Kinetics and mechanism of light-induced phase separation in a mixed-halide perovskite

Peng, Siying; Wang, Yanming; Braun, Michael; Yin, Yikai; Meng, Andrew C.; Tan, Wanliang; Saini, Balreen; Severson, Kayla; Marshall, Ann F.; Sytwu, Katherine; Baniecki, John D.; Dionne, Jennifer; Cai, Wei; McIntyre, Paul C.

doi:10.1016/j.matt.2023.04.025

Title: Kinetics and mechanism of light-induced phase separation in a mixed-halide perovskite

Journal Article · 22 May 2023 · Matter (Online)

DOI: https://doi.org/10.1016/j.matt.2023.04.025 · OSTI ID:2006862

^[1]; Wang, Yanming ^[2]; Braun, Michael ^[3]; Yin, Yikai ^[3]; Meng, Andrew C. ^[4]; Tan, Wanliang ^[3]; Saini, Balreen ^[3]; Severson, Kayla ^[3]; Marshall, Ann F. ^[3]; Sytwu, Katherine ^[3]; Baniecki, John D. ^[5]; Dionne, Jennifer ^[3]; Cai, Wei ^[3];

^[6]

Stanford Univ., CA (United States); Westlake Univ., Hangzhou (China); SLAC
Shanghai Jiao Tong Univ. (China)
Stanford Univ., CA (United States)
Stanford Univ., CA (United States); Univ. of Missouri, Columbia, MO (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Halide ion phase separation is a barrier to the application of mixed-halide perovskites, whereby the presence of large populations of photo-generated or injected carriers causes undesirable changes in the local band gap. Here, we investigate the mechanism of phase separation in CsPbI_xBr_3-x perovskite single crystals driven by light. The phase separation process and its dynamics are visualized at the nanometer scale at cryogenic temperatures using in-situ scanning transmission electron microscopy and cathodoluminescence. Combined with phase field modeling that accounts for the coupling between electronic and chemical driving forces, our observations point to a spinodal decomposition mechanism in which both the amplitude of composition fluctuation and the characteristic length scale grow non-linearly with time. Our findings provide microscopic insights that can assist in further engineering mixed-halide perovskites either for stability or for intentional programming of the local halide ion composition, opening pathways to a wide range of applications.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 2006862

Journal Information:: Matter (Online), Journal Name: Matter (Online) Journal Issue: 6 Vol. 6; ISSN 2590-2385

Publisher:: Cell Press/ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (37)

Visualizing Phase Segregation in Mixed-Halide Perovskite Single Crystals Mao, Wenxin; Hall, Christopher R.; Chesman, Anthony S. R. Angewandte Chemie International Edition, Vol. 58, Issue 9 https://doi.org/10.1002/anie.201810193	journal	January 2019
Complex evolution of photoluminescence during phase segregation of MAPb(I1-xBrx)3 mixed halide perovskite Suchan, Klara; Merdasa, Aboma; Rehermann, Carolin Journal of Luminescence, Vol. 221 https://doi.org/10.1016/j.jlumin.2020.117073	journal	May 2020
High-temperature structural evolution of caesium and rubidium triiodoplumbates Trots, D. M.; Myagkota, S. V. Journal of Physics and Chemistry of Solids, Vol. 69, Issue 10, p. 2520-2526 https://doi.org/10.1016/j.jpcs.2008.05.007	journal	October 2008
Structural Origins of Light-Induced Phase Segregation in Organic-Inorganic Halide Perovskite Photovoltaic Materials Beal, Rachel E.; Hagström, Nanna Zhou; Barrier, Julien Matter, Vol. 2, Issue 1 https://doi.org/10.1016/j.matt.2019.11.001	journal	January 2020
Cs _{1– x} Rb _x PbCl ₃ and Cs _{1– x} Rb _x PbBr ₃ Solid Solutions: Understanding Octahedral Tilting in Lead Halide Perovskites Linaburg, Matthew R.; McClure, Eric T.; Majher, Jackson D. Chemistry of Materials, Vol. 29, Issue 8 https://doi.org/10.1021/acs.chemmater.6b05372	journal	April 2017
Flash Formation of I-Rich Clusters during Multistage Halide Segregation Studied in MAPbI _1.5 Br _1.5 Babbe, Finn; Masquelier, Eloïse; Zheng, Zhi The Journal of Physical Chemistry C, Vol. 124, Issue 45 https://doi.org/10.1021/acs.jpcc.0c07063	journal	November 2020
Cesium Lead Halide Perovskites with Improved Stability for Tandem Solar Cells Beal, Rachel E.; Slotcavage, Daniel J.; Leijtens, Tomas The Journal of Physical Chemistry Letters, Vol. 7, Issue 5 https://doi.org/10.1021/acs.jpclett.6b00002	journal	February 2016
Long-Lived Photoinduced Polarons in Organohalide Perovskites Ivanovska, Tanja; Dionigi, Chiara; Mosconi, Edoardo The Journal of Physical Chemistry Letters, Vol. 8, Issue 13 https://doi.org/10.1021/acs.jpclett.7b01156	journal	June 2017
Phase Segregation and Photothermal Remixing of Mixed-Halide Lead Perovskites Vicente, Juvinch R.; Chen, Jixin The Journal of Physical Chemistry Letters, Vol. 11, Issue 5 https://doi.org/10.1021/acs.jpclett.9b03734	journal	January 2020
Origin of Reversible Photoinduced Phase Separation in Hybrid Perovskites Bischak, Connor G.; Hetherington, Craig L.; Wu, Hao Nano Letters, Vol. 17, Issue 2 https://doi.org/10.1021/acs.nanolett.6b04453	journal	January 2017
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
Distinguishing Models for Mixed Halide Lead Perovskite Photosegregation via Terminal Halide Stoichiometry Pavlovetc, Ilia M.; Ruth, Anthony; Gushchina, Irina ACS Energy Letters, Vol. 6, Issue 6 https://doi.org/10.1021/acsenergylett.1c00790	journal	May 2021
Tracking Iodide and Bromide Ion Segregation in Mixed Halide Lead Perovskites during Photoirradiation Yoon, Seog Joon; Draguta, Sergiu; Manser, Joseph S. ACS Energy Letters, Vol. 1, Issue 1 https://doi.org/10.1021/acsenergylett.6b00158	journal	June 2016
Light-Induced Phase Segregation in Halide-Perovskite Absorbers Slotcavage, Daniel J.; Karunadasa, Hemamala I.; McGehee, Michael D. ACS Energy Letters, Vol. 1, Issue 6 https://doi.org/10.1021/acsenergylett.6b00495	journal	November 2016
Light-Induced Anion Phase Segregation in Mixed Halide Perovskites Brennan, Michael C.; Draguta, Sergiu; Kamat, Prashant V. ACS Energy Letters, Vol. 3, Issue 1 https://doi.org/10.1021/acsenergylett.7b01151	journal	November 2017
Controlling the Phase Segregation in Mixed Halide Perovskites through Nanocrystal Size Gualdrón-Reyes, Andrés. F.; Yoon, Seog Joon; Barea, Eva M. ACS Energy Letters, Vol. 4, Issue 1 https://doi.org/10.1021/acsenergylett.8b02207	journal	November 2018
How Interplay between Photo and Thermal Activation Dictates Halide Ion Segregation in Mixed Halide Perovskites Elmelund, Tor; Seger, Brian; Kuno, Masaru ACS Energy Letters, Vol. 5, Issue 1 https://doi.org/10.1021/acsenergylett.9b02265	journal	November 2019
Epitaxial Halide Perovskite Lateral Double Heterostructure Wang, Yiping; Chen, Zhizhong; Deschler, Felix ACS Nano, Vol. 11, Issue 3 https://doi.org/10.1021/acsnano.7b00724	journal	February 2017
Single-Crystal Thin Films of Cesium Lead Bromide Perovskite Epitaxially Grown on Metal Oxide Perovskite (SrTiO ₃ ) Chen, Jie; Morrow, Darien J.; Fu, Yongping Journal of the American Chemical Society, Vol. 139, Issue 38 https://doi.org/10.1021/jacs.7b07506	journal	September 2017
Efficient planar heterojunction perovskite solar cells by vapour deposition Liu, Mingzhen; Johnston, Michael B.; Snaith, Henry J. Nature, Vol. 501, Issue 7467, p. 395-398 https://doi.org/10.1038/nature12509	journal	September 2013
Quantum-dot-in-perovskite solids Ning, Zhijun; Gong, Xiwen; Comin, Riccardo Nature, Vol. 523, Issue 7560 https://doi.org/10.1038/nature14563	journal	July 2015
Rationalizing the light-induced phase separation of mixed halide organic–inorganic perovskites Draguta, Sergiu; Sharia, Onise; Yoon, Seog Joon Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00284-2	journal	August 2017
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
Phase segregation due to ion migration in all-inorganic mixed-halide perovskite nanocrystals Zhang, Huichao; Fu, Xu; Tang, Ying Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09047-7	journal	March 2019
Unified theory for light-induced halide segregation in mixed halide perovskites Chen, Zehua; Brocks, Geert; Tao, Shuxia Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23008-z	journal	May 2021
Phase segregation in mixed-halide perovskites affects charge-carrier dynamics while preserving mobility Motti, Silvia G.; Patel, Jay B.; Oliver, Robert D. J. Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-26930-4	journal	November 2021
Large tunable photoeffect on ion conduction in halide perovskites and implications for photodecomposition Kim, Gee Yeong; Senocrate, Alessandro; Yang, Tae-Youl Nature Materials, Vol. 17, Issue 5 https://doi.org/10.1038/s41563-018-0038-0	journal	March 2018
Light-induced reversal of ion segregation in mixed-halide perovskites Mao, Wenxin; Hall, Christopher R.; Bernardi, Stefano Nature Materials, Vol. 20, Issue 1 https://doi.org/10.1038/s41563-020-00826-y	journal	October 2020
Perovskite light-emitting diodes with external quantum efficiency exceeding 20 per cent Lin, Kebin; Xing, Jun; Quan, Li Na Nature, Vol. 562, Issue 7726 https://doi.org/10.1038/s41586-018-0575-3	journal	October 2018
Pseudo-halide anion engineering for α-FAPbI3 perovskite solar cells Jeong, Jaeki; Kim, Minjin; Seo, Jongdeuk Nature, Vol. 592, Issue 7854 https://doi.org/10.1038/s41586-021-03406-5	journal	April 2021
Direct observation of spinodal decomposition phenomena in InAlN alloys during in-situ STEM heating Palisaitis, J.; Hsiao, C. -L.; Hultman, L. Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/srep44390	journal	March 2017
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
Light-induced annihilation of Frenkel defects in organo-lead halide perovskites Mosconi, Edoardo; Meggiolaro, Daniele; Snaith, Henry J. Energy & Environmental Science, Vol. 9, Issue 10 https://doi.org/10.1039/C6EE01504B	journal	January 2016
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
Stable deep blue emission with unity quantum yield in organic–inorganic halide perovskite 2D nanosheets doped with cerium and terbium at high concentrations Parveen, Sumaiya; Prasanna, Ponnappa Kechanda; Chakraborty, Sudip Journal of Materials Chemistry C, Vol. 9, Issue 7 https://doi.org/10.1039/D0TC04937A	journal	January 2021
Spontaneous pinning of domain growth during spinodal decomposition of off‐critical polymer mixtures Hashimoto, Takeji; Takenaka, Mikihito; Izumitani, Tatsuo The Journal of Chemical Physics, Vol. 97, Issue 1 https://doi.org/10.1063/1.463562	journal	July 1992
p40phox-Deficient Mice Exhibit Impaired Bacterial Clearance and Enhanced Pro-inflammatory Responses during Salmonella enterica serovar Typhimurium Infection Li, Yali; Lv, Meili; Su, Chienwen Frontiers in Immunology, Vol. 8 https://doi.org/10.3389/fimmu.2017.01270	journal	October 2017

Similar Records

Phase segregation dynamics in mixed-halide perovskites revealed by plunge-freeze cryo-electron microscopy

Journal Article · 2025 · Cell Reports Physical Science · OSTI ID:2574623

Fan, Qingyuan; Cui, Yi; Li, Yanbin; +8 more

Local A-Site Phase Segregation Leads to Cs-Rich Regions Showing Accelerated Photodegradation in Mixed-Cation Perovskite Semiconductor Films

Journal Article · 2024 · ACS Energy Letters · OSTI ID:2475135

Huang, Zixu; Jiang, Fangyuan; Song, Zhaoning; +4 more

Persistent dopants and phase segregation in organolead mixed-halide perovskites

Journal Article · 2016 · Chemistry of Materials · OSTI ID:1321908

Rosales, Bryan A.; Men, Long; Cady, Sarah D.; +3 more

Related Subjects

36 MATERIALS SCIENCE

Title: Kinetics and mechanism of light-induced phase separation in a mixed-halide perovskite

Citation Formats

References (37)

Similar Records

Related Subjects