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

Xu, Zhaojian; Kerner, Ross A.; Harvey, Steven P.; Zhu, Kai; Berry, Joseph J.; Rand, Barry P.

doi:10.1021/acsenergylett.2c02385

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

Journal Article · 14 December 2022 · ACS Energy Letters

DOI: https://doi.org/10.1021/acsenergylett.2c02385 · OSTI ID:1908586

^[1];

^[2];

^[2]; Berry, Joseph J. ^[3];

^[1]

Princeton University, NJ (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States); University of Colorado, Boulder, CO (United States)

Voltage-induced halide segregation greatly limits the optoelectronic applications of mixed-halide perovskite devices, but a mechanistic explanation behind this phenomenon remains unclear. In this work, we use electron microscopy and elemental mapping to directly measure the halide redistribution in mixed-halide perovskite solar cells with quasi-ion-impermeable contact layers under different bias polarities to find iodide and bromide accumulation at the cathode and anode, respectively. This is consistent with a mechanism based on preferential iodide oxidation at the anode, leading to unbalanced I$$^{+}_{i}$$, I$$^{-}_{X}$$, and Br$$^{-}_{X}$$ fluxes. Importantly, switching the anode from "inert" Au to "active" Ag prevents segregation because Ag oxidation precludes the oxidation of lattice iodide, which suggests employing redox-active additives as a general strategy to suppress halide segregation. Finally, these results show that halide perovskite devices operate as solid-state electrochemical cells when threshold voltages are exceeded, providing fresh insight to understand the impacts of voltage bias on halide perovskite devices.

View Accepted Manuscript (DOE)

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; US Department of the Navy, Office of Naval Research (ONR); National Science Foundation (NSF)

Grant/Contract Number:: AC36-08GO28308; N00014-21-1-2767; FOA-0000990; DMR-2011750

OSTI ID:: 1908586

Report Number(s):: NREL/JA-5900-84175; MainId:84948; UUID:20d77097-06ee-4f53-b074-53163403f12b; MainAdminID:68392

Journal Information:: ACS Energy Letters, Vol. 8, Issue 1; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (46)

Multicolored Organic/Inorganic Hybrid Perovskite Light-Emitting Diodes Kim, Young-Hoon; Cho, Himchan; Heo, Jin Hyuck Advanced Materials, Vol. 27, Issue 7 https://doi.org/10.1002/adma.201403751	journal	November 2014
Blue-Green Color Tunable Solution Processable Organolead Chloride–Bromide Mixed Halide Perovskites for Optoelectronic Applications Sadhanala, Aditya; Ahmad, Shahab; Zhao, Baodan Nano Letters, Vol. 15, Issue 9 https://doi.org/10.1021/acs.nanolett.5b02369	journal	August 2015
A mixed-cation lead mixed-halide perovskite absorber for tandem solar cells McMeekin, D. P.; Sadoughi, G.; Rehman, W. Science, Vol. 351, Issue 6269 https://doi.org/10.1126/science.aad5845	journal	January 2016
Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics Hoke, Eric T.; Slotcavage, Daniel J.; Dohner, Emma R. Chemical Science, Vol. 6, Issue 1 https://doi.org/10.1039/C4SC03141E	journal	January 2015
Photoinduced Anion Segregation in Mixed Halide Perovskites Brennan, Michael C.; Ruth, Anthony; Kamat, Prashant V. Trends in Chemistry, Vol. 2, Issue 4 https://doi.org/10.1016/j.trechm.2020.01.010	journal	April 2020
Current-Induced Phase Segregation in Mixed Halide Hybrid Perovskites and its Impact on Two-Terminal Tandem Solar Cell Design Braly, Ian L.; Stoddard, Ryan J.; Rajagopal, Adharsh ACS Energy Letters, Vol. 2, Issue 8 https://doi.org/10.1021/acsenergylett.7b00525	journal	July 2017
Mixed-Halide Perovskites with Stabilized Bandgaps Xiao, Zhengguo; Zhao, Lianfeng; Tran, Nhu L. Nano Letters, Vol. 17, Issue 11 https://doi.org/10.1021/acs.nanolett.7b03179	journal	October 2017
Iodine Electrochemistry Dictates Voltage‐Induced Halide Segregation Thresholds in Mixed‐Halide Perovskite Devices Xu, Zhaojian; Kerner, Ross A.; Berry, Joseph J. Advanced Functional Materials, Vol. 32, Issue 33 https://doi.org/10.1002/adfm.202203432	journal	June 2022
Preventing phase segregation in mixed-halide perovskites: a perspective Knight, Alexander J.; Herz, Laura M. Energy & Environmental Science, Vol. 13, Issue 7 https://doi.org/10.1039/D0EE00788A	journal	January 2020
Hole Trapping in Halide Perovskites Induces Phase Segregation DuBose, Jeffrey T.; Kamat, Prashant V. Accounts of Materials Research, Vol. 3, Issue 7 https://doi.org/10.1021/accountsmr.2c00076	journal	June 2022
The role of halide oxidation in perovskite halide phase separation Kerner, Ross A.; Xu, Zhaojian; Larson, Bryon W. Joule, Vol. 5, Issue 9 https://doi.org/10.1016/j.joule.2021.07.011	journal	September 2021
Halide Photoredox Chemistry Troian-Gautier, Ludovic; Turlington, Michael D.; Wehlin, Sara A. M. Chemical Reviews, Vol. 119, Issue 7 https://doi.org/10.1021/acs.chemrev.8b00732	journal	March 2019
Combatting temperature and reverse-bias challenges facing perovskite solar cells Lan, Dongchen; Green, Martin A. Joule, Vol. 6, Issue 8 https://doi.org/10.1016/j.joule.2022.06.014	journal	August 2022
Reverse Bias Behavior of Halide Perovskite Solar Cells Bowring, Andrea R.; Bertoluzzi, Luca; O'Regan, Brian C. Advanced Energy Materials, Vol. 8, Issue 8 https://doi.org/10.1002/aenm.201702365	journal	December 2017
Instability of p–i–n perovskite solar cells under reverse bias Razera, Ricardo A. Z.; Jacobs, Daniel A.; Fu, Fan Journal of Materials Chemistry A, Vol. 8, Issue 1 https://doi.org/10.1039/C9TA12032G	journal	January 2020
Designing Modules to Prevent Reverse Bias Degradation in Perovskite Solar Cells when Partial Shading Occurs Wolf, Eli J.; Gould, Isaac E.; Bliss, Lyle B. Solar RRL https://doi.org/10.1002/solr.202100239	journal	May 2021
Perovskite Photovoltaic Devices with Carbon‐Based Electrodes Withstanding Reverse‐Bias Voltages up to –9 V and Surpassing IEC 61215:2016 International Standard Bogachuk, Dmitry; Saddedine, Karima; Martineau, David Solar RRL, Vol. 6, Issue 3 https://doi.org/10.1002/solr.202100527	journal	October 2021
Reverse-Bias and Temperature Behaviors of Perovskite Solar Cells at Extended Voltage Range Najafi, Leyla; Bellani, Sebastiano; Gabatel, Luca ACS Applied Energy Materials, Vol. 5, Issue 2 https://doi.org/10.1021/acsaem.1c03206	journal	February 2022
Perovskite light-emitting diodes Fakharuddin, Azhar; Gangishetty, Mahesh K.; Abdi-Jalebi, Mojtaba Nature Electronics, Vol. 5, Issue 4 https://doi.org/10.1038/s41928-022-00745-7	journal	April 2022
Improved Outcoupling Efficiency and Stability of Perovskite Light-Emitting Diodes using Thin Emitting Layers Zhao, Lianfeng; Lee, Kyung Min; Roh, Kwangdong Advanced Materials, Vol. 31, Issue 2 https://doi.org/10.1002/adma.201805836	journal	November 2018
Efficient perovskite light-emitting diodes featuring nanometre-sized crystallites Xiao, Zhengguo; Kerner, Ross A.; Zhao, Lianfeng Nature Photonics, Vol. 11, Issue 2 https://doi.org/10.1038/nphoton.2016.269	journal	January 2017
Electrical Stress Influences the Efficiency of CH ₃ NH ₃ PbI ₃ Perovskite Light Emitting Devices Zhao, Lianfeng; Gao, Jia; Lin, YunHui L. Advanced Materials, Vol. 29, Issue 24 https://doi.org/10.1002/adma.201605317	journal	April 2017
Thermal Management Enables Bright and Stable Perovskite Light‐Emitting Diodes Zhao, Lianfeng; Roh, Kwangdong; Kacmoli, Sara Advanced Materials, Vol. 32, Issue 25 https://doi.org/10.1002/adma.202000752	journal	May 2020
Color-stable highly luminescent sky-blue perovskite light-emitting diodes Xing, Jun; Zhao, Yongbiao; Askerka, Mikhail Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05909-8	journal	August 2018
Organic Hole Transport Material Ionization Potential Dictates Diffusion Kinetics of Iodine Species in Halide Perovskite Devices Kerner, Ross A.; Heo, Sungyeon; Roh, Kwangdong ACS Energy Letters, Vol. 6, Issue 2 https://doi.org/10.1021/acsenergylett.0c02495	journal	January 2021
Redox Chemistry Dominates the Degradation and Decomposition of Metal Halide Perovskite Optoelectronic Devices Zhao, Lianfeng; Kerner, Ross A.; Xiao, Zhengguo ACS Energy Letters, Vol. 1, Issue 3 https://doi.org/10.1021/acsenergylett.6b00320	journal	August 2016
In Situ TEM Monitoring of Phase-Segregation in Inorganic Mixed Halide Perovskite Funk, Hannah; Shargaieva, Oleksandra; Eljarrat, Alberto The Journal of Physical Chemistry Letters, Vol. 11, Issue 13 https://doi.org/10.1021/acs.jpclett.0c01296	journal	June 2020
Electrochemical and Thermal Etching of Indium Tin Oxide by Solid-State Hybrid Organic–Inorganic Perovskites Kerner, Ross A.; Rand, Barry P. ACS Applied Energy Materials, Vol. 2, Issue 8 https://doi.org/10.1021/acsaem.9b01356	journal	July 2019
Organometallic-functionalized interfaces for highly efficient inverted perovskite solar cells Li, Zhen; Li, Bo; Wu, Xin Science, Vol. 376, Issue 6591 https://doi.org/10.1126/science.abm8566	journal	April 2022
Roadmap on organic–inorganic hybrid perovskite semiconductors and devices Schmidt-Mende, Lukas; Dyakonov, Vladimir; Olthof, Selina APL Materials, Vol. 9, Issue 10 https://doi.org/10.1063/5.0047616	journal	October 2021
Interfacial Passivation of Perovskite Solar Cells by Reactive Ion Scavengers Teymourinia, Hakimeh; Gonzales, Cedric; Gallardo, Juan Jesús ACS Applied Energy Materials, Vol. 4, Issue 2 https://doi.org/10.1021/acsaem.0c01804	journal	February 2021
Inorganic CsPb ₁₋ _x Sn _x IBr ₂ for Efficient Wide-Bandgap Perovskite Solar Cells Li, Nan; Zhu, Zonglong; Li, Jiangwei Advanced Energy Materials, Vol. 8, Issue 22 https://doi.org/10.1002/aenm.201800525	journal	May 2018
Stabilized Wide Bandgap Perovskite Solar Cells by Tin Substitution Yang, Zhibin; Rajagopal, Adharsh; Jo, Sae Byeok Nano Letters, Vol. 16, Issue 12 https://doi.org/10.1021/acs.nanolett.6b03857	journal	November 2016
Negligible Ion Migration in Tin‐Based and Tin‐Doped Perovskites Ighodalo, Kester O.; Chen, Wenjing; Liang, Zheng Angewandte Chemie International Edition https://doi.org/10.1002/anie.202213932	journal	December 2022
Tin versus Lead Redox Chemistry Modulates Charge Trapping and Self-Doping in Tin/Lead Iodide Perovskites Meggiolaro, Daniele; Ricciarelli, Damiano; Alasmari, Ahmed A. The Journal of Physical Chemistry Letters, Vol. 11, Issue 9 https://doi.org/10.1021/acs.jpclett.0c00725	journal	April 2020
Defect activity in metal halide perovskites with wide and narrow bandgap Zhou, Yang; Poli, Isabella; Meggiolaro, Daniele Nature Reviews Materials, Vol. 6, Issue 11 https://doi.org/10.1038/s41578-021-00331-x	journal	June 2021
Spectral Instability of Layered Mixed Halide Perovskites Results from Anion Phase Redistribution and Selective Hole Injection Nah, Yoonseo; Allam, Omar; Kim, Han Seul ACS Nano, Vol. 15, Issue 1 https://doi.org/10.1021/acsnano.0c08897	journal	December 2020
Elucidating and Mitigating Degradation Processes in Perovskite Light‐Emitting Diodes Andaji‐Garmaroudi, Zahra; Abdi‐Jalebi, Mojtaba; Kosasih, Felix U. Advanced Energy Materials, Vol. 10, Issue 48 https://doi.org/10.1002/aenm.202002676	journal	November 2020
Quantification of Ionic Diffusion in Lead Halide Perovskite Single Crystals Peng, Wei; Aranda, Clara; Bakr, Osman M. ACS Energy Letters, Vol. 3, Issue 7 https://doi.org/10.1021/acsenergylett.8b00641	journal	May 2018
Stabilized Wide Bandgap MAPbBr _x I _{3- x} Perovskite by Enhanced Grain Size and Improved Crystallinity Hu, Miao; Bi, Cheng; Yuan, Yongbo Advanced Science, Vol. 3, Issue 6 https://doi.org/10.1002/advs.201500301	journal	December 2015
Local Observation of Phase Segregation in Mixed-Halide Perovskite Tang, Xiaofeng; van den Berg, Marius; Gu, Ening Nano Letters, Vol. 18, Issue 3 https://doi.org/10.1021/acs.nanolett.8b00505	journal	February 2018
Suppressed phase separation of mixed-halide perovskites confined in endotaxial matrices Wang, Xi; Ling, Yichuan; Lian, Xiujun Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-08610-6	journal	February 2019
Impact of Surfaces on Photoinduced Halide Segregation in Mixed-Halide Perovskites Belisle, Rebecca A.; Bush, Kevin A.; Bertoluzzi, Luca ACS Energy Letters, Vol. 3, Issue 11 https://doi.org/10.1021/acsenergylett.8b01562	journal	October 2018
Vacancy-Mediated Anion Photosegregation Kinetics in Mixed Halide Hybrid Perovskites: Coupled Kinetic Monte Carlo and Optical Measurements Ruth, Anthony; Brennan, Michael C.; Draguta, Sergiu ACS Energy Letters, Vol. 3, Issue 10 https://doi.org/10.1021/acsenergylett.8b01369	journal	September 2018
Performance-limiting nanoscale trap clusters at grain junctions in halide perovskites Doherty, Tiarnan A. S.; Winchester, Andrew J.; Macpherson, Stuart Nature, Vol. 580, Issue 7803 https://doi.org/10.1038/s41586-020-2184-1	journal	April 2020
Impact of Hole‐Transport Layer and Interface Passivation on Halide Segregation in Mixed‐Halide Perovskites Lim, Vincent J. ‐Y.; Knight, Alexander J.; Oliver, Robert D. J. Advanced Functional Materials, Vol. 32, Issue 41 https://doi.org/10.1002/adfm.202204825	journal	August 2022

Similar Records

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

Journal Article · 2022 · Advanced Functional Materials · OSTI ID:1873036

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

Origins of Photoluminescence Instabilities at Halide Perovskite/Organic Hole Transport Layer Interfaces

Journal Article · 2023 · Journal of the American Chemical Society · OSTI ID:1986070

Xu, Zhaojian; Astridge, Daniel D.; Kerner, Ross A.; +9 more

Electrochemical Hole Injection Selectively Expels Iodide from Mixed Halide Perovskite Films

Journal Article · 2019 · Journal of the American Chemical Society · OSTI ID:1530479

Samu, Gergely F.; Balog, Ádám; De Angelis, Filippo; +3 more

Related Subjects

14 SOLAR ENERGY
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
electrochemistry
halide peroskites
halide segregation
phase separation
voltage-induced

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

Citation Formats

References (46)

Similar Records

Related Subjects