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Title: Direct Observation of Halide Migration and its Effect on the Photoluminescence of Methylammonium Lead Bromide Perovskite Single Crystals

Abstract

Optoelectronic devices based on hybrid perovskites have demonstrated outstanding performance within a few years of intense study. However, commercialization of these devices requires barriers to their development to be overcome, such as their chemical instability under operating conditions. In order to investigate this instability and its consequences, the electric field applied to single crystals of methylammonium lead bromide (CH3NH3PbBr3) is varied, and changes are mapped in both their elemental composition and photo-luminescence. Synchrotron-based nanoprobe X-ray fluorescence (nano-XRF) with 250 nm resolution reveals quasi-reversible field-assisted halide migration, with corresponding changes in photoluminescence. It is observed that higher local bromide concentration is correlated to superior optoelectronic performance in CH3NH3PbBr3. A lower limit on the electromigration rate is calculated from these experiments and the motion is interpreted as vacancy-mediated migration based on nudged elastic band density functional theory (DFT) simulations. The XRF mapping data provide direct evidence of field-assisted ionic migration in a model hybrid-perovskite thin single crystal, while the link with photoluminescence proves that the halide stoichiometry plays a key role in the optoelectronic properties of the perovskite.

Authors:
 [1];  [1];  [2];  [1];  [3];  [1];  [2]; ORCiD logo [1]
  1. Univ. of California, San Diego, CA (United States). Dept. of Nanoengineering
  2. FOM Inst. for Atomic and Molecular Physics (AMOLF), Amsterdam (Netherlands). Center for Nanophotonics
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; Netherlands Organization for Scientific Research (NWO); European Research Council (ERC); Koninklijke Philips N.V., Amsterdam (Netherlands); National Science Foundation (NSF)
Contributing Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
OSTI Identifier:
1468624
Alternate Identifier(s):
OSTI ID: 1395604
Grant/Contract Number:  
AC02-06CH11357; FP/2007‐2013; 337328; SC0012118; ACI‐1053575
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 43; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nudged elastic band (NEB); DFT computation; halide migration; hybrid perovskites; nanoprobe x-ray fluorescence; spatially resolved photoluminescence mapping

Citation Formats

Luo, Yanqi, Khoram, Parisa, Brittman, Sarah, Zhu, Zhuoying, Lai, Barry, Ong, Shyue Ping, Garnett, Erik C., and Fenning, David P. Direct Observation of Halide Migration and its Effect on the Photoluminescence of Methylammonium Lead Bromide Perovskite Single Crystals. United States: N. p., 2017. Web. doi:10.1002/adma.201703451.
Luo, Yanqi, Khoram, Parisa, Brittman, Sarah, Zhu, Zhuoying, Lai, Barry, Ong, Shyue Ping, Garnett, Erik C., & Fenning, David P. Direct Observation of Halide Migration and its Effect on the Photoluminescence of Methylammonium Lead Bromide Perovskite Single Crystals. United States. doi:10.1002/adma.201703451.
Luo, Yanqi, Khoram, Parisa, Brittman, Sarah, Zhu, Zhuoying, Lai, Barry, Ong, Shyue Ping, Garnett, Erik C., and Fenning, David P. Fri . "Direct Observation of Halide Migration and its Effect on the Photoluminescence of Methylammonium Lead Bromide Perovskite Single Crystals". United States. doi:10.1002/adma.201703451. https://www.osti.gov/servlets/purl/1468624.
@article{osti_1468624,
title = {Direct Observation of Halide Migration and its Effect on the Photoluminescence of Methylammonium Lead Bromide Perovskite Single Crystals},
author = {Luo, Yanqi and Khoram, Parisa and Brittman, Sarah and Zhu, Zhuoying and Lai, Barry and Ong, Shyue Ping and Garnett, Erik C. and Fenning, David P.},
abstractNote = {Optoelectronic devices based on hybrid perovskites have demonstrated outstanding performance within a few years of intense study. However, commercialization of these devices requires barriers to their development to be overcome, such as their chemical instability under operating conditions. In order to investigate this instability and its consequences, the electric field applied to single crystals of methylammonium lead bromide (CH3NH3PbBr3) is varied, and changes are mapped in both their elemental composition and photo-luminescence. Synchrotron-based nanoprobe X-ray fluorescence (nano-XRF) with 250 nm resolution reveals quasi-reversible field-assisted halide migration, with corresponding changes in photoluminescence. It is observed that higher local bromide concentration is correlated to superior optoelectronic performance in CH3NH3PbBr3. A lower limit on the electromigration rate is calculated from these experiments and the motion is interpreted as vacancy-mediated migration based on nudged elastic band density functional theory (DFT) simulations. The XRF mapping data provide direct evidence of field-assisted ionic migration in a model hybrid-perovskite thin single crystal, while the link with photoluminescence proves that the halide stoichiometry plays a key role in the optoelectronic properties of the perovskite.},
doi = {10.1002/adma.201703451},
journal = {Advanced Materials},
number = 43,
volume = 29,
place = {United States},
year = {2017},
month = {9}
}

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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

Self-Regulation Mechanism for Charged Point Defects in Hybrid Halide Perovskites
journal, December 2014

  • Walsh, Aron; Scanlon, David O.; Chen, Shiyou
  • Angewandte Chemie International Edition, Vol. 54, Issue 6
  • DOI: 10.1002/anie.201409740

Effects of Light and Electron Beam Irradiation on Halide Perovskites and Their Solar Cells
journal, January 2016


Fast self-diffusion of ions in CH 3 NH 3 PbI 3 : the interstiticaly mechanism versus vacancy-assisted mechanism
journal, January 2016

  • Yang, Ji-Hui; Yin, Wan-Jian; Park, Ji-Sang
  • Journal of Materials Chemistry A, Vol. 4, Issue 34
  • DOI: 10.1039/C6TA03599J

Chemical Analysis of Inorganic and Organic Surfaces and Thin Films by Static Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS)
journal, June 1994

  • Benninghoven, Alfred
  • Angewandte Chemie International Edition in English, Vol. 33, Issue 10
  • DOI: 10.1002/anie.199410231

Not All That Glitters Is Gold: Metal-Migration-Induced Degradation in Perovskite Solar Cells
journal, May 2016

  • Domanski, Konrad; Correa-Baena, Juan-Pablo; Mine, Nicolas
  • ACS Nano, Vol. 10, Issue 6
  • DOI: 10.1021/acsnano.6b02613

Photo-induced halide redistribution in organic–inorganic perovskite films
journal, May 2016

  • deQuilettes, Dane W.; Zhang, Wei; Burlakov, Victor M.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11683

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

Improving the Photoluminescence Properties of Perovskite CH 3 NH 3 PbBr 3-x Cl x Films by Modulating Organic Cation and Chlorine Concentrations
journal, May 2016

  • Yan, Jun; Zhang, Bing; Chen, Yunlin
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 20
  • DOI: 10.1021/acsami.6b01303

High Tolerance to Iron Contamination in Lead Halide Perovskite Solar Cells
journal, July 2017


Iodine Migration and its Effect on Hysteresis in Perovskite Solar Cells
journal, January 2016

  • Li, Cheng; Tscheuschner, Steffen; Paulus, Fabian
  • Advanced Materials, Vol. 28, Issue 12
  • DOI: 10.1002/adma.201503832

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


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

The rapid evolution of highly efficient perovskite solar cells
journal, January 2017

  • Correa-Baena, Juan-Pablo; Abate, Antonio; Saliba, Michael
  • Energy & Environmental Science, Vol. 10, Issue 3
  • DOI: 10.1039/C6EE03397K

Modeling Anomalous Hysteresis in Perovskite Solar Cells
journal, September 2015

  • van Reenen, Stephan; Kemerink, Martijn; Snaith, Henry J.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 19
  • DOI: 10.1021/acs.jpclett.5b01645

Unreacted PbI 2 as a Double-Edged Sword for Enhancing the Performance of Perovskite Solar Cells
journal, August 2016

  • Jacobsson, T. Jesper; Correa-Baena, Juan-Pablo; Halvani Anaraki, Elham
  • Journal of the American Chemical Society, Vol. 138, Issue 32
  • DOI: 10.1021/jacs.6b06320

Heterojunction Modification for Highly Efficient Organic–Inorganic Perovskite Solar Cells
journal, November 2014

  • Wojciechowski, Konrad; Stranks, Samuel D.; Abate, Antonio
  • ACS Nano, Vol. 8, Issue 12
  • DOI: 10.1021/nn505723h

Field Control of the Quantum Efficiency of Radiative Recombination in Semiconductors
journal, May 1965


Intrinsic Thermal Instability of Methylammonium Lead Trihalide Perovskite
journal, June 2015

  • Conings, Bert; Drijkoningen, Jeroen; Gauquelin, Nicolas
  • Advanced Energy Materials, Vol. 5, Issue 15
  • DOI: 10.1002/aenm.201500477

Lead halide perovskite nanowire lasers with low lasing thresholds and high quality factors
journal, April 2015

  • Zhu, Haiming; Fu, Yongping; Meng, Fei
  • Nature Materials, Vol. 14, Issue 6
  • DOI: 10.1038/nmat4271

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


Rational Composition Optimization of the Lithium-Rich Li 3 OCl 1– x Br x Anti-Perovskite Superionic Conductors
journal, May 2015


A hard X-ray nanoprobe beamline for nanoscale microscopy
journal, September 2012

  • Winarski, Robert P.; Holt, Martin V.; Rose, Volker
  • Journal of Synchrotron Radiation, Vol. 19, Issue 6
  • DOI: 10.1107/S0909049512036783

Direct Experimental Evidence for Photoinduced Strong-Coupling Polarons in Organolead Halide Perovskite Nanoparticles
journal, November 2016

  • Zheng, Kaibo; Abdellah, Mohamed; Zhu, Qiushi
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 22
  • DOI: 10.1021/acs.jpclett.6b02046

The Importance of Moisture in Hybrid Lead Halide Perovskite Thin Film Fabrication
journal, August 2015

  • Eperon, Giles E.; Habisreutinger, Severin N.; Leijtens, Tomas
  • ACS Nano, Vol. 9, Issue 9
  • DOI: 10.1021/acsnano.5b03626

Radiative efficiency of state-of-the-art photovoltaic cells
journal, September 2011

  • Green, Martin A.
  • Progress in Photovoltaics: Research and Applications, Vol. 20, Issue 4, p. 472-476
  • DOI: 10.1002/pip.1147

Growth and Characterization of PDMS-Stamped Halide Perovskite Single Microcrystals
journal, March 2016

  • Khoram, Parisa; Brittman, Sarah; Dzik, Wojciech I.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 12
  • DOI: 10.1021/acs.jpcc.6b02011

Oxygen Ion Migration in Perovskite-Type Oxides
journal, August 1995

  • Cherry, M.; Islam, M. S.; Catlow, C. R. A.
  • Journal of Solid State Chemistry, Vol. 118, Issue 1
  • DOI: 10.1006/jssc.1995.1320

Spatially Heterogeneous Chlorine Incorporation in Organic–Inorganic Perovskite Solar Cells
journal, September 2016


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

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

Engineering solar cells based on correlative X-ray microscopy
journal, May 2017

  • Stuckelberger, Michael; West, Bradley; Nietzold, Tara
  • Journal of Materials Research, Vol. 32, Issue 10
  • DOI: 10.1557/jmr.2017.108

Bias‐dependent photoluminescence intensities in n ‐InP Schottky diodes
journal, December 1980

  • Ando, Koushi; Yamamoto, Akio; Yamaguchi, Masafumi
  • Journal of Applied Physics, Vol. 51, Issue 12
  • DOI: 10.1063/1.327595

Voltage dependent electromodulated photoluminescence of chalcopyrite solar cells
journal, September 2003

  • Beckers, I. E.; Fiedeler, U.; Siebentritt, S.
  • Journal of Physics and Chemistry of Solids, Vol. 64, Issue 9-10
  • DOI: 10.1016/S0022-3697(03)00091-X

Disordered Configuration of Methylammonium of CH 3 NH 3 PbBr 3 Determined by Single Crystal Neutron Diffractometry
journal, March 2007