Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

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

Journal Article · · APL Materials
DOI: https://doi.org/10.1063/1.5083812 · OSTI ID:1510426
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
+ Show Author Affiliations

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.

Research Organization:
National Renewable Energy Laboratory (NREL), Golden, CO (United States); Princeton Univ., NJ (United States); CNRS Ile-de-France Photovoltaic Inst. (IPVF), Palaiseau (France)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Solar Energy Technologies Office; Office of Naval Research (ONR) (United States); National Research Agency (ANR) (France)
Grant/Contract Number:
AC36-08GO28308; N00014-17-1-2005; ANR-17-MPGA-0012; SC00014664
OSTI ID:
1510426
Alternate ID(s):
OSTI ID: 1504999
Report Number(s):
NREL/JA-5K00-73840
Journal Information:
APL Materials, Vol. 7, Issue 4; ISSN 2166-532X
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 68 works
Citation information provided by
Web of Science

References (42)

Recent Advances in Perovskite Micro- and Nanolasers journal June 2018
Solution-Grown Monocrystalline Hybrid Perovskite Films for Hole-Transporter-Free Solar Cells journal March 2016
Light-Induced Degradation of CH 3 NH 3 PbI 3 Hybrid Perovskite Thin Film journal February 2017
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
Not All That Glitters Is Gold: Metal-Migration-Induced Degradation in Perovskite Solar Cells journal May 2016
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
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
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
Anodic underpotential deposition and cathodic stripping of iodine at polycrystalline and single-crystal gold: studies by LEED, AES, XPS, and electrochemistry journal June 1991
On the Thermal and Thermodynamic (In)Stability of Methylammonium Lead Halide Perovskites journal August 2016
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
Electric-Field-Driven Reversible Conversion Between Methylammonium Lead Triiodide Perovskites and Lead Iodide at Elevated Temperatures journal December 2015
Giant switchable photovoltaic effect in organometal trihalide perovskite devices journal December 2014
Air-Exposure Induced Dopant Redistribution and Energy Level Shifts in Spin-Coated Spiro-MeOTAD Films journal January 2015
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
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
Non-nanogold catalyzed aerobic oxidation of secondary amines to imines journal January 2007
Strong Covalency-Induced Recombination Centers in Perovskite Solar Cell Material CH 3 NH 3 PbI 3 journal October 2014
Surface coordination chemistry of noble-metal electrocatalysts: Oxidative addition and reductive elimination of iodide at iridium, platinum and gold in aqueous solutions journal August 1988
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
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
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
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
Underpotential Deposition and Adsorption of Lead on Gold Polycrystalline Electrodes: I. XPS and TOF-SIMS Investigations in 0.1 M NaCl Electrolytes journal January 1999
Review—SEI: Past, Present and Future journal January 2017
Non-Nanogold Catalyzed Aerobic Oxidation of Secondary Amines to Imines. journal October 2007
Complexities of Contact Potential Difference Measurements on Metal Halide Perovskite Surfaces conference December 2019

Cited By (6)

Optically Pumped Lasing from Hybrid Perovskite Light‐Emitting Diodes journal November 2019
Enhanced Nucleation of Atomic Layer Deposited Contacts Improves Operational Stability of Perovskite Solar Cells in Air journal October 2019
Quantifying Charge‐Carrier Mobilities and Recombination Rates in Metal Halide Perovskites from Time‐Resolved Microwave Photoconductivity Measurements journal February 2020
Understanding the mechanism of metal-induced degradation in perovskite nanocrystals journal January 2019
Perovskite semiconductors for next generation optoelectronic applications journal August 2019
Operational stability of perovskite light emitting diodes journal January 2020

Figures / Tables (7)

FIG. 1(p. 3)figure FIG. 1
FIG. 2(p. 4)figure FIG. 2
FIG. 3(p. 5)figure FIG. 3
FIG. 4(p. 5)figure FIG. 4
FIG. 5(p. 6)figure FIG. 5
FIG. 6(p. 7)figure FIG. 6
FIG. 7(p. 8)figure FIG. 7

Similar Records

Related Subjects

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