skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Reactions at noble metal contacts with methylammonium lead triiodide perovskites: Role of underpotential deposition and electrochemistry

Abstract

Chemical reactivity of halide perovskites coupled with a low energy of formation makes it a challenge to characterize material properties and achieve long-term device stability. In this study, we elucidate electrochemical reactions occurring at the methylammonium lead triiodide (MAPbI3)/Au interface. X-ray photoemission spectroscopy is used to identify a type of reduction/oxidation reaction termed underpotential deposition (UPD) involving lead, iodine, and hydrogen occurring at interfaces with noble metals. Changes in surface compositions and oxidation states suggest that UPD derived adsorbates at MAPbI3/Au interfaces lower the energy barrier for release of volatile HI and/or I2 catalyzing degradation at exposed contacts. Additionally, comparison to PbI2/Au interfaces demonstrates that the presence of methylammonium/methylamine accelerates the formation of a Pb0 adlayer on the Au. Reactions involving UPD Pb0 can transform the typically anodic (hole collecting) Au to a cathode in a photovoltaic measurement. Cyclic voltammetry reveals electrochemical reaction peaks in indium tin oxide (ITO)/MAPbI3/Au devices occurring within voltage ranges commonly used for perovskite characterization. The electrochemical stability window of this device architecture is measured to be between -0.5 V and 0.9 V. Voltage induced interfacial reactions contribute to reversible electrochemical peaks, hysteresis, switchable perovskite diode polarity, and permanent degradation at larger voltages. These types ofmore » surface reactions alter the interface/interphase composition beyond ion accumulation, provide a source for the diffusion of defects, and contribute to electrode material dependent current-voltage hysteresis. Moreover, the results imply fundamental limitations to achieving high device stability with noble metals and/or methylammonium containing perovskites.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [1]; ORCiD logo [6]; ORCiD logo [6]; ORCiD logo [7]
  1. Princeton Univ., NJ (United States). Dept. of Electrical Engineering
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States); CNRS Ile-de-France Photovoltaic Inst. (IPVF), Palaiseau (France)
  3. National Renewable Energy Lab. (NREL), Golden, CO (United States); Hope College, Holland, MI (United States). Dept. of Engineering
  4. National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States). Materials Science and Engineering Program. Renewable and Sustainable Energy Inst.
  5. National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States). Dept. of Electrical, Computer, and Energy Engineering
  6. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  7. Princeton Univ., NJ (United States). Dept. of Electrical Engineering. Andlinger Center for Energy and the Environment
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States); Princeton Univ., NJ (United States); CNRS Ile-de-France Photovoltaic Inst. (IPVF), Palaiseau (France)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Solar Energy Technologies Office (EE-4S); Office of Naval Research (ONR) (United States); National Research Agency (ANR) (France)
OSTI Identifier:
1510426
Alternate Identifier(s):
OSTI ID: 1504999
Report Number(s):
NREL/JA-5K00-73840
Journal ID: ISSN 2166-532X
Grant/Contract Number:  
AC36-08GO28308; N00014-17-1-2005; ANR-17-MPGA-0012; SC00014664
Resource Type:
Accepted Manuscript
Journal Name:
APL Materials
Additional Journal Information:
Journal Volume: 7; Journal Issue: 4; Journal ID: ISSN 2166-532X
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; chemical compounds and components; electrodeposition; electrochemistry; chemical elements; reaction mechanisms; interphases; perovskites; electrical properties and parameters; electrochemical reactions

Citation Formats

Kerner, Ross A., Schulz, Philip, Christians, Jeffrey A., Dunfield, Sean P., Dou, Benjia, Zhao, Lianfeng, Teeter, Glenn, Berry, Joseph J., and Rand, Barry P. Reactions at noble metal contacts with methylammonium lead triiodide perovskites: Role of underpotential deposition and electrochemistry. United States: N. p., 2019. Web. doi:10.1063/1.5083812.
Kerner, Ross A., Schulz, Philip, Christians, Jeffrey A., Dunfield, Sean P., Dou, Benjia, Zhao, Lianfeng, Teeter, Glenn, Berry, Joseph J., & Rand, Barry P. Reactions at noble metal contacts with methylammonium lead triiodide perovskites: Role of underpotential deposition and electrochemistry. United States. doi:10.1063/1.5083812.
Kerner, Ross A., Schulz, Philip, Christians, Jeffrey A., Dunfield, Sean P., Dou, Benjia, Zhao, Lianfeng, Teeter, Glenn, Berry, Joseph J., and Rand, Barry P. Thu . "Reactions at noble metal contacts with methylammonium lead triiodide perovskites: Role of underpotential deposition and electrochemistry". United States. doi:10.1063/1.5083812. https://www.osti.gov/servlets/purl/1510426.
@article{osti_1510426,
title = {Reactions at noble metal contacts with methylammonium lead triiodide perovskites: Role of underpotential deposition and electrochemistry},
author = {Kerner, Ross A. and Schulz, Philip and Christians, Jeffrey A. and Dunfield, Sean P. and Dou, Benjia and Zhao, Lianfeng and Teeter, Glenn and Berry, Joseph J. and Rand, Barry P.},
abstractNote = {Chemical reactivity of halide perovskites coupled with a low energy of formation makes it a challenge to characterize material properties and achieve long-term device stability. In this study, we elucidate electrochemical reactions occurring at the methylammonium lead triiodide (MAPbI3)/Au interface. X-ray photoemission spectroscopy is used to identify a type of reduction/oxidation reaction termed underpotential deposition (UPD) involving lead, iodine, and hydrogen occurring at interfaces with noble metals. Changes in surface compositions and oxidation states suggest that UPD derived adsorbates at MAPbI3/Au interfaces lower the energy barrier for release of volatile HI and/or I2 catalyzing degradation at exposed contacts. Additionally, comparison to PbI2/Au interfaces demonstrates that the presence of methylammonium/methylamine accelerates the formation of a Pb0 adlayer on the Au. Reactions involving UPD Pb0 can transform the typically anodic (hole collecting) Au to a cathode in a photovoltaic measurement. Cyclic voltammetry reveals electrochemical reaction peaks in indium tin oxide (ITO)/MAPbI3/Au devices occurring within voltage ranges commonly used for perovskite characterization. The electrochemical stability window of this device architecture is measured to be between -0.5 V and 0.9 V. Voltage induced interfacial reactions contribute to reversible electrochemical peaks, hysteresis, switchable perovskite diode polarity, and permanent degradation at larger voltages. These types of surface reactions alter the interface/interphase composition beyond ion accumulation, provide a source for the diffusion of defects, and contribute to electrode material dependent current-voltage hysteresis. Moreover, the results imply fundamental limitations to achieving high device stability with noble metals and/or methylammonium containing perovskites.},
doi = {10.1063/1.5083812},
journal = {APL Materials},
number = 4,
volume = 7,
place = {United States},
year = {2019},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Figures / Tables:

FIG. 1 FIG. 1: Consecutive XPS measurements of the Pb 4f region of (a) MAPbI3 and (b) PbI2 coated with thick (50 nm) Au films.

Save / Share:

Works referenced in this record:

Recent Advances in Perovskite Micro- and Nanolasers
journal, June 2018

  • Wang, Kaiyang; Wang, Shuai; Xiao, Shumin
  • Advanced Optical Materials, Vol. 6, Issue 18
  • DOI: 10.1002/adom.201800278

Solution-Grown Monocrystalline Hybrid Perovskite Films for Hole-Transporter-Free Solar Cells
journal, March 2016

  • Peng, Wei; Wang, Lingfei; Murali, Banavoth
  • Advanced Materials, Vol. 28, Issue 17
  • DOI: 10.1002/adma.201506292

Light-Induced Degradation of CH 3 NH 3 PbI 3 Hybrid Perovskite Thin Film
journal, February 2017

  • Li, Youzhen; Xu, Xuemei; Wang, Congcong
  • The Journal of Physical Chemistry C, Vol. 121, Issue 7
  • DOI: 10.1021/acs.jpcc.6b11853

Organic-Inorganic Hybrid Halide Perovskites for Memories, Transistors, and Artificial Synapses
journal, May 2018


Direct Observation of Halide Migration and its Effect on the Photoluminescence of Methylammonium Lead Bromide Perovskite Single Crystals
journal, September 2017

  • Luo, Yanqi; Khoram, Parisa; Brittman, Sarah
  • Advanced Materials, Vol. 29, Issue 43
  • DOI: 10.1002/adma.201703451

Influence of mobile ions on the electroluminescence characteristics of methylammonium lead iodide perovskite diodes
journal, January 2016

  • Bandiello, Enrico; Ávila, Jorge; Gil-Escrig, Lidón
  • Journal of Materials Chemistry A, Vol. 4, Issue 47
  • DOI: 10.1039/c6ta06854e

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

Tailored interfaces of unencapsulated perovskite solar cells for >1,000 hour operational stability
journal, January 2018


Extended carrier lifetimes and diffusion in hybrid perovskites revealed by Hall effect and photoconductivity measurements
journal, August 2016


Reductive Desorption of Iodine Chemisorbed on Smooth Polycrystalline Gold Electrodes
journal, January 1988

  • Rodriguez, Jose F.
  • Journal of The Electrochemical Society, Vol. 135, Issue 3
  • DOI: 10.1149/1.2095673

Ionic–Electronic Ambipolar Transport in Metal Halide Perovskites: Can Electronic Conductivity Limit Ionic Diffusion?
journal, December 2017


Hydrogenative/cathodic stripping of iodine chemisorbed on smooth polycrystalline platinum electrodes
journal, March 1987

  • Mebrahtu, Thomas; Rodriguez, Jose F.; Bravo, Beatriz G.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 219, Issue 1-2
  • DOI: 10.1016/0022-0728(87)85050-7

Stability in Perovskite Photovoltaics: A Paradigm for Newfangled Technologies
journal, August 2018


Redox Chemistry Dominates the Degradation and Decomposition of Metal Halide Perovskite Optoelectronic Devices
journal, August 2016


Lead underpotential deposition on Au(110)
journal, January 2003

  • Hale, Penny; Thurgate, Stephen; Wilkie, Peter
  • Surface and Interface Analysis, Vol. 35, Issue 10
  • DOI: 10.1002/sia.1614

Anodic underpotential deposition and cathodic stripping of iodine at polycrystalline and single-crystal gold: studies by LEED, AES, XPS, and electrochemistry
journal, June 1991

  • Bravo, Beatriz G.; Michelhaugh, Susan L.; Soriaga, Manuel P.
  • The Journal of Physical Chemistry, Vol. 95, Issue 13
  • DOI: 10.1021/j100166a060

On the Thermal and Thermodynamic (In)Stability of Methylammonium Lead Halide Perovskites
journal, August 2016

  • Brunetti, Bruno; Cavallo, Carmen; Ciccioli, Andrea
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep31896

Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design
journal, March 2016


Large-area perovskite solar cells – a review of recent progress and issues
journal, January 2018

  • Chen, Yichuan; Zhang, Linrui; Zhang, Yongzhe
  • RSC Advances, Vol. 8, Issue 19
  • DOI: 10.1039/c8ra00384j

Electric-Field-Driven Reversible Conversion Between Methylammonium Lead Triiodide Perovskites and Lead Iodide at Elevated Temperatures
journal, December 2015

  • Yuan, Yongbo; Wang, Qi; Shao, Yuchuan
  • Advanced Energy Materials, Vol. 6, Issue 2
  • DOI: 10.1002/aenm.201501803

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

Air-Exposure Induced Dopant Redistribution and Energy Level Shifts in Spin-Coated Spiro-MeOTAD Films
journal, January 2015

  • Hawash, Zafer; Ono, Luis K.; Raga, Sonia R.
  • Chemistry of Materials, Vol. 27, Issue 2
  • DOI: 10.1021/cm504022q

Metal Halide Perovskites: From Crystal Formations to Light-Emitting-Diode Applications
journal, July 2018


Photodecomposition and thermal decomposition in methylammonium halide lead perovskites and inferred design principles to increase photovoltaic device stability
journal, January 2018

  • Juarez-Perez, Emilio J.; Ono, Luis K.; Maeda, Maki
  • Journal of Materials Chemistry A, Vol. 6, Issue 20
  • DOI: 10.1039/c8ta03501f

Au Exchange or Au Deposition: Dual Reaction Pathways in Au–CsPbBr 3 Heterostructure Nanoparticles
journal, August 2017


Evidence of band bending induced by hole trapping at MAPbI 3 perovskite/metal interface
journal, January 2016

  • Chen, Y. -F.; Tsai, Y. -T.; Bassani, D. M.
  • Journal of Materials Chemistry A, Vol. 4, Issue 44
  • DOI: 10.1039/c6ta08979h

Non-nanogold catalyzed aerobic oxidation of secondary amines to imines
journal, January 2007

  • Zhu, Bolin; Angelici, Robert J.
  • Chemical Communications, Issue 21
  • DOI: 10.1039/b700555e

Strong Covalency-Induced Recombination Centers in Perovskite Solar Cell Material CH 3 NH 3 PbI 3
journal, October 2014

  • Agiorgousis, Michael L.; Sun, Yi-Yang; Zeng, Hao
  • Journal of the American Chemical Society, Vol. 136, Issue 41
  • DOI: 10.1021/ja5079305

The Bromine Electrode. Part I: Adsorption Phenomena at Polycrystalline Platinum Electrodes
journal, October 2004


Interface-Dependent Ion Migration/Accumulation Controls Hysteresis in MAPbI 3 Solar Cells
journal, July 2016

  • Levine, Igal; Nayak, Pabitra K.; Wang, Jacob Tse-Wei
  • The Journal of Physical Chemistry C, Vol. 120, Issue 30
  • DOI: 10.1021/acs.jpcc.6b04233

The metal-solid electrolyte interphase
journal, May 1974


Thermodynamics and the Intrinsic Stability of Lead Halide Perovskites CH 3 NH 3 PbX 3
journal, June 2018


Investigating the Role of 4- Tert Butylpyridine in Perovskite Solar Cells
journal, September 2016

  • Habisreutinger, Severin N.; Noel, Nakita K.; Snaith, Henry J.
  • Advanced Energy Materials, Vol. 7, Issue 1
  • DOI: 10.1002/aenm.201601079

Ethanol dehydrogenation by gold catalysts: The effect of the gold particle size and the presence of oxygen
journal, June 2009


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


Underpotential Deposition at Single Crystal Surfaces of Au, Pt, Ag and Other Materials
journal, July 2001

  • Herrero, Enrique; Buller, Lisa J.; Abruña, Héctor D.
  • Chemical Reviews, Vol. 101, Issue 7
  • DOI: 10.1021/cr9600363

Interface Design for Metal Halide Perovskite Solar Cells
journal, May 2018


Complexities of Contact Potential Difference Measurements on Metal Halide Perovskite Surfaces
journal, February 2019

  • Zhang, Fengyu; Ullrich, Florian; Silver, Scott
  • The Journal of Physical Chemistry Letters, Vol. 10, Issue 4
  • DOI: 10.1021/acs.jpclett.8b03878

Review—SEI: Past, Present and Future
journal, January 2017

  • Peled, E.; Menkin, S.
  • Journal of The Electrochemical Society, Vol. 164, Issue 7
  • DOI: 10.1149/2.1441707jes

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