Yanagida, Masatoshi; Tripathi, Neeti
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 12
  • DOI: 10.1021/acs.jpclett.6b00579

Formation of Perovskite Heterostructures by Ion Exchange
journal, November 2016

  • Shewmon, Nathan T.; Yu, Hyeonggeun; Constantinou, Iordania
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 48
  • DOI: 10.1021/acsami.6b10034

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

Room-Temperature Coherent Optical Phonon in 2D Electronic Spectra of CH 3 NH 3 PbI 3 Perovskite as a Possible Cooling Bottleneck
journal, June 2017

  • Monahan, Daniele M.; Guo, Liang; Lin, Jia
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 14
  • DOI: 10.1021/acs.jpclett.7b01357

Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics
journal, January 2015

  • Hoke, Eric T.; Slotcavage, Daniel J.; Dohner, Emma R.
  • Chemical Science, Vol. 6, Issue 1
  • DOI: 10.1039/C4SC03141E

Ultralow thermal conductivity in all-inorganic halide perovskites
journal, July 2017

  • Lee, Woochul; Li, Huashan; Wong, Andrew B.
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 33
  • DOI: 10.1073/pnas.1711744114

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

Impact of microstructure on local carrier lifetime in perovskite solar cells
journal, April 2015


Ionic polarization-induced current–voltage hysteresis in CH3NH3PbX3 perovskite solar cells
journal, February 2016

  • Meloni, Simone; Moehl, Thomas; Tress, Wolfgang
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms10334

Ionic conduction of the perovskite-type halides
journal, November 1983


Calculation of point-defect entropy in metals
journal, November 2001

  • Mishin, Yuri; S⊘rensen, Mads R.; Voter, Arthur F.
  • Philosophical Magazine A, Vol. 81, Issue 11
  • DOI: 10.1080/01418610108216657

Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions
journal, August 2015

  • Akkerman, Quinten A.; D’Innocenzo, Valerio; Accornero, Sara
  • Journal of the American Chemical Society, Vol. 137, Issue 32
  • DOI: 10.1021/jacs.5b05602

Giant switchable photovoltaic effect in organometal trihalide perovskite devices
journal, December 2014

  • Xiao, Zhengguo; Yuan, Yongbo; Shao, Yuchuan
  • Nature Materials, Vol. 14, Issue 2
  • DOI: 10.1038/nmat4150

Calculation of Diffusion Penetration Curves for Surface and Grain Boundary Diffusion
journal, January 1951


Atomically thin two-dimensional organic-inorganic hybrid perovskites
journal, September 2015


Origin of Reversible Photoinduced Phase Separation in Hybrid Perovskites
journal, January 2017


Interdiffusion in the System MnxO-MgO
journal, July 1971


Visualization and Studies of Ion-Diffusion Kinetics in Cesium Lead Bromide Perovskite Nanowires
journal, February 2018


Nonequilibrium Equality for Free Energy Differences
journal, April 1997


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


Spatially resolved multicolor CsPbX 3 nanowire heterojunctions via anion exchange
journal, June 2017

  • Dou, Letian; Lai, Minliang; Kley, Christopher S.
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 28
  • DOI: 10.1073/pnas.1703860114

Anomalous Hysteresis in Perovskite Solar Cells
journal, April 2014

  • Snaith, Henry J.; Abate, Antonio; Ball, James M.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 9
  • DOI: 10.1021/jz500113x

First-Principles Study of Ion Diffusion in Perovskite Solar Cell Sensitizers
journal, August 2015

  • Haruyama, Jun; Sodeyama, Keitaro; Han, Liyuan
  • Journal of the American Chemical Society, Vol. 137, Issue 32
  • DOI: 10.1021/jacs.5b03615

Analysis of interdiffusion via vacancy-pairs in strongly ionic solids
journal, December 2004


Free energy calculation from steered molecular dynamics simulations using Jarzynski’s equality
journal, August 2003

  • Park, Sanghyun; Khalili-Araghi, Fatemeh; Tajkhorshid, Emad
  • The Journal of Chemical Physics, Vol. 119, Issue 6
  • DOI: 10.1063/1.1590311

Surface- vs Diffusion-Limited Mechanisms of Anion Exchange in CsPbBr 3 Nanocrystal Cubes Revealed through Kinetic Studies
journal, September 2016

  • Koscher, Brent A.; Bronstein, Noah D.; Olshansky, Jacob H.
  • Journal of the American Chemical Society, Vol. 138, Issue 37
  • DOI: 10.1021/jacs.6b08178

The Significance of Ion Conduction in a Hybrid Organic-Inorganic Lead-Iodide-Based Perovskite Photosensitizer
journal, May 2015

  • Yang, Tae-Youl; Gregori, Giuliano; Pellet, Norman
  • Angewandte Chemie International Edition, Vol. 54, Issue 27
  • DOI: 10.1002/anie.201500014

Perovskite solar cells with a planar heterojunction structure prepared using room-temperature solution processing techniques
journal, December 2013