Electrochemical Doping of Halide Perovskites by Noble Metal Interstitial Cations

Kerner, Ross A.; Cohen, Ayala V.; Xu, Zhaojian; Kirmani, Ahmad R.; Park, So Yeon; Harvey, Steven P.; Murphy, John P.; Cawthorn, Robert C.; Giebink, Noel C.; Luther, Joseph M.; Zhu, Kai; Berry, Joseph J.; Kronik, Leeor; Rand, Barry P.

doi:10.1002/adma.202302206

Title: Electrochemical Doping of Halide Perovskites by Noble Metal Interstitial Cations

Journal Article · Fri Jun 02 00:00:00 EDT 2023 · Advanced Materials

DOI:https://doi.org/10.1002/adma.202302206· OSTI ID:1983474

^[1]; Cohen, Ayala V. ^[2];

^[3];

^[1];

^[4]; Cawthorn, Robert C. ^[4];

^[4];

^[1];

^[5];

^[2];

^[6]

National Renewable Energy Laboratory Golden CO 80401 USA
Department of Molecular Chemistry and Materials Science Weizmann Institute of Science Rehovoth 76100 Israel
Department of Electrical Engineering Princeton University Princeton NJ 08544 USA
Department of Electrical Engineering The Pennsylvania State University University Park PA 16802 USA
National Renewable Energy Laboratory Golden CO 80401 USA, Department of Physics University of Colorado Boulder Boulder CO 80309 USA, Renewable and Sustainable Energy Institute University of Colorado Boulder Boulder CO 80309 USA
Department of Electrical Engineering Princeton University Princeton NJ 08544 USA, Andlinger Center for Energy and the Environment Princeton University Princeton NJ 08544 USA

Abstract Metal halide perovskites are an attractive class of semiconductors, but it has proven difficult to control their electronic doping by conventional strategies due to screening and compensation by mobile ions or ionic defects. Noble‐metal interstitials represent an under‐studied class of extrinsic defects that plausibly influence many perovskite‐based devices. In this work, doping of metal halide perovskites is studied by electrochemically formed Au ⁺ interstitial ions, combining experimental data on devices with a computational analysis of Au ⁺ interstitial defects based on density functional theory (DFT). Analysis suggests that Au ⁺ cations can be easily formed and migrate through the perovskite bulk via the same sites as iodine interstitials (I _i ⁺ ). However, whereas I _i ⁺ compensates n‐type doping by electron capture, the noble‐metal interstitials act as quasi‐stable n‐dopants. Experimentally, voltage‐dependent, dynamic doping by current density–time ( J–t ), electrochemical impedance, and photoluminescence measurements are characterized. These results provide deeper insight into the potential beneficial and detrimental impacts of metal electrode reactions on long‐term performance of perovskite photovoltaic and light‐emitting diodes, as well as offer an alternative doping explanation for the valence switching mechanism of halide‐perovskite‐based neuromorphic and memristive devices.

View Journal Article

Cite

Export

Save

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Solar Energy Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES); US Department of the Navy, Office of Naval Research (ONR); Defense Advanced Research Projects Agency (DARPA); Minerva Centre for Self-Repairing Systems for Energy & Sustainability

Grant/Contract Number:: DE‐AC36‐08GO28308; AC36-08GO28308; N00014-21-1-2767; NN66001-20-1-4052

OSTI ID:: 1983474

Alternate ID(s):: OSTI ID: 1971886; OSTI ID: 1983475

Report Number(s):: NREL/JA-5900-83484; 2302206

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Vol. 35 Journal Issue: 29; ISSN 0935-9648

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (63)

Impact of Sn doping on methylammonium lead chloride perovskite: An experimental study Sarkar, P.; Srivastava, A.; Tripathy, S. K. Journal of Applied Physics, Vol. 127, Issue 12 https://doi.org/10.1063/1.5133457	journal	March 2020
Low Threshold Voltages Electrochemically Drive Gold Migration in Halide Perovskite Devices Kerner, Ross A.; Zhao, Lianfeng; Harvey, Steven P. ACS Energy Letters, Vol. 5, Issue 11 https://doi.org/10.1021/acsenergylett.0c01805	journal	October 2020
p-Type molecular doping by charge transfer in halide perovskite Euvrard, Julie; Gunawan, Oki; Zhong, Xinjue Materials Advances, Vol. 2, Issue 9 https://doi.org/10.1039/D1MA00160D	journal	January 2021
Emerging perovskite materials for high density data storage and artificial synapses Wang, Yan; Lv, Ziyu; Zhou, Li Journal of Materials Chemistry C, Vol. 6, Issue 7 https://doi.org/10.1039/C7TC05326F	journal	January 2018
Conductivity Tuning via Doping with Electron Donating and Withdrawing Molecules in Perovskite CsPbI ₃ Nanocrystal Films Gaulding, E. Ashley; Hao, Ji; Kang, Hyun Suk Advanced Materials, Vol. 31, Issue 27 https://doi.org/10.1002/adma.201902250	journal	May 2019
The Doping Mechanism of Halide Perovskite Unveiled by Alkaline Earth Metals Phung, Nga; Félix, Roberto; Meggiolaro, Daniele Journal of the American Chemical Society, Vol. 142, Issue 5 https://doi.org/10.1021/jacs.9b11637	journal	January 2020
Electrical doping in halide perovskites Euvrard, Julie; Yan, Yanfa; Mitzi, David B. Nature Reviews Materials https://doi.org/10.1038/s41578-021-00286-z	journal	March 2021
Anchored Ligands Facilitate Efficient B-Site Doping in Metal Halide Perovskites Yang, Zhenyu; Wei, Mingyang; Voznyy, Oleksandr Journal of the American Chemical Society https://doi.org/10.1021/jacs.9b02565	journal	May 2019
Electrochemically n-Doped CsPbBr₃ Nanocrystal Thin Films Heo, Sungyeon; Roh, Kwangdong; Zhang, Fengyu ACS Energy Letters, Vol. 7, Issue 1 https://doi.org/10.1021/acsenergylett.1c02554	journal	December 2021
Electrochemical p-Doping of CsPbBr₃ Perovskite Nanocrystals Mulder, Jence T.; du Fossé, Indy; Alimoradi Jazi, Maryam ACS Energy Letters, Vol. 6, Issue 7 https://doi.org/10.1021/acsenergylett.1c00970	journal	June 2021
Deep levels in cesium lead bromide from native defects and hydrogen Swift, Michael W.; Lyons, John L. Journal of Materials Chemistry A, Vol. 9, Issue 12 https://doi.org/10.1039/D0TA11742K	journal	January 2021
Density Functional Calculations of Native Defects in CH ₃ NH ₃ PbI ₃ : Effects of Spin–Orbit Coupling and Self-Interaction Error Du, Mao-Hua The Journal of Physical Chemistry Letters, Vol. 6, Issue 8 https://doi.org/10.1021/acs.jpclett.5b00199	journal	April 2015
Investigation of Electrode Electrochemical Reactions in CH ₃ NH ₃ PbBr ₃ Perovskite Single‐Crystal Field‐Effect Transistors Wang, Junzhan; Senanayak, Satyaprasad P.; Liu, Jie Advanced Materials, Vol. 31, Issue 35 https://doi.org/10.1002/adma.201902618	journal	July 2019
Giant switchable photovoltaic effect in organometal trihalide perovskite devices Xiao, Zhengguo; Yuan, Yongbo; Shao, Yuchuan Nature Materials, Vol. 14, Issue 2 https://doi.org/10.1038/nmat4150	journal	December 2014
Electronic Level Alignment in Inverted Organometal Perovskite Solar Cells Schulz, Philip; Whittaker-Brooks, Luisa L.; MacLeod, Bradley A. Advanced Materials Interfaces, Vol. 2, Issue 7 https://doi.org/10.1002/admi.201400532	journal	March 2015
Breakdown of the Static Picture of Defect Energetics in Halide Perovskites: The Case of the Br Vacancy in CsPbBr ₃ Cohen, Ayala V.; Egger, David A.; Rappe, Andrew M. The Journal of Physical Chemistry Letters, Vol. 10, Issue 16 https://doi.org/10.1021/acs.jpclett.9b01855	journal	July 2019
Molecular dopants: Tools to control the electronic structure of metal halide perovskite interfaces Zhang, Fengyu; Smith, Hannah L.; Kahn, Antoine Applied Physics Reviews, Vol. 8, Issue 4 https://doi.org/10.1063/5.0060129	journal	December 2021
Formation and Diffusion of Metal Impurities in Perovskite Solar Cell Material CH ₃ NH ₃ PbI ₃ : Implications on Solar Cell Degradation and Choice of Electrode Ming, Wenmei; Yang, Dongwen; Li, Tianshu Advanced Science, Vol. 5, Issue 2 https://doi.org/10.1002/advs.201700662	journal	December 2017
The Nature of Ion Conduction in Methylammonium Lead Iodide: A Multimethod Approach Senocrate, Alessandro; Moudrakovski, Igor; Kim, Gee Yeong Angewandte Chemie International Edition, Vol. 56, Issue 27 https://doi.org/10.1002/anie.201701724	journal	May 2017
Interfacial charge-transfer doping of metal halide perovskites for high performance photovoltaics Noel, Nakita K.; Habisreutinger, Severin N.; Pellaroque, Alba Energy & Environmental Science, Vol. 12, Issue 10 https://doi.org/10.1039/C9EE01773A	journal	January 2019
Light-induced reactivity of gold and hybrid perovskite as a new possible degradation mechanism in perovskite solar cells Shlenskaya, Natalia N.; Belich, Nikolai A.; Grätzel, Michael Journal of Materials Chemistry A, Vol. 6, Issue 4 https://doi.org/10.1039/C7TA10217H	journal	January 2018
Recombination Kinetics in Organic-Inorganic Perovskites: Excitons, Free Charge, and Subgap States Stranks, Samuel D.; Burlakov, Victor M.; Leijtens, Tomas Physical Review Applied, Vol. 2, Issue 3 https://doi.org/10.1103/PhysRevApplied.2.034007	journal	September 2014
B-Site doped lead halide perovskites: synthesis, band engineering, photophysics, and light emission applications Luo, Binbin; Li, Fei; Xu, Ke Journal of Materials Chemistry C, Vol. 7, Issue 10 https://doi.org/10.1039/C8TC05741A	journal	January 2019
Lead-Free All-Inorganic Cesium Tin Iodide Perovskite for Filamentary and Interface-Type Resistive Switching toward Environment-Friendly and Temperature-Tolerant Nonvolatile Memories Han, Ji Su; Le, Quyet Van; Choi, Jaeho ACS Applied Materials & Interfaces, Vol. 11, Issue 8 https://doi.org/10.1021/acsami.8b15769	journal	January 2019
Complexities of Contact Potential Difference Measurements on Metal Halide Perovskite Surfaces Zhang, Fengyu; Ullrich, Florian; Silver, Scott The Journal of Physical Chemistry Letters, Vol. 10, Issue 4 https://doi.org/10.1021/acs.jpclett.8b03878	journal	February 2019
Multiple resistive switching behaviours of CH3NH3PbI3 perovskite film with different metal electrodes How, Gregory Thien Soon; Talik, Noor Azrina; Yap, Boon Kar Applied Surface Science, Vol. 473 https://doi.org/10.1016/j.apsusc.2018.12.124	journal	April 2019
Controlling competing photochemical reactions stabilizes perovskite solar cells Motti, Silvia G.; Meggiolaro, Daniele; Barker, Alex J. Nature Photonics, Vol. 13, Issue 8 https://doi.org/10.1038/s41566-019-0435-1	journal	May 2019
Heterovalent Dopant Incorporation for Bandgap and Type Engineering of Perovskite Crystals Abdelhady, Ahmed L.; Saidaminov, Makhsud I.; Murali, Banavoth The Journal of Physical Chemistry Letters, Vol. 7, Issue 2 https://doi.org/10.1021/acs.jpclett.5b02681	journal	January 2016
Fast Diffusion of Native Defects and Impurities in Perovskite Solar Cell Material CH ₃ NH ₃ PbI ₃ Yang, Dongwen; Ming, Wenmei; Shi, Hongliang Chemistry of Materials, Vol. 28, Issue 12 https://doi.org/10.1021/acs.chemmater.6b01348	journal	June 2016
Competition between Metallic and Vacancy Defect Conductive Filaments in a CH₃NH₃PbI₃-Based Memory Device Sun, Yiming; Tai, Meiqian; Song, Cheng The Journal of Physical Chemistry C, Vol. 122, Issue 11 https://doi.org/10.1021/acs.jpcc.7b12817	journal	March 2018
Electrode-induced impurities in tin halide perovskite solar cell material CsSnBr3 from first principles Liang, Yuhang; Cui, Xiangyuan; Li, Feng npj Computational Materials, Vol. 7, Issue 1 https://doi.org/10.1038/s41524-021-00533-5	journal	May 2021
Not All That Glitters Is Gold: Metal-Migration-Induced Degradation in Perovskite Solar Cells Domanski, Konrad; Correa-Baena, Juan-Pablo; Mine, Nicolas ACS Nano, Vol. 10, Issue 6 https://doi.org/10.1021/acsnano.6b02613	journal	May 2016
A Multi-Dimensional Perspective on Electronic Doping in Metal Halide Perovskites Amerling, Eric; Lu, Haipeng; Larson, Bryon W. ACS Energy Letters, Vol. 6, Issue 3 https://doi.org/10.1021/acsenergylett.0c02476	journal	March 2021
Shedding light on electronically doped perovskites Stewart, A. W.; Julien, A.; Regaldo, D. Materials Today Chemistry, Vol. 29 https://doi.org/10.1016/j.mtchem.2023.101380	journal	April 2023
Can slow-moving ions explain hysteresis in the current–voltage curves of perovskite solar cells? Richardson, Giles; O'Kane, Simon E. J.; Niemann, Ralf G. Energy & Environmental Science, Vol. 9, Issue 4 https://doi.org/10.1039/C5EE02740C	journal	January 2016
First-Principles Survey of Acceptor Dopants for p-Type Cesium Lead Bromide Swift, Michael W.; Lyons, John L. The Journal of Physical Chemistry C, Vol. 126, Issue 29 https://doi.org/10.1021/acs.jpcc.2c03456	journal	July 2022
What Is the Mechanism of MAPbI ₃ p-Doping by I ₂ ? Insights from Optoelectronic Properties Zohar, Arava; Levine, Igal; Gupta, Satyajit ACS Energy Letters, Vol. 2, Issue 10 https://doi.org/10.1021/acsenergylett.7b00698	journal	September 2017
Mitigation of Vacuum and Illumination-Induced Degradation in Perovskite Solar Cells by Structure Engineering Jiang, Yan; Yang, Shih-Chi; Jeangros, Quentin Joule, Vol. 4, Issue 5 https://doi.org/10.1016/j.joule.2020.03.017	journal	May 2020
Iodine Vacancy Redistribution in Organic-Inorganic Halide Perovskite Films and Resistive Switching Effects Zhu, Xiaojian; Lee, Jihang; Lu, Wei D. Advanced Materials, Vol. 29, Issue 29 https://doi.org/10.1002/adma.201700527	journal	June 2017
N-Type Surface Doping of MAPbI ₃ via Charge Transfer from Small Molecules Perry, Erin E.; Labram, John G.; Venkatesan, Naveen R. Advanced Electronic Materials, Vol. 4, Issue 7 https://doi.org/10.1002/aelm.201800087	journal	June 2018
Iodine chemistry determines the defect tolerance of lead-halide perovskites Meggiolaro, Daniele; Motti, Silvia G.; Mosconi, Edoardo Energy & Environmental Science, Vol. 11, Issue 3 https://doi.org/10.1039/C8EE00124C	journal	January 2018
Anomalously large interface charge in polarity-switchable photovoltaic devices: an indication of mobile ions in organic–inorganic halide perovskites Zhao, Yong; Liang, Chunjun; Zhang, Huimin Energy & Environmental Science, Vol. 8, Issue 4 https://doi.org/10.1039/C4EE04064C	journal	January 2015
Reactions at noble metal contacts with methylammonium lead triiodide perovskites: Role of underpotential deposition and electrochemistry Kerner, Ross A.; Schulz, Philip; Christians, Jeffrey A. APL Materials, Vol. 7, Issue 4 https://doi.org/10.1063/1.5083812	journal	April 2019
Metal-Doped Lead Halide Perovskites: Synthesis, Properties, and Optoelectronic Applications Zhou, Yang; Chen, Jie; Bakr, Osman M. Chemistry of Materials, Vol. 30, Issue 19 https://doi.org/10.1021/acs.chemmater.8b02989	journal	August 2018
Gold and iodine diffusion in large area perovskite solar cells under illumination Cacovich, S.; Ciná, L.; Matteocci, F. Nanoscale, Vol. 9, Issue 14 https://doi.org/10.1039/C7NR00784A	journal	January 2017
Studies of mixed-valence states in three-dimensional halogen-bridged gold compounds, Cs2Au I Au III X6(X = Cl, Br or I). Part 1. Synthesis, X-ray powder diffraction, and electron spin resonance studies of CsAu0.6Br2.6 Kitagawa, Hiroshi; Kojima, Norimichi; Matsushita, Nobuyuki Journal of the Chemical Society, Dalton Transactions, Issue 11 https://doi.org/10.1039/dt9910003115	journal	January 1991
Engineering Interfacial Charge Transfer in CsPbBr ₃ Perovskite Nanocrystals by Heterovalent Doping Begum, Raihana; Parida, Manas R.; Abdelhady, Ahmed L. Journal of the American Chemical Society, Vol. 139, Issue 2 https://doi.org/10.1021/jacs.6b09575	journal	December 2016
Electronic properties of metal halide perovskites and their interfaces: the basics Zu, Fengshuo; Shin, Dongguen; Koch, Norbert Materials Horizons, Vol. 9, Issue 1 https://doi.org/10.1039/D1MH01106E	journal	January 2022
Iodine interstitials as a cause of nonradiative recombination in hybrid perovskites Zhang, Xie; Turiansky, Mark E.; Shen, Jimmy-Xuan Physical Review B, Vol. 101, Issue 14 https://doi.org/10.1103/PhysRevB.101.140101	journal	April 2020
Mechanism and Timescales of Reversible p‐Doping of Methylammonium Lead Triiodide by Oxygen Shin, Dongguen; Zu, Fengshuo; Cohen, Ayala V. Advanced Materials, Vol. 33, Issue 23 https://doi.org/10.1002/adma.202100211	journal	May 2021
First-principles calculations for point defects in solids Freysoldt, Christoph; Grabowski, Blazej; Hickel, Tilmann Reviews of Modern Physics, Vol. 86, Issue 1 https://doi.org/10.1103/RevModPhys.86.253	journal	March 2014
Facile and noninvasive passivation, doping and chemical tuning of macroscopic hybrid perovskite crystals Kirmani, Ahmad R.; Mansour, Ahmed E.; Yang, Chen PLOS ONE, Vol. 15, Issue 3 https://doi.org/10.1371/journal.pone.0230540	journal	March 2020
Ag-Doped Halide Perovskite Nanocrystals for Tunable Band Structure and Efficient Charge Transport Zhou, Shu; Ma, Yaping; Zhou, Guodong ACS Energy Letters, Vol. 4, Issue 2 https://doi.org/10.1021/acsenergylett.8b02478	journal	January 2019
Electrochemical Lithium Doping Induced Property Changes In Halide Perovskite CsPbBr ₃ Crystal Jiang, Qinglong; Zeng, Xiaoqiao; Wang, Ning ACS Energy Letters, Vol. 3, Issue 1 https://doi.org/10.1021/acsenergylett.7b01230	journal	November 2017
Halogen Migration in Hybrid Perovskites: The Organic Cation Matters Oranskaia, Aleksandra; Yin, Jun; Bakr, Osman M. The Journal of Physical Chemistry Letters, Vol. 9, Issue 18 https://doi.org/10.1021/acs.jpclett.8b02522	journal	September 2018
The pursuit of stability in halide perovskites: the monovalent cation and the key for surface and bulk self-healing Ceratti, D. R.; Cohen, A. V.; Tenne, R. Materials Horizons, Vol. 8, Issue 5 https://doi.org/10.1039/D1MH00006C	journal	January 2021
Studies of mixed-valence states in three-dimensional halogen-bridged gold compounds, Cs2Au I Au III X6, (X = Cl, Br or I). Part 2. X-Ray photoelectron spectroscopic study Kitagawa, Hiroshi; Kojima, Norimichi; Nakajima, Tsuyoshi Journal of the Chemical Society, Dalton Transactions, Issue 11 https://doi.org/10.1039/dt9910003121	journal	January 1991
Unraveling the Electronic Properties of Lead Halide Perovskites with Surface Photovoltage in Photoemission Studies Zu, Fengshuo; Wolff, Christian M.; Ralaiarisoa, Maryline ACS Applied Materials & Interfaces, Vol. 11, Issue 24 https://doi.org/10.1021/acsami.9b05293	journal	May 2019
Electrochemical Doping of Halide Perovskites with Ion Intercalation Jiang, Qinglong; Chen, Mingming; Li, Junqiang ACS Nano, Vol. 11, Issue 1 https://doi.org/10.1021/acsnano.6b08004	journal	January 2017
Nonchemical n- and p-Type Charge Transfer Doping of FAPbI₃ Perovskite Ma, Chunqing; Kim, Bosung; Kang, Dong-Ho ACS Energy Letters, Vol. 6, Issue 8 https://doi.org/10.1021/acsenergylett.1c01233	journal	July 2021
Understanding Charge Transport in All-Inorganic Halide Perovskite Nanocrystal Thin-Film Field Effect Transistors Zhou, Shu; Zhou, Guodong; Li, Yuhao ACS Energy Letters, Vol. 5, Issue 8 https://doi.org/10.1021/acsenergylett.0c01295	journal	July 2020
Formation of Stable Metal Halide Perovskite/Perovskite Heterojunctions Clark, Catherine P.; Mann, Jennifer E.; Bangsund, John S. ACS Energy Letters, Vol. 5, Issue 11 https://doi.org/10.1021/acsenergylett.0c01609	journal	October 2020
Defect Tolerance in Methylammonium Lead Triiodide Perovskite Steirer, K. Xerxes; Schulz, Philip; Teeter, Glenn ACS Energy Letters, Vol. 1, Issue 2 https://doi.org/10.1021/acsenergylett.6b00196	journal	July 2016

Similar Records

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

Journal Article · Thu Apr 04 00:00:00 EDT 2019 · APL Materials · OSTI ID:1983474

Kerner, Ross A.; Schulz, Philip; Christians, Jeffrey A.; +6 more

Halogen Redox Shuttle Explains Voltage-Induced Halide Redistribution in Mixed-Halide Perovskite Devices

Journal Article · Wed Dec 14 00:00:00 EST 2022 · ACS Energy Letters · OSTI ID:1983474

Xu, Zhaojian; Kerner, Ross A.; Harvey, Steven P.; +3 more

Iodine Electrochemistry Dictates Voltage‐Induced Halide Segregation Thresholds in Mixed‐Halide Perovskite Devices

Journal Article · Fri Jun 17 00:00:00 EDT 2022 · Advanced Functional Materials · OSTI ID:1983474

Xu, Zhaojian; Kerner, Ross A.; Berry, Joseph J.; +1 more

Related Subjects

36 MATERIALS SCIENCE
14 SOLAR ENERGY
electrochemical doping
halide perovskite
interstitial defects

Title: Electrochemical Doping of Halide Perovskites by Noble Metal Interstitial Cations

Citation Formats

References (63)

Similar Records

Related Subjects