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Title: Electrochemical Hole Injection Selectively Expels Iodide from Mixed Halide Perovskite Films

Abstract

Halide ion mobility in metal halide perovskites remains an intriguing phenomenon, influencing their optical and photovoltaic properties. Selective injection of holes through electrochemical anodic bias has allowed us to probe the effect of hole trapping at iodide (0.9 V) and bromide (1.15 V) in mixed halide perovskite (CH3NH3PbBr1.5I1.5) films. Upon trapping holes at the iodide site, the iodide gradually gets expelled from the mixed halide film (as iodine and/or triiodide ion), leaving behind re-formed CH3NH3PbBr3 domains. The weakening of the Pb-I bond following the hole trapping (oxidation of the iodide site) and its expulsion from the lattice in the form of iodine provided further insight into the photoinduced segregation of halide ions in mixed halide perovskite films. Transient absorption spectroscopy revealed that the iodide expulsion process leaves a defect-rich perovskite lattice behind as charge carrier recombination in the re-formed lattice is greatly accelerated. The selective mobility of iodide species provides insight into the photoinduced phase segregation and its implication in the stable operation of perovskite solar cells.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [6]
  1. Department of Physical Chemistry and Materials Science, Interdisciplinary Excellence Centre, University of Szeged, Rerrich Square 1, Szeged, H-6720, Hungary, ELI-ALPS Research Institute, Dugonics Square 13, Szeged, 6720, Hungary, Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States
  2. Department of Physical Chemistry and Materials Science, Interdisciplinary Excellence Centre, University of Szeged, Rerrich Square 1, Szeged, H-6720, Hungary
  3. Department of Chemistry, Biology and Biotechnology, University of Perugia, Via Elce di Sotto, 8I-06123 Perugia, Italy, Computational Laboratory for Hybrid/Organic Photovoltaics (CLHYO), CNR-ISTM, Via Elce di Sotto 8, 06123 Perugia, Italy, CompuNet, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy
  4. Computational Laboratory for Hybrid/Organic Photovoltaics (CLHYO), CNR-ISTM, Via Elce di Sotto 8, 06123 Perugia, Italy, CompuNet, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy
  5. Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States, Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556, United States
  6. Department of Physical Chemistry and Materials Science, Interdisciplinary Excellence Centre, University of Szeged, Rerrich Square 1, Szeged, H-6720, Hungary, ELI-ALPS Research Institute, Dugonics Square 13, Szeged, 6720, Hungary
Publication Date:
Research Org.:
Univ. of Szeged (Hungary)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1530479
Alternate Identifier(s):
OSTI ID: 1542124
Grant/Contract Number:  
FC02-04ER15533
Resource Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society Journal Volume: 141 Journal Issue: 27; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Samu, Gergely F., Balog, Ádám, De Angelis, Filippo, Meggiolaro, Daniele, Kamat, Prashant V., and Janáky, Csaba. Electrochemical Hole Injection Selectively Expels Iodide from Mixed Halide Perovskite Films. United States: N. p., 2019. Web. https://doi.org/10.1021/jacs.9b04568.
Samu, Gergely F., Balog, Ádám, De Angelis, Filippo, Meggiolaro, Daniele, Kamat, Prashant V., & Janáky, Csaba. Electrochemical Hole Injection Selectively Expels Iodide from Mixed Halide Perovskite Films. United States. https://doi.org/10.1021/jacs.9b04568
Samu, Gergely F., Balog, Ádám, De Angelis, Filippo, Meggiolaro, Daniele, Kamat, Prashant V., and Janáky, Csaba. Wed . "Electrochemical Hole Injection Selectively Expels Iodide from Mixed Halide Perovskite Films". United States. https://doi.org/10.1021/jacs.9b04568.
@article{osti_1530479,
title = {Electrochemical Hole Injection Selectively Expels Iodide from Mixed Halide Perovskite Films},
author = {Samu, Gergely F. and Balog, Ádám and De Angelis, Filippo and Meggiolaro, Daniele and Kamat, Prashant V. and Janáky, Csaba},
abstractNote = {Halide ion mobility in metal halide perovskites remains an intriguing phenomenon, influencing their optical and photovoltaic properties. Selective injection of holes through electrochemical anodic bias has allowed us to probe the effect of hole trapping at iodide (0.9 V) and bromide (1.15 V) in mixed halide perovskite (CH3NH3PbBr1.5I1.5) films. Upon trapping holes at the iodide site, the iodide gradually gets expelled from the mixed halide film (as iodine and/or triiodide ion), leaving behind re-formed CH3NH3PbBr3 domains. The weakening of the Pb-I bond following the hole trapping (oxidation of the iodide site) and its expulsion from the lattice in the form of iodine provided further insight into the photoinduced segregation of halide ions in mixed halide perovskite films. Transient absorption spectroscopy revealed that the iodide expulsion process leaves a defect-rich perovskite lattice behind as charge carrier recombination in the re-formed lattice is greatly accelerated. The selective mobility of iodide species provides insight into the photoinduced phase segregation and its implication in the stable operation of perovskite solar cells.},
doi = {10.1021/jacs.9b04568},
journal = {Journal of the American Chemical Society},
number = 27,
volume = 141,
place = {United States},
year = {2019},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/jacs.9b04568

Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: (A) Linear sweep voltammograms of FTO/MAPbBrxI3−x films in 0.1 M Bu4NPF6/DCM electrolyte (5 mV s−1 sweep rate). (B) Band diagram of MAPbBr1.5I1.5 together with the peak onset of the observed Faradaic events. (C) Variation of the peak currents of the first two redox waves as a function ofmore » MHP composition, with solid lines to guide the eye.« less

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Works referenced in this record:

Chemical Management for Colorful, Efficient, and Stable Inorganic–Organic Hybrid Nanostructured Solar Cells
journal, March 2013

  • Noh, Jun Hong; Im, Sang Hyuk; Heo, Jin Hyuck
  • Nano Letters, Vol. 13, Issue 4, p. 1764-1769
  • DOI: 10.1021/nl400349b

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

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

  • Zhou, Chunhua; Ou, Qingdong; Chen, Weijian
  • Advanced Optical Materials, Vol. 6, Issue 24
  • DOI: 10.1002/adom.201801107

Modulation of Charge Recombination in CsPbBr 3 Perovskite Films with Electrochemical Bias
journal, November 2017

  • Scheidt, Rebecca A.; Samu, Gergely F.; Janáky, Csaba
  • Journal of the American Chemical Society, Vol. 140, Issue 1
  • DOI: 10.1021/jacs.7b10958

Quantification of Ionic Diffusion in Lead Halide Perovskite Single Crystals
journal, May 2018


First-Principles Modeling of Defects in Lead Halide Perovskites: Best Practices and Open Issues
journal, August 2018


Modeling the Interaction of Molecular Iodine with MAPbI 3 : A Probe of Lead-Halide Perovskites Defect Chemistry
journal, January 2018


23.6%-efficient monolithic perovskite/silicon tandem solar cells with improved stability
journal, February 2017

  • Bush, Kevin A.; Palmstrom, Axel F.; Yu, Zhengshan J.
  • Nature Energy, Vol. 2, Issue 4
  • DOI: 10.1038/nenergy.2017.9

Four-Terminal All-Perovskite Tandem Solar Cells Achieving Power Conversion Efficiencies Exceeding 23%
journal, January 2018


Opportunities and challenges for tandem solar cells using metal halide perovskite semiconductors
journal, July 2018


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

Shift Happens . How Halide Ion Defects Influence Photoinduced Segregation in Mixed Halide Perovskites
journal, June 2017


A Victim of Halide Ion Segregation. How Light Soaking Affects Solar Cell Performance of Mixed Halide Lead Perovskites
journal, July 2017


Electrochemistry and Spectroelectrochemistry of Lead Halide Perovskite Films: Materials Science Aspects and Boundary Conditions
journal, December 2017


Large tunable photoeffect on ion conduction in halide perovskites and implications for photodecomposition
journal, March 2018


Local Observation of Phase Segregation in Mixed-Halide Perovskite
journal, February 2018


Vacancy-Mediated Anion Photosegregation Kinetics in Mixed Halide Hybrid Perovskites: Coupled Kinetic Monte Carlo and Optical Measurements
journal, September 2018


Transformation of Sintered CsPbBr 3 Nanocrystals to Cubic CsPbI 3 and Gradient CsPbBr x I 3– x through Halide Exchange
journal, June 2016

  • Hoffman, Jacob B.; Schleper, A. Lennart; Kamat, Prashant V.
  • Journal of the American Chemical Society, Vol. 138, Issue 27
  • DOI: 10.1021/jacs.6b04661

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


Ion Migration in Organometal Trihalide Perovskite and Its Impact on Photovoltaic Efficiency and Stability
journal, January 2016


Defect-Assisted Photoinduced Halide Segregation in Mixed-Halide Perovskite Thin Films
journal, May 2017


Impact of Surfaces on Photoinduced Halide Segregation in Mixed-Halide Perovskites
journal, October 2018


Light-Induced Phase Segregation in Halide-Perovskite Absorbers
journal, November 2016


Controlling the Phase Segregation in Mixed Halide Perovskites through Nanocrystal Size
journal, November 2018


To Exchange or Not to Exchange . Suppressing Anion Exchange in Cesium Lead Halide Perovskites with PbSO 4 –Oleate Capping
journal, March 2018


How Lead Halide Complex Chemistry Dictates the Composition of Mixed Halide Perovskites
journal, March 2016

  • Yoon, Seog Joon; Stamplecoskie, Kevin G.; Kamat, Prashant V.
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 7
  • DOI: 10.1021/acs.jpclett.6b00433

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

Electronic Traps and Phase Segregation in Lead Mixed-Halide Perovskite
journal, November 2018


Current-Induced Phase Segregation in Mixed Halide Hybrid Perovskites and its Impact on Two-Terminal Tandem Solar Cell Design
journal, July 2017


Iodine chemistry determines the defect tolerance of lead-halide perovskites
journal, January 2018

  • Meggiolaro, Daniele; Motti, Silvia G.; Mosconi, Edoardo
  • Energy & Environmental Science, Vol. 11, Issue 3
  • DOI: 10.1039/C8EE00124C

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


Stabilized Wide Bandgap MAPbBr x I 3- x Perovskite by Enhanced Grain Size and Improved Crystallinity
journal, December 2015


Rationalizing the light-induced phase separation of mixed halide organic–inorganic perovskites
journal, August 2017


Cesium Lead Halide Perovskites with Improved Stability for Tandem Solar Cells
journal, February 2016

  • Beal, Rachel E.; Slotcavage, Daniel J.; Leijtens, Tomas
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 5
  • DOI: 10.1021/acs.jpclett.6b00002

Excess charge-carrier induced instability of hybrid perovskites
journal, November 2018


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

  • Stranks, S. D.; Eperon, G. E.; Grancini, G.
  • Science, Vol. 342, Issue 6156, p. 341-344
  • DOI: 10.1126/science.1243982

Long-Range Balanced Electron- and Hole-Transport Lengths in Organic-Inorganic CH3NH3PbI3
journal, October 2013


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


Making and Breaking of Lead Halide Perovskites
journal, January 2016

  • Manser, Joseph S.; Saidaminov, Makhsud I.; Christians, Jeffrey A.
  • Accounts of Chemical Research, Vol. 49, Issue 2
  • DOI: 10.1021/acs.accounts.5b00455

Light and Electrically Induced Phase Segregation and Its Impact on the Stability of Quadruple Cation High Bandgap Perovskite Solar Cells
journal, August 2017

  • Duong, The; Mulmudi, Hemant Kumar; Wu, YiLiang
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 32
  • DOI: 10.1021/acsami.7b06816

Tunable Polaron Distortions Control the Extent of Halide Demixing in Lead Halide Perovskites
journal, June 2018

  • Bischak, Connor G.; Wong, Andrew B.; Lin, Elbert
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 14
  • DOI: 10.1021/acs.jpclett.8b01512

Halogen Migration in Hybrid Perovskites: The Organic Cation Matters
journal, September 2018

  • Oranskaia, Aleksandra; Yin, Jun; Bakr, Osman M.
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 18
  • DOI: 10.1021/acs.jpclett.8b02522

A mixed-cation lead mixed-halide perovskite absorber for tandem solar cells
journal, January 2016


The Bandgap as a Moving Target: Reversible Bandgap Instabilities in Multiple-Cation Mixed-Halide Perovskite Solar Cells
journal, November 2018


Perovskite-perovskite tandem photovoltaics with optimized band gaps
journal, October 2016


Tracking Iodide and Bromide Ion Segregation in Mixed Halide Lead Perovskites during Photoirradiation
journal, June 2016


Visualizing Phase Segregation in Mixed-Halide Perovskite Single Crystals
journal, January 2019

  • Mao, Wenxin; Hall, Christopher R.; Chesman, Anthony S. R.
  • Angewandte Chemie International Edition, Vol. 58, Issue 9
  • DOI: 10.1002/anie.201810193

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