High-Resolution In-Situ Synchrotron X-Ray Studies of Inorganic Perovskite CsPbBr3: New Symmetry Assignments and Structural Phase Transitions
Abstract
Perovskite photovoltaic ABX3 systems are being studied due to their high energy-conversion efficiencies with current emphasis placed on pure inorganic systems. In this work, synchrotron single-crystal diffraction measurements combined with second harmonic generation measurements reveal the absence of inversion symmetry below room temperature in CsPbBr3. Local structural analysis by pair distribution function and X-ray absorption fine structure methods are performed to ascertain the local ordering, atomic pair correlations, and phase evolution in a broad range of temperatures. The currently accepted space group assignments for CsPbBr3 are found to be incorrect in a manner that profoundly impacts physical properties. New assignments are obtained for the bulk structure: (above ≈410 K), P21/m (between ≈300 K and ≈410 K), and the polar group Pm (below ≈300 K), respectively. The newly observed structural distortions exist in the bulk structure consistent with the expectation of previous photoluminescence and Raman measurements. High-pressure measurements reveal multiple low-pressure phases, one of which exists as a metastable phase at ambient pressure. This work should help guide research in the perovskite photovoltaic community to better control the structure under operational conditions and further improve transport and optical properties.
- Authors:
-
[1]
- New Jersey Institute of Technology, Newark, NJ (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Univ. of Illinois, Chicago, IL (United States)
- Univ. of Chicago, IL (United States). Center for Advanced Radiation Sources (CARS)
- Univ. of Michigan, Ann Arbor, MI (United States)
- San Diego State Univ., CA (United States)
- Department of Chemistry and Biochemistry San Diego State University San Diego CA 92182 USA
- Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States); Univ. of Illinois, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); US Air Force Office of Scientific Research (AFOSR); USDOE National Nuclear Security Administration (NNSA), Office of Defense Programs (DP)
- OSTI Identifier:
- 1811460
- Alternate Identifier(s):
- OSTI ID: 1820158; OSTI ID: 1846035
- Report Number(s):
- BNL-221932-2021-JAAM
Journal ID: ISSN 2198-3844
- Grant/Contract Number:
- SC0012704; CHE-1834750; NA0003975; AC02-06CH11357; AC02-05CH11231; DMR-174774; FA9550-21-1-0065
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Advanced Science
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 18; Journal ID: ISSN 2198-3844
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; CsPbBr3; all-inorganic perovskites; in-situ single-crystal diffraction; local structure; phase transitions; space groups
Citation Formats
Liu, Sizhan, DeFilippo, Alexander R., Balasubramanian, Mahalingam, Liu, Zhenxian, Wang, SuYin Grass, Chen, Yu‐Sheng, Chariton, Stella, Prakapenka, Vitali, Luo, Xiangpeng, Zhao, Liuyan, Martin, Jovan San, Lin, Yixiong, Yan, Yong, Ghose, Sanjit K., and Tyson, Trevor A. High-Resolution In-Situ Synchrotron X-Ray Studies of Inorganic Perovskite CsPbBr3: New Symmetry Assignments and Structural Phase Transitions. United States: N. p., 2021.
Web. doi:10.1002/advs.202003046.
Liu, Sizhan, DeFilippo, Alexander R., Balasubramanian, Mahalingam, Liu, Zhenxian, Wang, SuYin Grass, Chen, Yu‐Sheng, Chariton, Stella, Prakapenka, Vitali, Luo, Xiangpeng, Zhao, Liuyan, Martin, Jovan San, Lin, Yixiong, Yan, Yong, Ghose, Sanjit K., & Tyson, Trevor A. High-Resolution In-Situ Synchrotron X-Ray Studies of Inorganic Perovskite CsPbBr3: New Symmetry Assignments and Structural Phase Transitions. United States. https://doi.org/10.1002/advs.202003046
Liu, Sizhan, DeFilippo, Alexander R., Balasubramanian, Mahalingam, Liu, Zhenxian, Wang, SuYin Grass, Chen, Yu‐Sheng, Chariton, Stella, Prakapenka, Vitali, Luo, Xiangpeng, Zhao, Liuyan, Martin, Jovan San, Lin, Yixiong, Yan, Yong, Ghose, Sanjit K., and Tyson, Trevor A. Sun .
"High-Resolution In-Situ Synchrotron X-Ray Studies of Inorganic Perovskite CsPbBr3: New Symmetry Assignments and Structural Phase Transitions". United States. https://doi.org/10.1002/advs.202003046. https://www.osti.gov/servlets/purl/1811460.
@article{osti_1811460,
title = {High-Resolution In-Situ Synchrotron X-Ray Studies of Inorganic Perovskite CsPbBr3: New Symmetry Assignments and Structural Phase Transitions},
author = {Liu, Sizhan and DeFilippo, Alexander R. and Balasubramanian, Mahalingam and Liu, Zhenxian and Wang, SuYin Grass and Chen, Yu‐Sheng and Chariton, Stella and Prakapenka, Vitali and Luo, Xiangpeng and Zhao, Liuyan and Martin, Jovan San and Lin, Yixiong and Yan, Yong and Ghose, Sanjit K. and Tyson, Trevor A.},
abstractNote = {Perovskite photovoltaic ABX3 systems are being studied due to their high energy-conversion efficiencies with current emphasis placed on pure inorganic systems. In this work, synchrotron single-crystal diffraction measurements combined with second harmonic generation measurements reveal the absence of inversion symmetry below room temperature in CsPbBr3. Local structural analysis by pair distribution function and X-ray absorption fine structure methods are performed to ascertain the local ordering, atomic pair correlations, and phase evolution in a broad range of temperatures. The currently accepted space group assignments for CsPbBr3 are found to be incorrect in a manner that profoundly impacts physical properties. New assignments are obtained for the bulk structure: I m 3 ¯ (above ≈410 K), P21/m (between ≈300 K and ≈410 K), and the polar group Pm (below ≈300 K), respectively. The newly observed structural distortions exist in the bulk structure consistent with the expectation of previous photoluminescence and Raman measurements. High-pressure measurements reveal multiple low-pressure phases, one of which exists as a metastable phase at ambient pressure. This work should help guide research in the perovskite photovoltaic community to better control the structure under operational conditions and further improve transport and optical properties.},
doi = {10.1002/advs.202003046},
journal = {Advanced Science},
number = 18,
volume = 8,
place = {United States},
year = {Sun Jul 11 00:00:00 EDT 2021},
month = {Sun Jul 11 00:00:00 EDT 2021}
}
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