Local halide heterogeneity drives surface wrinkling in mixed-halide wide-bandgap perovskites

Datta, Kunal; van Laar, Simone C. W.; Taddei, Margherita; Hidalgo, Juanita; Kodalle, Tim; Aalbers, Guus J. W.; Lai, Barry; Li, Ruipeng; Tamura, Nobumichi; Frencken, Jordi T. W.; Quiroz Monnens, Simon V.; Westbrook, Robert E.; Graham, Daniel J.; Sutter-Fella, Carolin M.; Correa-Baena, Juan-Pablo; Ginger, David S.; Wienk, Martijn M.; Janssen, René A. J.

doi:10.1038/s41467-025-57010-6

Local halide heterogeneity drives surface wrinkling in mixed-halide wide-bandgap perovskites

Journal Article · Tue Feb 25 00:00:00 EST 2025 · Nature Communications

DOI:https://doi.org/10.1038/s41467-025-57010-6· OSTI ID:2538435

^[1]; van Laar, Simone C. W. ^[2]; Taddei, Margherita ^[3]; Hidalgo, Juanita ^[4]; ^[5]; ^[2]; Lai, Barry ^[6]; ^[7]; ^[8]; ^[2]; Quiroz Monnens, Simon V. ^[2]; Westbrook, Robert E. ^[3]; ^[3]; ^[9]; ^[4]; ^[10]; Wienk, Martijn M. ^[2]; ^[11]

Eindhoven University of Technology (Netherlands); Georgia Institute of Technology, Atlanta, GA (United States)
Eindhoven University of Technology (Netherlands)
University of Washington, Seattle, WA (United States)
Georgia Institute of Technology, Atlanta, GA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry
University of Washington, Seattle, WA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Eindhoven University of Technology (Netherlands); Dutch Institute for Fundamental Energy Research (DIFFER), Eindhoven (Netherlands)

Compositional heterogeneity in wide-bandgap (1.8 - 2.1 eV) mixed-halide perovskites is a key bottleneck in the processing of high-quality solution-processed thin films and prevents their application in efficient multijunction solar cells. Notably, mixed-cation (formamidinium-methylammonium) wide-bandgap perovskite films are prone to form micrometer-scale wrinkles which can interfere with the smooth surfaces ideal for multijunction devices. Here, we study the formation dynamics of wrinkled mixed-halide perovskite films and its impact on the local composition and optoelectronic properties. We use in situ X-ray scattering during perovskite film formation to show that crystallization of bromide-rich perovskites precedes that of mixed-halide phases in wrinkled films cast using an antisolvent-based process. Using nanoscopic X-ray fluorescence and hyperspectral photoluminescence imaging, we also demonstrate the formation of iodide- and bromide-rich phases in the wrinkled domains. This intrinsic spatial halide segregation results in an increased local bandgap variation and Urbach energy. Morphological disorder and compositional heterogeneity also aggravate the formation of sub-bandgap electronic defects, reducing photostability and accelerating light-induced segregation of iodide and bromide ions in thin films and solar cells.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: National Science Foundation (NSF); US Department of the Navy, Office of Naval Research (ONR); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357; AC05-76RL01830; SC0012704

OSTI ID:: 2538435

Alternate ID(s):: OSTI ID: 2549236
OSTI ID: 2566026

Report Number(s):: BNL--227980-2025-JAAM; PNNL-SA--197271; ark:/13030/qt8dt4644d

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 16; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (63)

Insights into Fullerene Passivation of SnO ₂ Electron Transport Layers in Perovskite Solar Cells Wang, Junke; Datta, Kunal; Weijtens, Christ H. L. Advanced Functional Materials, Vol. 29, Issue 46 https://doi.org/10.1002/adfm.201905883	journal	September 2019
Tailored Local Bandgap Modulation as a Strategy to Maximize Luminescence Yields in Mixed‐Halide Perovskites Feldmann, Sascha; Neumann, Timo; Ciesielski, Richard Advanced Optical Materials, Vol. 9, Issue 18 https://doi.org/10.1002/adom.202100635	journal	June 2021
The Intrinsic Photoluminescence Spectrum of Perovskite Films van der Pol, Tom P. A.; Datta, Kunal; Wienk, Martijn M. Advanced Optical Materials, Vol. 10, Issue 8 https://doi.org/10.1002/adom.202102557	journal	March 2022
Engineering Stress in Perovskite Solar Cells to Improve Stability Rolston, Nicholas; Bush, Kevin A.; Printz, Adam D. Advanced Energy Materials, Vol. 8, Issue 29 https://doi.org/10.1002/aenm.201802139	journal	September 2018
How to Report Record Open‐Circuit Voltages in Lead‐Halide Perovskite Solar Cells Krückemeier, Lisa; Rau, Uwe; Stolterfoht, Martin Advanced Energy Materials, Vol. 10, Issue 1 https://doi.org/10.1002/aenm.201902573	journal	November 2019
Challenges and Perspectives toward Future Wide‐Bandgap Mixed‐Halide Perovskite Photovoltaics Xu, Fan; Zhang, Meng; Li, Zikun Advanced Energy Materials, Vol. 13, Issue 13 https://doi.org/10.1002/aenm.202203911	journal	February 2023
New approach for designing wrinkled and porous ZnO thin films for photocatalytic applications Daher, Elie A.; Riachi, Bassam; Chamoun, Jean Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 658 https://doi.org/10.1016/j.colsurfa.2022.130628	journal	February 2023
Multi-cation Synergy Suppresses Phase Segregation in Mixed-Halide Perovskites Dang, Hoang X.; Wang, Kai; Ghasemi, Masoud Joule, Vol. 3, Issue 7 https://doi.org/10.1016/j.joule.2019.05.016	journal	July 2019
Robot-Based High-Throughput Screening of Antisolvents for Lead Halide Perovskites Gu, Ening; Tang, Xiaofeng; Langner, Stefan Joule, Vol. 4, Issue 8 https://doi.org/10.1016/j.joule.2020.06.013	journal	August 2020
Concurrent cationic and anionic perovskite defect passivation enables 27.4% perovskite/silicon tandems with suppression of halide segregation Isikgor, Furkan H.; Furlan, Francesco; Liu, Jiang Joule, Vol. 5, Issue 6 https://doi.org/10.1016/j.joule.2021.05.013	journal	June 2021
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
High-performance methylammonium-free ideal-band-gap perovskite solar cells Tong, Jinhui; Gong, Jue; Hu, Mingyu Matter, Vol. 4, Issue 4 https://doi.org/10.1016/j.matt.2021.01.003	journal	April 2021
Revealing the internal luminescence quantum efficiency of perovskite films via accurate quantification of photon recycling Fassl, Paul; Lami, Vincent; Berger, Felix J. Matter, Vol. 4, Issue 4 https://doi.org/10.1016/j.matt.2021.01.019	journal	April 2021
Formamidinium Haloplumbate Intermediates: The Missing Link in a Chain of Hybrid Perovskites Crystallization Petrov, Andrey A.; Fateev, Sergey A.; Khrustalev, Victor N. Chemistry of Materials, Vol. 32, Issue 18 https://doi.org/10.1021/acs.chemmater.0c02156	journal	August 2020
Solvent and A-Site Cation Control Preferred Crystallographic Orientation in Bromine-Based Perovskite Thin Films Hidalgo, Juanita; An, Yu; Yehorova, Dariia Chemistry of Materials, Vol. 35, Issue 11 https://doi.org/10.1021/acs.chemmater.3c00075	journal	May 2023
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
Cs _x FA _{1– x} Pb(I _{1– y} Br _y ) ₃ Perovskite Compositions: the Appearance of Wrinkled Morphology and its Impact on Solar Cell Performance Braunger, Steffen; Mundt, Laura E.; Wolff, Christian M. The Journal of Physical Chemistry C, Vol. 122, Issue 30 https://doi.org/10.1021/acs.jpcc.8b06459	journal	March 2018
Spatial Inhomogeneity Analysis of Cesium-Rich Wrinkles in Triple-Cation Perovskite Bercegol, Adrien; Ramos, F. Javier; Rebai, Amelle The Journal of Physical Chemistry C, Vol. 122, Issue 41 https://doi.org/10.1021/acs.jpcc.8b07436	journal	June 2018
Static Disorder in Lead Halide Perovskites Zeiske, Stefan; Sandberg, Oskar J.; Zarrabi, Nasim The Journal of Physical Chemistry Letters, Vol. 13, Issue 31 https://doi.org/10.1021/acs.jpclett.2c01652	journal	August 2022
Thermodynamic Origin of Photoinstability in the CH ₃ NH ₃ Pb(I _{1– x} Br _x ) ₃ Hybrid Halide Perovskite Alloy Brivio, Federico; Caetano, Clovis; Walsh, Aron The Journal of Physical Chemistry Letters, Vol. 7, Issue 6 https://doi.org/10.1021/acs.jpclett.6b00226	journal	March 2016
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
Effect of Light-Induced Halide Segregation on the Performance of Mixed-Halide Perovskite Solar Cells Datta, Kunal; van Gorkom, Bas T.; Chen, Zehua ACS Applied Energy Materials, Vol. 4, Issue 7 https://doi.org/10.1021/acsaem.1c00707	journal	July 2021
Origin of Ionic Inhomogeneity in MAPb(I _x Br _{1– x} ) ₃ Perovskite Thin Films Revealed by In-Situ Spectroscopy during Spin Coating and Annealing Rehermann, Carolin; Merdasa, Aboma; Suchan, Klara ACS Applied Materials & Interfaces, Vol. 12, Issue 27 https://doi.org/10.1021/acsami.0c05894	journal	June 2020
Urbach Energy and Open-Circuit Voltage Deficit for Mixed Anion–Cation Perovskite Solar Cells Subedi, Biwas; Li, Chongwen; Chen, Cong ACS Applied Materials & Interfaces, Vol. 14, Issue 6 https://doi.org/10.1021/acsami.1c19122	journal	February 2022
Solution-Processed Monolithic All-Perovskite Triple-Junction Solar Cells with Efficiency Exceeding 20% Xiao, Ke; Wen, Jin; Han, Qiaolei ACS Energy Letters, Vol. 5, Issue 9 https://doi.org/10.1021/acsenergylett.0c01184	journal	August 2020
Mixing Matters: Nanoscale Heterogeneity and Stability in Metal Halide Perovskite Solar Cells Mundt, Laura E.; Zhang, Fei; Palmstrom, Axel F. ACS Energy Letters, Vol. 7, Issue 1 https://doi.org/10.1021/acsenergylett.1c02338	journal	December 2021
Ethylenediamine Addition Improves Performance and Suppresses Phase Instabilities in Mixed-Halide Perovskites Taddei, Margherita; Smith, Joel A.; Gallant, Benjamin M. ACS Energy Letters, Vol. 7, Issue 12 https://doi.org/10.1021/acsenergylett.2c01998	journal	November 2022
The Electronic Disorder Landscape of Mixed Halide Perovskites Liu, Yun; Banon, Jean-Philippe; Frohna, Kyle ACS Energy Letters, Vol. 8, Issue 1 https://doi.org/10.1021/acsenergylett.2c02352	journal	November 2022
Atomic Layer Deposition-Free Monolithic Perovskite/Perovskite/Silicon Triple-Junction Solar Cells Choi, Yeo Jin; Lim, Sung Yeon; Park, Jae Hyun ACS Energy Letters, Vol. 8, Issue 7 https://doi.org/10.1021/acsenergylett.3c00919	journal	June 2023
In situ Stress Monitoring Reveals Tension and Wrinkling Evolutions during Halide Perovskite Film Formation Guo, Boyu; Chauhan, Mihirsinh; Woodward, Nathaniel R. ACS Energy Letters, Vol. 9, Issue 1 https://doi.org/10.1021/acsenergylett.3c02079	journal	December 2023
Local A-Site Phase Segregation Leads to Cs-Rich Regions Showing Accelerated Photodegradation in Mixed-Cation Perovskite Semiconductor Films Huang, Zixu; Jiang, Fangyuan; Song, Zhaoning ACS Energy Letters, Vol. 9, Issue 6 https://doi.org/10.1021/acsenergylett.4c00960	journal	May 2024
Band Tailing and Deep Defect States in CH ₃ NH ₃ Pb(I _{1– x} Br _x ) ₃ Perovskites As Revealed by Sub-Bandgap Photocurrent Sutter-Fella, Carolin M.; Miller, D. Westley; Ngo, Quynh P. ACS Energy Letters, Vol. 2, Issue 3 https://doi.org/10.1021/acsenergylett.6b00727	journal	February 2017
Defect-Assisted Photoinduced Halide Segregation in Mixed-Halide Perovskite Thin Films Barker, Alex J.; Sadhanala, Aditya; Deschler, Felix ACS Energy Letters, Vol. 2, Issue 6 https://doi.org/10.1021/acsenergylett.7b00282	journal	May 2017
The Potential of Multijunction Perovskite Solar Cells Hörantner, Maximilian T.; Leijtens, Tomas; Ziffer, Mark E. ACS Energy Letters, Vol. 2, Issue 10 https://doi.org/10.1021/acsenergylett.7b00647	journal	October 2017
The Many Faces of Mixed Ion Perovskites: Unraveling and Understanding the Crystallization Process Gratia, Paul; Zimmermann, Iwan; Schouwink, Pascal ACS Energy Letters, Vol. 2, Issue 12 https://doi.org/10.1021/acsenergylett.7b00981	journal	November 2017
Controlling Thin-Film Stress and Wrinkling during Perovskite Film Formation Bush, Kevin A.; Rolston, Nicholas; Gold-Parker, Aryeh ACS Energy Letters, Vol. 3, Issue 6 https://doi.org/10.1021/acsenergylett.8b00544	journal	May 2018
Synergistic Effects of Interfacial Energy Level Regulation and Stress Relaxation via a Buried Interface for Highly Efficient Perovskite Solar Cells Fu, Jianfei; Zhang, Jiajia; Zhang, Taoyi ACS Nano, Vol. 17, Issue 3 https://doi.org/10.1021/acsnano.2c11091	journal	January 2023
Residual Film Stresses in Perovskite Solar Cells: Origins, Effects, and Mitigation Strategies Dailey, Matthew; Li, Yanan; Printz, Adam D. ACS Omega, Vol. 6, Issue 45 https://doi.org/10.1021/acsomega.1c04814	journal	November 2021
Intrinsic Halide Segregation at Nanometer Scale Determines the High Efficiency of Mixed Cation/Mixed Halide Perovskite Solar Cells Gratia, Paul; Grancini, Giulia; Audinot, Jean-Nicolas Journal of the American Chemical Society, Vol. 138, Issue 49 https://doi.org/10.1021/jacs.6b10049	journal	December 2016
How antisolvent miscibility affects perovskite film wrinkling and photovoltaic properties Kim, Seul-Gi; Kim, Jeong-Hyeon; Ramming, Philipp Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-21803-2	journal	March 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
Revealing defective interfaces in perovskite solar cells from highly sensitive sub-bandgap photocurrent spectroscopy using optical cavities van Gorkom, Bas T.; van der Pol, Tom P. A.; Datta, Kunal Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-021-27560-6	journal	January 2022
Effect of sub-bandgap defects on radiative and non-radiative open-circuit voltage losses in perovskite solar cells Aalbers, Guus J. W.; van der Pol, Tom P. A.; Datta, Kunal Nature Communications, Vol. 15, Issue 1 https://doi.org/10.1038/s41467-024-45512-8	journal	February 2024
Halide homogenization for low energy loss in 2-eV-bandgap perovskites and increased efficiency in all-perovskite triple-junction solar cells Wang, Junke; Zeng, Lewei; Zhang, Dong Nature Energy, Vol. 9, Issue 1 https://doi.org/10.1038/s41560-023-01406-5	journal	November 2023
Nanoscale chemical heterogeneity dominates the optoelectronic response of alloyed perovskite solar cells Frohna, Kyle; Anaya, Miguel; Macpherson, Stuart Nature Nanotechnology, Vol. 17, Issue 2 https://doi.org/10.1038/s41565-021-01019-7	journal	November 2021
Metal halide perovskite tandem and multiple-junction photovoltaics Eperon, Giles E.; Hörantner, Maximilian T.; Snaith, Henry J. Nature Reviews Chemistry, Vol. 1, Issue 12 https://doi.org/10.1038/s41570-017-0095	journal	November 2017
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
Regulating surface potential maximizes voltage in all-perovskite tandems Chen, Hao; Maxwell, Aidan; Li, Chongwen Nature, Vol. 613, Issue 7945 https://doi.org/10.1038/s41586-022-05541-z	journal	November 2022
Suppressed phase segregation for triple-junction perovskite solar cells Wang, Zaiwei; Zeng, Lewei; Zhu, Tong Nature, Vol. 618, Issue 7963 https://doi.org/10.1038/s41586-023-06006-7	journal	March 2023
All-perovskite tandem solar cells with 3D/3D bilayer perovskite heterojunction Lin, Renxing; Wang, Yurui; Lu, Qianwen Nature, Vol. 620, Issue 7976 https://doi.org/10.1038/s41586-023-06278-z	journal	June 2023
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
Exploration of the compositional space for mixed lead halogen perovskites for high efficiency solar cells Jesper Jacobsson, T.; Correa-Baena, Juan-Pablo; Pazoki, Meysam Energy & Environmental Science, Vol. 9, Issue 5 https://doi.org/10.1039/C6EE00030D	journal	January 2016
Revealing the origin of voltage loss in mixed-halide perovskite solar cells Mahesh, Suhas; Ball, James M.; Oliver, Robert D. J. Energy & Environmental Science, Vol. 13, Issue 1 https://doi.org/10.1039/C9EE02162K	journal	January 2020
Conformal monolayer contacts with lossless interfaces for perovskite single junction and monolithic tandem solar cells Al-Ashouri, Amran; Magomedov, Artiom; Roß, Marcel Energy & Environmental Science, Vol. 12, Issue 11 https://doi.org/10.1039/C9EE02268F	journal	January 2019
Unraveling the varied nature and roles of defects in hybrid halide perovskites with time-resolved photoemission electron microscopy Kosar, Sofiia; Winchester, Andrew J.; Doherty, Tiarnan A. S. Energy & Environmental Science, Vol. 14, Issue 12 https://doi.org/10.1039/D1EE02055B	journal	January 2021
Role of spinodal-like wrinkling as a prenucleation process in crystallization of sol-gel derived thin films Valant, Matjaz; Fanetti, Mattia; Luin, Uros Applied Physics Letters, Vol. 108, Issue 15 https://doi.org/10.1063/1.4946764	journal	April 2016
Optical characterization and bandgap engineering of flat and wrinkle-textured FA _0.83 Cs _0.17 Pb(I _1– _x Br _x ) ₃ perovskite thin films Tejada, A.; Braunger, S.; Korte, L. Journal of Applied Physics, Vol. 123, Issue 17 https://doi.org/10.1063/1.5025728	journal	May 2018
Wrinkling of a sol-gel-derived thin film Kwon, S. Joon; Park, Jae-Hwan; Park, Jae-Gwan Physical Review E, Vol. 71, Issue 1 https://doi.org/10.1103/PhysRevE.71.011604	journal	January 2005
Evolution of a Stress-Driven Pattern in Thin Bilayer Films: Spinodal Wrinkling Yoo, Pil J.; Lee, Hong H. Physical Review Letters, Vol. 91, Issue 15 https://doi.org/10.1103/PhysRevLett.91.154502	journal	October 2003
Evolution of Wrinkles in Elastic-Viscoelastic Bilayer Thin Films Im, S. H.; Huang, R. Journal of Applied Mechanics, Vol. 72, Issue 6 https://doi.org/10.1115/1.2043191	journal	March 2005
Performance-limiting formation dynamics in mixed-halide perovskites Huang, Tianyi; Tan, Shaun; Nuryyeva, Selbi Science Advances, Vol. 7, Issue 46 https://doi.org/10.1126/sciadv.abj1799	journal	November 2021
Homogenized halides and alkali cation segregation in alloyed organic-inorganic perovskites Correa-Baena, Juan-Pablo; Luo, Yanqi; Brenner, Thomas M. Science, Vol. 363, Issue 6427 https://doi.org/10.1126/science.aah5065	journal	February 2019
Interface engineering for high-performance, triple-halide perovskite–silicon tandem solar cells Mariotti, Silvia; Köhnen, Eike; Scheler, Florian Science, Vol. 381, Issue 6653 https://doi.org/10.1126/science.adf5872	journal	July 2023

Similar Records

Enhanced Photostability of “Hollow” Mixed Halide Wide-Bandgap Perovskite Films

Journal Article · Tue Nov 28 19:00:00 EST 2023 · ACS Energy Letters · OSTI ID:2521018

Related Subjects

36 MATERIALS SCIENCE
Solar cells

Local halide heterogeneity drives surface wrinkling in mixed-halide wide-bandgap perovskites

Citation Formats

References (63)

Similar Records

Related Subjects