Humidity Disrupts Structural and Chiroptical Properties of Chiral 2D Perovskites

Nurdillayeva, Raushan N.; Moral, Raphael F.; Pols, Mike; Lee, Do-Kyoung; Altoe, Virginia; Schwartz, Craig P.; Tao, Shuxia; Sutter-Fella, Carolin M.

doi:10.1021/acsnano.5c00480

Humidity Disrupts Structural and Chiroptical Properties of Chiral 2D Perovskites

Journal Article · Sun Mar 16 00:00:00 EDT 2025 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.5c00480· OSTI ID:2539860

^[1]; ^[2]; ^[3]; Lee, Do-Kyoung ^[2]; Altoe, Virginia ^[4]; ^[5]; ^[3]; ^[4]

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Khoja Akhmet Yassawi International Kazakh-Turkish University (Kazakhstan)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of Nevada, Las Vegas, NV (United States)
Eindhoven University of Technology (The Netherlands)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
University of Nevada, Las Vegas, NV (United States)

Chiral two-dimensional (2D) hybrid organic–inorganic metal halide perovskite semiconductors have emerged as an exceptional material platform with many design opportunities for spintronic applications. However, a comprehensive understanding of changes to the crystal structure and chiroptical properties upon exposure to atmospheric humidity has not been established. We demonstrate phase degradation to the 1D (MBA)PbI₃ (MBA = methylbenzylammonium) and the hypothetical (MBA)₃PbI₅·H₂O hydrate phases, accompanied by a reduction and disappearance of the chiroptical response. Firstprinciple simulations show that water molecules preferentially locate at the interface between the organic cations and the inorganic framework, thereby disrupting the hydrogen bonding, impacting both the structural chirality and stability of the material. These findings provide critical insights into phase degradation mechanisms and their impact on chiroptical activity in chiral 2D perovskites.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; SC0023355

OSTI ID:: 2539860

Alternate ID(s):: OSTI ID: 2538438

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 11 Vol. 19; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (52)

Secondary Ion Mass Spectrometry (SIMS) for Chemical Characterization of Metal Halide Perovskites Liu, Yongtao; Lorenz, Matthias; Ievlev, Anton V. Advanced Functional Materials https://doi.org/10.1002/adfm.202002201	journal	June 2020
Imprinting Chirality onto the Electronic States of Colloidal Perovskite Nanoplatelets Georgieva, Zheni N.; Bloom, Brian P.; Ghosh, Supriya Advanced Materials, Vol. 30, Issue 23 https://doi.org/10.1002/adma.201800097	journal	April 2018
Moisture‐Resistant Chiral Perovskites for White‐Light Circularly Polarized Photoluminescence Peng, Yu; Wang, Xing; Li, Lina Advanced Optical Materials, Vol. 11, Issue 1 https://doi.org/10.1002/adom.202201888	journal	November 2022
Tuning Phase Purity in Chiral 2D Perovskites Scalon, Lucas; Brunner, Julius; Guaita, Maria Gabriella Detone Advanced Optical Materials, Vol. 12, Issue 2 https://doi.org/10.1002/adom.202300776	journal	July 2023
Dimensional Engineering of a Graded 3D-2D Halide Perovskite Interface Enables Ultrahigh V _oc Enhanced Stability in the p-i-n Photovoltaics Bai, Yang; Xiao, Shuang; Hu, Chen Advanced Energy Materials, Vol. 7, Issue 20 https://doi.org/10.1002/aenm.201701038	journal	July 2017
One and Two‐Dimensional 1,4‐Xylylenediammonium (pXDA) Lead Halides: Powders and Thin Films García‐Espejo, Gonzalo; Konidaris, Konstantis F.; Anzini, Pietro European Journal of Inorganic Chemistry, Vol. 26, Issue 23 https://doi.org/10.1002/ejic.202300282	journal	June 2023
Effect of the damping function in dispersion corrected density functional theory Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars Journal of Computational Chemistry, Vol. 32, Issue 7 https://doi.org/10.1002/jcc.21759	journal	March 2011
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Revealing the vertical structure of in-situ fabricated perovskite nanocrystals films toward efficient pure red light-emitting diodes Wu, Xian-gang; Sun, Shipei; Song, Tinglu Fundamental Research, Vol. 4, Issue 2 https://doi.org/10.1016/j.fmre.2022.05.004	journal	March 2024
Chiral halide perovskite crystals for optoelectronic applications Dang, Yangyang; Liu, Xiaolong; Cao, Bingqiang Matter, Vol. 4, Issue 3 https://doi.org/10.1016/j.matt.2020.12.018	journal	March 2021
Database of Two-Dimensional Hybrid Perovskite Materials: Open-Access Collection of Crystal Structures, Band Gaps, and Atomic Partial Charges Predicted by Machine Learning Marchenko, Ekaterina I.; Fateev, Sergey A.; Petrov, Andrey A. Chemistry of Materials, Vol. 32, Issue 17 https://doi.org/10.1021/acs.chemmater.0c02290	journal	August 2020
Understanding and Controlling the Photoluminescence Line Shapes of 2D Perovskites with Chiral Methylbenzylammonium-Based Cations Scalon, Lucas; New, Arianne; Ge, Ziyuan Chemistry of Materials, Vol. 36, Issue 9 https://doi.org/10.1021/acs.chemmater.3c03234	journal	April 2024
Ruddlesden–Popper Hybrid Lead Iodide Perovskite 2D Homologous Semiconductors Stoumpos, Constantinos C.; Cao, Duyen H.; Clark, Daniel J. Chemistry of Materials, Vol. 28, Issue 8, p. 2852-2867 https://doi.org/10.1021/acs.chemmater.6b00847	journal	April 2016
The 2D Halide Perovskite Rulebook: How the Spacer Influences Everything from the Structure to Optoelectronic Device Efficiency Li, Xiaotong; Hoffman, Justin M.; Kanatzidis, Mercouri G. Chemical Reviews, Vol. 121, Issue 4 https://doi.org/10.1021/acs.chemrev.0c01006	journal	January 2021
Understanding Degradation Mechanisms and Improving Stability of Perovskite Photovoltaics Boyd, Caleb C.; Cheacharoen, Rongrong; Leijtens, Tomas Chemical Reviews, Vol. 119, Issue 5 https://doi.org/10.1021/acs.chemrev.8b00336	journal	November 2018
Tuning the Luminescence of Layered Halide Perovskites Smith, Matthew D.; Connor, Bridget A.; Karunadasa, Hemamala I. Chemical Reviews, Vol. 119, Issue 5 https://doi.org/10.1021/acs.chemrev.8b00477	journal	January 2019
The Role of Alkyl Chain Length and Halide Counter Ion in Layered Dion−Jacobson Perovskites with Aromatic Spacers Dučinskas, Algirdas; Fish, George C.; Hope, Michael A. The Journal of Physical Chemistry Letters, Vol. 12, Issue 42 https://doi.org/10.1021/acs.jpclett.1c02937	journal	October 2021
Temperature-Dependent Chirality in Halide Perovskites Pols, Mike; Brocks, Geert; Calero, Sofía The Journal of Physical Chemistry Letters, Vol. 15, Issue 31, p. 8057-8064 https://doi.org/10.1021/acs.jpclett.4c01629	journal	July 2024
Unravelling the Behavior of Dion–Jacobson Layered Hybrid Perovskites in Humid Environments Dučinskas, Algirdas; Kim, Gee Yeong; Moia, Davide ACS Energy Letters, Vol. 6, Issue 2 https://doi.org/10.1021/acsenergylett.0c02344	journal	December 2020
Spin-Dependent Photovoltaic and Photogalvanic Responses of Optoelectronic Devices Based on Chiral Two-Dimensional Hybrid Organic–Inorganic Perovskites Wang, Jingying; Lu, Haipeng; Pan, Xin ACS Nano, Vol. 15, Issue 1 https://doi.org/10.1021/acsnano.0c05980	journal	November 2020
Highly Tunable Colloidal Perovskite Nanoplatelets through Variable Cation, Metal, and Halide Composition Weidman, Mark C.; Seitz, Michael; Stranks, Samuel D. ACS Nano, Vol. 10, Issue 8 https://doi.org/10.1021/acsnano.6b03496	journal	July 2016
Chiral 2D Perovskites with a High Degree of Circularly Polarized Photoluminescence Ma, Jiaqi; Fang, Chen; Chen, Chao ACS Nano, Vol. 13, Issue 3 https://doi.org/10.1021/acsnano.9b00302	journal	March 2019
Transformation of the Excited State and Photovoltaic Efficiency of CH ₃ NH ₃ PbI ₃ Perovskite upon Controlled Exposure to Humidified Air Christians, Jeffrey A.; Miranda Herrera, Pierre A.; Kamat, Prashant V. Journal of the American Chemical Society, Vol. 137, Issue 4 https://doi.org/10.1021/ja511132a	journal	January 2015
Two-Dimensional Hybrid Halide Perovskites: Principles and Promises Mao, Lingling; Stoumpos, Constantinos C.; Kanatzidis, Mercouri G. Journal of the American Chemical Society, Vol. 141, Issue 3 https://doi.org/10.1021/jacs.8b10851	journal	November 2018
Bulk Photovoltaic Effect in a Pair of Chiral–Polar Layered Perovskite-Type Lead Iodides Altered by Chirality of Organic Cations Huang, Po-Jung; Taniguchi, Kouji; Miyasaka, Hitoshi Journal of the American Chemical Society, Vol. 141, Issue 37 https://doi.org/10.1021/jacs.9b06815	journal	September 2019
Chiral 2D Organic Inorganic Hybrid Perovskite with Circular Dichroism Tunable Over Wide Wavelength Range Ahn, Jihoon; Ma, Sunihl; Kim, Ji-Young Journal of the American Chemical Society, Vol. 142, Issue 9 https://doi.org/10.1021/jacs.9b11453	journal	February 2020
The Raman Spectrum of the CH ₃ NH ₃ PbI ₃ Hybrid Perovskite: Interplay of Theory and Experiment Quarti, Claudio; Grancini, Giulia; Mosconi, Edoardo The Journal of Physical Chemistry Letters, Vol. 5, Issue 2 https://doi.org/10.1021/jz402589q	journal	December 2013
Atomistic Origins of High-Performance in Hybrid Halide Perovskite Solar Cells Frost, Jarvist M.; Butler, Keith T.; Brivio, Federico Nano Letters, Vol. 14, Issue 5 https://doi.org/10.1021/nl500390f	journal	April 2014
Trapped charge-driven degradation of perovskite solar cells Ahn, Namyoung; Kwak, Kwisung; Jang, Min Seok Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13422	journal	November 2016
Circularly polarized light detection using chiral hybrid perovskite Chen, Chao; Gao, Liang; Gao, Wanru Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09942-z	journal	April 2019
Unraveling chirality transfer mechanism by structural isomer-derived hydrogen bonding interaction in 2D chiral perovskite Son, Jaehyun; Ma, Sunihl; Jung, Young-Kwang Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-38927-2	journal	May 2023
A dual spin-controlled chiral two-/three-dimensional perovskite artificial leaf for efficient overall photoelectrochemical water splitting Lee, Hyungsoo; Lee, Chan Uk; Yun, Juwon Nature Communications, Vol. 15, Issue 1 https://doi.org/10.1038/s41467-024-49216-x	journal	June 2024
Chiral molecules and the electron spin Naaman, Ron; Paltiel, Yossi; Waldeck, David H. Nature Reviews Chemistry, Vol. 3, Issue 4 https://doi.org/10.1038/s41570-019-0087-1	journal	March 2019
Control of light, spin and charge with chiral metal halide semiconductors Lu, Haipeng; Vardeny, Zeev Valy; Beard, Matthew C. Nature Reviews Chemistry, Vol. 6, Issue 7 https://doi.org/10.1038/s41570-022-00399-1	journal	June 2022
Dimensional tailoring of hybrid perovskites for photovoltaics Grancini, Giulia; Nazeeruddin, Mohammad Khaja Nature Reviews Materials, Vol. 4, Issue 1 https://doi.org/10.1038/s41578-018-0065-0	journal	November 2018
Chiral-perovskite optoelectronics Long, Guankui; Sabatini, Randy; Saidaminov, Makhsud I. Nature Reviews Materials, Vol. 5, Issue 6 https://doi.org/10.1038/s41578-020-0181-5	journal	March 2020
Deterministic delivery of remote entanglement on a quantum network Humphreys, Peter C.; Kalb, Norbert; Morits, Jaco P. J. Nature, Vol. 558, Issue 7709 https://doi.org/10.1038/s41586-018-0200-5	journal	June 2018
Nomenclature of Organic Chemistry Favre, Henri A.; Powell, Warren H. https://doi.org/10.1039/9781849733069	book	December 2013
Synthesis and crystal structures of inorganic–organic hybrids incorporating an aromatic amine with a chiral functional group Billing, David G.; Lemmerer, Andreas CrystEngComm, Vol. 8, Issue 9 https://doi.org/10.1039/B606987H	journal	January 2006
A new class of chiral semiconductors: chiral-organic-molecule-incorporating organic–inorganic hybrid perovskites Ahn, Jihoon; Lee, Eunsong; Tan, Jeiwan Materials Horizons, Vol. 4, Issue 5 https://doi.org/10.1039/C7MH00197E	journal	January 2017
Degradation mechanisms in mixed-cation and mixed-halide Cs _x FA _1−x Pb(Br _y I _1−y ) ₃ perovskite films under ambient conditions Marchezi, Paulo Ernesto; Therézio, Eralci Moreira; Szostak, Rodrigo Journal of Materials Chemistry A, Vol. 8, Issue 18 https://doi.org/10.1039/D0TA01201G	journal	January 2020
Pathways to increase the dissymmetry in the interaction of chiral light and chiral molecules Greenfield, Jake L.; Wade, Jessica; Brandt, Jochen R. Chemical Science, Vol. 12, Issue 25 https://doi.org/10.1039/D1SC02335G	journal	January 2021
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Excitons in ultrathin organic-inorganic perovskite crystals Yaffe, Omer; Chernikov, Alexey; Norman, Zachariah M. Physical Review B, Vol. 92, Issue 4 https://doi.org/10.1103/PhysRevB.92.045414	journal	July 2015
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Irena : tool suite for modeling and analysis of small-angle scattering Ilavsky, Jan; Jemian, Peter R. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889809002222	journal	February 2009
Nika : software for two-dimensional data reduction Ilavsky, Jan Journal of Applied Crystallography, Vol. 45, Issue 2 https://doi.org/10.1107/S0021889812004037	journal	March 2012
Bis(1-phenylethylammonium) tetraiodoplumbate(II) Billing, David G. Acta Crystallographica Section E Structure Reports Online, Vol. 58, Issue 11 https://doi.org/10.1107/S1600536802019025	journal	October 2002
Direct detection of circular polarized light in helical 1D perovskite-based photodiode Ishii, A.; Miyasaka, T. Science Advances, Vol. 6, Issue 46 https://doi.org/10.1126/sciadv.abd3274	journal	November 2020
Deterministic fabrication of 3D/2D perovskite bilayer stacks for durable and efficient solar cells Sidhik, Siraj; Wang, Yafei; De Siena, Michael Science, Vol. 377, Issue 6613 https://doi.org/10.1126/science.abq7652	journal	September 2022

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Humidity Disrupts Structural and Chiroptical Properties of Chiral 2D Perovskites

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References (52)

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