Entropy Stabilization Effects and Ion Migration in 3D “Hollow” Halide Perovskites

Jayanthi, K.; Spanopoulos, Ioannis; Zibouche, Nourdine; Voskanyan, Albert A.; Vasileiadou, Eugenia S.; Islam, M. Saiful; Navrotsky, Alexandra; Kanatzidis, Mercouri G.

doi:10.1021/jacs.2c01383

Entropy Stabilization Effects and Ion Migration in 3D “Hollow” Halide Perovskites

Journal Article · Thu Apr 28 00:00:00 EDT 2022 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.2c01383· OSTI ID:1869303

^[1]; ^[2]; Zibouche, Nourdine ^[3]; ^[4]; ^[5]; Islam, M. Saiful ^[6]; ^[4]; ^[5]

Arizona State Univ., Tempe, AZ (United States); Northwestern University
Northwestern Univ., Evanston, IL (United States); Univ. of South Florida, Tampa, FL (United States)
Univ. of Bath (United Kingdom)
Arizona State Univ., Tempe, AZ (United States)
Northwestern Univ., Evanston, IL (United States)
Univ. of Bath (United Kingdom); Univ. of Oxford (United Kingdom)

A recently discovered new family of 3D halide perovskites with the general formula (A)_1–x(en)_x(Pb)_1–0.7x(X)_3–0.4x (A = MA, FA; X = Br, I; MA = methylammonium, FA = formamidinium, en = ethylenediammonium) is referred to as “hollow” perovskites owing to extensive Pb and X vacancies created on incorporation of en cations in the 3D network. The “hollow” motif allows fine tuning of optical, electronic, and transport properties and bestowing good environmental stability proportional to en loading. To shed light on the origin of the apparent stability of these materials, we performed detailed thermochemical studies, using room temperature solution calorimetry combined with density functional theory simulations on three different families of “hollow” perovskites namely en/FAPbI₃, en/MAPbI₃, and en/FAPbBr₃. We found that the bromide perovskites are more energetically stable compared to iodide perovskites in the FA-based hollow compounds, as shown by the measured enthalpies of formation and the calculated formation energies. The least stable FAPbI₃ gains stability on incorporation of the en cation, whereas FAPbBr₃ becomes less stable with en loading. This behavior is attributed to the difference in the 3D cage size in the bromide and iodide perovskites. Configurational entropy, which arises from randomly distributed cation and anion vacancies, plays a significant role in stabilizing these “hollow” perovskite structures despite small differences in their formation enthalpies. With the increased vacancy defect population, we have also examined halide ion migration in the FA-based “hollow” perovskites and found that the migration energy barriers become smaller with the increasing en content.

View Accepted Manuscript (DOE)

Research Organization:: Northwestern Univ., Evanston, IL (United States); Univ. of California, Santa Barbara, CA (United States)

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

Grant/Contract Number:: SC0012541; SC0021987

OSTI ID:: 1869303

Alternate ID(s):: OSTI ID: 1870313

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 18 Vol. 144; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (47)

Unique Properties of Halide Perovskites as Possible Origins of the Superior Solar Cell Performance Yin, Wan-Jian; Shi, Tingting; Yan, Yanfa Advanced Materials, Vol. 26, Issue 27 https://doi.org/10.1002/adma.201306281	journal	May 2014
Halide Perovskites: Poor Man's High-Performance Semiconductors Stoumpos, Constantinos C.; Kanatzidis, Mercouri G. Advanced Materials, Vol. 28, Issue 28 https://doi.org/10.1002/adma.201600265	journal	May 2016
Intrinsic Instability of Inorganic–Organic Hybrid Halide Perovskite Materials Park, Byung‐wook; Seok, Sang Il Advanced Materials, Vol. 31, Issue 20 https://doi.org/10.1002/adma.201805337	journal	December 2018
Impact of White Light Illumination on the Electronic and Chemical Structures of Mixed Halide and Single Crystal Perovskites Zu, Feng-Shuo; Amsalem, Patrick; Salzmann, Ingo Advanced Optical Materials, Vol. 5, Issue 9 https://doi.org/10.1002/adom.201700139	journal	March 2017
Reentrant Structural and Optical Properties and Large Positive Thermal Expansion in Perovskite Formamidinium Lead Iodide Fabini, Douglas H.; Stoumpos, Constantinos C.; Laurita, Geneva Angewandte Chemie International Edition, Vol. 55, Issue 49 https://doi.org/10.1002/anie.201609538	journal	November 2016
In Quest of Environmentally Stable Perovskite Solar Cells: A Perspective Spanopoulos, Ioannis; Ke, Weijun; Kanatzidis, Mercouri G. Helvetica Chimica Acta, Vol. 104, Issue 1 https://doi.org/10.1002/hlca.202000173	journal	December 2020
Die Gesetze der Krystallochemie Goldschmidt, V. M. Die Naturwissenschaften, Vol. 14, Issue 21 https://doi.org/10.1007/bf01507527	journal	May 1926
Thermodynamics of formation of hybrid perovskite-type methylammonium lead halides Ivanov, I. L.; Steparuk, A. S.; Bolyachkina, M. S. The Journal of Chemical Thermodynamics, Vol. 116 https://doi.org/10.1016/j.jct.2017.09.026	journal	January 2018
Germanium-on-Nothing for Epitaxial Liftoff of GaAs Solar Cells Park, Sanghyun; Simon, John; Schulte, Kevin L. Joule, Vol. 3, Issue 7 https://doi.org/10.1016/j.joule.2019.05.013	journal	July 2019
The Renaissance of Halide Perovskites and Their Evolution as Emerging Semiconductors Stoumpos, Constantinos C.; Kanatzidis, Mercouri G. Accounts of Chemical Research, Vol. 48, Issue 10 https://doi.org/10.1021/acs.accounts.5b00229	journal	September 2015
Tuning Ionic and Electronic Conductivities in the “Hollow” Perovskite { en }MAPbI ₃ Senocrate, Alessandro; Spanopoulos, Ioannis; Zibouche, Nourdine Chemistry of Materials, Vol. 33, Issue 2 https://doi.org/10.1021/acs.chemmater.0c04139	journal	January 2021
Mixed A-Cation Perovskites for Solar Cells: Atomic-Scale Insights Into Structural Distortion, Hydrogen Bonding, and Electronic Properties Ghosh, Dibyajyoti; Smith, Alexander R.; Walker, Alison B. Chemistry of Materials, Vol. 30, Issue 15 https://doi.org/10.1021/acs.chemmater.8b01851	journal	July 2018
Long-Distance Ionic Diffusion in Cesium Lead Mixed Halide Perovskite Induced by Focused Illumination Chen, Weijian; Li, Wei; Gan, Zhixing Chemistry of Materials, Vol. 31, Issue 21 https://doi.org/10.1021/acs.chemmater.9b03320	journal	October 2019
Structure–Electronic Property Relationships of 2D Ruddlesden–Popper Tin- and Lead-based Iodide Perovskites Zibouche, Nourdine; Islam, M. Saiful ACS Applied Materials & Interfaces, Vol. 12, Issue 13 https://doi.org/10.1021/acsami.0c03061	journal	March 2020
Progress on Perovskite Materials and Solar Cells with Mixed Cations and Halide Anions Ono, Luis K.; Juarez-Perez, Emilio J.; Qi, Yabing ACS Applied Materials & Interfaces, Vol. 9, Issue 36 https://doi.org/10.1021/acsami.7b06001	journal	July 2017
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
Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties Stoumpos, Constantinos C.; Malliakas, Christos D.; Kanatzidis, Mercouri G. Inorganic Chemistry, Vol. 52, Issue 15, p. 9019-9038 https://doi.org/10.1021/ic401215x	journal	July 2013
Insight on the Stability of Thick Layers in 2D Ruddlesden–Popper and Dion–Jacobson Lead Iodide Perovskites Vasileiadou, Eugenia S.; Wang, Bin; Spanopoulos, Ioannis Journal of the American Chemical Society, Vol. 143, Issue 6 https://doi.org/10.1021/jacs.0c11328	journal	February 2021
Synergistic Effect of Fluorinated Passivator and Hole Transport Dopant Enables Stable Perovskite Solar Cells with an Efficiency Near 24% Zhu, Hongwei; Ren, Yameng; Pan, Linfeng Journal of the American Chemical Society, Vol. 143, Issue 8 https://doi.org/10.1021/jacs.0c12802	journal	February 2021
Tunable Broad Light Emission from 3D “Hollow” Bromide Perovskites through Defect Engineering Spanopoulos, Ioannis; Hadar, Ido; Ke, Weijun Journal of the American Chemical Society, Vol. 143, Issue 18 https://doi.org/10.1021/jacs.1c01727	journal	April 2021
Sulfonate-Assisted Surface Iodide Management for High-Performance Perovskite Solar Cells and Modules Chen, Ruihao; Wang, Yongke; Nie, Siqing Journal of the American Chemical Society, Vol. 143, Issue 28 https://doi.org/10.1021/jacs.1c03419	journal	July 2021
Formation of Stable Mixed Guanidinium–Methylammonium Phases with Exceptionally Long Carrier Lifetimes for High-Efficiency Lead Iodide-Based Perovskite Photovoltaics Kubicki, Dominik J.; Prochowicz, Daniel; Hofstetter, Albert Journal of the American Chemical Society, Vol. 140, Issue 9 https://doi.org/10.1021/jacs.7b12860	journal	February 2018
Unraveling the Chemical Nature of the 3D “Hollow” Hybrid Halide Perovskites Spanopoulos, Ioannis; Ke, Weijun; Stoumpos, Constantinos C. Journal of the American Chemical Society, Vol. 140, Issue 17 https://doi.org/10.1021/jacs.8b01034	journal	April 2018
Optoelectronic Dichotomy of Mixed Halide CH ₃ NH ₃ Pb(Br _{1– x} Cl _x ) ₃ Single Crystals: Surface versus Bulk Photoluminescence Li, Zhongguo; Kolodziej, Charles; Zhang, Taiyang Journal of the American Chemical Society, Vol. 140, Issue 37 https://doi.org/10.1021/jacs.8b07560	journal	August 2018
Phase Transitions of Formamidinium Lead Iodide Perovskite under Pressure Jiang, Shaojie; Luan, Yiliang; Jang, Joon I. Journal of the American Chemical Society, Vol. 140, Issue 42 https://doi.org/10.1021/jacs.8b09316	journal	September 2018
Probing the Degradation Chemistry and Enhanced Stability of 2D Organolead Halide Perovskites Wygant, Bryan R.; Ye, Alexandre Z.; Dolocan, Andrei Journal of the American Chemical Society, Vol. 141, Issue 45 https://doi.org/10.1021/jacs.9b08895	journal	October 2019
Crystal Structure and Photoconductivity of Cæsium Plumbohalides MØLler, Chr. Kn. Nature, Vol. 182, Issue 4647 https://doi.org/10.1038/1821436a0	journal	November 1958
All-solid-state dye-sensitized solar cells with high efficiency Chung, In; Lee, Byunghong; He, Jiaqing Nature, Vol. 485, Issue 7399, p. 486-489 https://doi.org/10.1038/nature11067	journal	May 2012
Compositional engineering of perovskite materials for high-performance solar cells Jeon, Nam Joong; Noh, Jun Hong; Yang, Woon Seok Nature, Vol. 517, Issue 7535 https://doi.org/10.1038/nature14133	journal	January 2015
Ionic transport in hybrid lead iodide perovskite solar cells Eames, Christopher; Frost, Jarvist M.; Barnes, Piers R. F. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8497	journal	June 2015
Exceeding 20% efficiency with in situ group V doping in polycrystalline CdTe solar cells Metzger, W. K.; Grover, S.; Lu, D. Nature Energy, Vol. 4, Issue 10 https://doi.org/10.1038/s41560-019-0446-7	journal	August 2019
Passivating contacts for crystalline silicon solar cells Allen, Thomas G.; Bullock, James; Yang, Xinbo Nature Energy, Vol. 4, Issue 11 https://doi.org/10.1038/s41560-019-0463-6	journal	September 2019
Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9% Kim, Hui-Seon; Lee, Chang-Ryul; Im, Jeong-Hyeok Scientific Reports, Vol. 2, Issue 1 https://doi.org/10.1038/srep00591	journal	August 2012
On the Thermal and Thermodynamic (In)Stability of Methylammonium Lead Halide Perovskites Brunetti, Bruno; Cavallo, Carmen; Ciccioli, Andrea Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep31896	journal	August 2016
Structures, Phase Transitions and Tricritical Behavior of the Hybrid Perovskite Methyl Ammonium Lead Iodide Whitfield, P. S.; Herron, N.; Guise, W. E. Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep35685	journal	October 2016
Entropic stabilization of mixed A-cation ABX ₃ metal halide perovskites for high performance perovskite solar cells Yi, Chenyi; Luo, Jingshan; Meloni, Simone Energy & Environmental Science, Vol. 9, Issue 2 https://doi.org/10.1039/c5ee03255e	journal	January 2016
Cesium-containing triple cation perovskite solar cells: improved stability, reproducibility and high efficiency Saliba, Michael; Matsui, Taisuke; Seo, Ji-Youn Energy & Environmental Science, Vol. 9, Issue 6 https://doi.org/10.1039/c5ee03874j	journal	January 2016
Synthesis, optoelectronic properties and applications of halide perovskites Chouhan, Lata; Ghimire, Sushant; Subrahmanyam, Challapalli Chemical Society Reviews, Vol. 49, Issue 10 https://doi.org/10.1039/c9cs00848a	journal	January 2020
Partial cation substitution reduces iodide ion transport in lead iodide perovskite solar cells Ferdani, Dominic W.; Pering, Samuel R.; Ghosh, Dibyajyoti Energy & Environmental Science, Vol. 12, Issue 7 https://doi.org/10.1039/c9ee00476a	journal	January 2019
Towards commercialization: the operational stability of perovskite solar cells Li, Nengxu; Niu, Xiuxiu; Chen, Qi Chemical Society Reviews, Vol. 49, Issue 22 https://doi.org/10.1039/d0cs00573h	journal	January 2020
Dipolar cation accumulation at the interfaces of perovskite light-emitting solar cells Gets, D. S.; Verkhogliadov, G. A.; Danilovskiy, E. Y. Journal of Materials Chemistry C, Vol. 8, Issue 47 https://doi.org/10.1039/d0tc02654a	journal	January 2020
Direct calorimetric verification of thermodynamic instability of lead halide hybrid perovskites Nagabhushana, G. P.; Shivaramaiah, Radha; Navrotsky, Alexandra Proceedings of the National Academy of Sciences, Vol. 113, Issue 28 https://doi.org/10.1073/pnas.1607850113	journal	June 2016
Enhanced photovoltaic performance and stability with a new type of hollow 3D perovskite {en}FASnI ₃ Ke, Weijun; Stoumpos, Constantinos C.; Zhu, Menghua Science Advances, Vol. 3, Issue 8 https://doi.org/10.1126/sciadv.1701293	journal	August 2017
Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber Stranks, S. D.; Eperon, G. E.; Grancini, G. Science, Vol. 342, Issue 6156, p. 341-344 https://doi.org/10.1126/science.1243982	journal	October 2013
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
A vacuum flash–assisted solution process for high-efficiency large-area perovskite solar cells Li, Xiong; Bi, Dongqin; Yi, Chenyi Science, Vol. 353, Issue 6294 https://doi.org/10.1126/science.aaf8060	journal	June 2016
A Review: Thermal Stability of Methylammonium Lead Halide Based Perovskite Solar Cells Ava, Tanzila Tasnim; Al Mamun, Abdullah; Marsillac, Sylvain Applied Sciences, Vol. 9, Issue 1 https://doi.org/10.3390/app9010188	journal	January 2019

Similar Records

Tunable Broad Light Emission from 3D “Hollow” Bromide Perovskites through Defect Engineering

Journal Article · Mon Apr 26 20:00:00 EDT 2021 · Journal of the American Chemical Society · OSTI ID:1864311

Unraveling the Chemical Nature of the 3D “Hollow” Hybrid Halide Perovskites

Journal Article · Tue Apr 03 20:00:00 EDT 2018 · Journal of the American Chemical Society · OSTI ID:1599736

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Entropy Stabilization Effects and Ion Migration in 3D “Hollow” Halide Perovskites

Citation Formats

References (47)

Similar Records

Related Subjects