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Pressure-Dependent Polymorphism and Band-Gap Tuning of Methylammonium Lead Iodide Perovskite

Jiang, Shaojie and Fang, Yanan and Li, Ruipeng and Xiao, Hai and Crowley, Jason and Wang, Chenyu and White, Timothy J. and Goddard, William A., III and Wang, Zhongwu and Baikie, Tom and Fang, Jiye (2016) Pressure-Dependent Polymorphism and Band-Gap Tuning of Methylammonium Lead Iodide Perovskite. Angewandte Chemie International Edition, 55 (22). pp. 6540-6544. ISSN 1433-7851. doi:10.1002/anie.201601788.

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We report the pressure-induced crystallographic transitions and optical behavior of MAPbI_3 (MA=methylammonium) using in situ synchrotron X-ray diffraction and laser-excited photoluminescence spectroscopy, supported by density functional theory (DFT) calculations using the hybrid functional B3PW91 with spin-orbit coupling. The tetragonal polymorph determined at ambient pressure transforms to a ReO_3-type cubic phase at 0.3 GPa. Upon continuous compression to 2.7 GPa this cubic polymorph converts into a putative orthorhombic structure. Beyond 4.7 GPa it separates into crystalline and amorphous fractions. During decompression, this phase-mixed material undergoes distinct restoration pathways depending on the peak pressure. In situ pressure photoluminescence investigation suggests a reduction in band gap with increasing pressure up to ≈0.3 GPa and then an increase in band gap up to a pressure of 2.7 GPa, in excellent agreement with our DFT calculation prediction.

Item Type:Article
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URLURL TypeDescription ItemSupporting Information
Xiao, Hai0000-0001-9399-1584
White, Timothy J.0000-0001-8006-7173
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2016 Wiley-VCH Verlag GmbH & Co. Received: February 19, 2016. Article first published online: 21 Apr 2016. This work is partially supported by NRF-CRP14-2014-03, Custom Electronics, Inc., and 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. CHESS is supported by the NSF award DMR-1332208. S.J. acknowledges the support by Binghamton University.
Funding AgencyGrant Number
National Research Foundation of Korea (NRF)NRF-CRP14-2014-03
Custom Electronics Inc.UNSPECIFIED
Joint Center for Artificial PhotosynthesisUNSPECIFIED
Department of Energy (DOE)DE-SC0004993
Binghamton UniversityUNSPECIFIED
Subject Keywords:band gap · halide perovskite · high-pressure chemistry · phase transitions · photoluminescence
Issue or Number:22
Record Number:CaltechAUTHORS:20160427-103659758
Persistent URL:
Official Citation:S. Jiang, Y. Fang, R. Li, H. Xiao, J. Crowley, C. Wang, T. J. White, W. A. Goddard, Z. Wang, T. Baikie, J. Fang, Angew. Chem. Int. Ed. 2016, 55, 6540.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:66511
Deposited By: Ruth Sustaita
Deposited On:27 Apr 2016 18:38
Last Modified:10 Nov 2021 23:59

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