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Layer-by-Layer Degradation of Methylammonium Lead Tri-iodide Perovskite Microplates

Fan, Zheng and Xiao, Hai and Wang, Yiliu and Zhao, Zipeng and Lin, Zhaoyang and Cheng, Hung-Chieh and Lee, Sung-Joon and Wang, Gongming and Feng, Ziying and Goddard, William A., III and Huang, Yu and Duan, Xiangfeng (2017) Layer-by-Layer Degradation of Methylammonium Lead Tri-iodide Perovskite Microplates. Joule, 1 (3). pp. 548-562. ISSN 2542-4351. doi:10.1016/j.joule.2017.08.005.

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The methylammonium lead iodide (MAPbI3) perovskite has attracted considerable interest for its high-efficiency, low-cost solar cells, but is currently plagued by its poor environmental and thermal stability. To aid the development of robust devices, we investigate here the microscopic degradation pathways of MAPbI3 microplates. Using in situ transmission electron microscopy to follow the thermal degradation process, we find that under moderate heating at 85°C the crystalline structure shows a gradual evolution from tetragonal MAPbI3 to trigonal lead iodide layered crystals with a fixed crystallographic direction. Our solid-state nudged elastic band calculations confirm that the surface-initiated layer-by-layer degradation path exhibits the lowest energy barrier for crystal transition. We further show experimentally and theoretically that encapsulation of the perovskites with boron nitride flakes suppresses the surface degradation, greatly improving its thermal stability. These studies provide mechanistic insight into the thermal stability of perovskites that suggests new designs for improved stability.

Item Type:Article
Related URLs:
URLURL TypeDescription
Xiao, Hai0000-0001-9399-1584
Lin, Zhaoyang0000-0002-6474-7184
Goddard, William A., III0000-0003-0097-5716
Huang, Yu0000-0003-1793-0741
Duan, Xiangfeng0000-0002-4321-6288
Additional Information:© 2017 Elsevier B.V. Received 15 June 2017, Revised 24 June 2017, Accepted 4 August 2017, Available online 20 September 2017. Published: September 20, 2017. X.D. acknowledges the support by National Science Foundation DMR1508144. Y.H. acknowledges the financial support from National Science Foundation EFRI-1433541. W.A.G. and H.X. acknowledge support by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award no. DE-SC0004993. Author Contributions: X.D., Y.H., and Z. Fan designed the research and experimental studies. W.A.G. and H.X. designed and conducted the theoretical studies. Z. Fan carried out the in situ HRTEM characterization. H.X. performed the theoretical calculations. Y.W., G.W., and Z.L. synthesized the material and conducted the XRD characterization. Z. Feng and Z.Z. analyzed the data. H.C.-C., S.-J.L., and Z. Fan prepared the hBN-perovskite-hBN heterostructure. X.D., Z. Fan, and H.X. wrote the manuscript. All the authors participated in discussions of the research.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Subject Keywords:hybrid perovskite; thermal stability; in situ TEM
Issue or Number:3
Record Number:CaltechAUTHORS:20170921-103249191
Persistent URL:
Official Citation:Zheng Fan, Hai Xiao, Yiliu Wang, Zipeng Zhao, Zhaoyang Lin, Hung-Chieh Cheng, Sung-Joon Lee, Gongming Wang, Ziying Feng, William A. Goddard, Yu Huang, Xiangfeng Duan, Layer-by-Layer Degradation of Methylammonium Lead Tri-iodide Perovskite Microplates, In Joule, Volume 1, Issue 3, 2017, Pages 548-562, ISSN 2542-4351, (
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:81674
Deposited By: Ruth Sustaita
Deposited On:21 Sep 2017 17:56
Last Modified:15 Nov 2021 19:45

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