Metal cation s lone-pairs increase octahedral tilting instabilities in halide perovskites
Abstract
Halide perovskites exhibit beneficial opto-electronic properties (e.g. long carrier lifetimes and low defect densities), and their dynamic structural instabilities and anharmonic thermal fluctuations are directly implicated in these properties. In this work, we combine in-depth analysis of Raman spectroscopy and ab initio calculations to uncover the critical roles of Group 14 M2+ (M = Pb, Sn, Ge) metal cation s orbital lone pairs in the dynamic instabilities of CsMBr3 and particularly in governing the octahedral tilting. Previous studies concluded that the lone-pair stereochemical activity primarily leads to the off-centering motion of the metal cation, and the tilting is usually ascribed to ionic size effects. Here, we show that the lone-pair stereochemical activity contributes to strong octahedral tilting instabilities that induce liquid-like behavior in all examined crystals, which underlies the robustness of halide perovskites to charged defects. In addition, the lone-pairs induce a local, molecule-like behavior of the Ge2+ with a pyramidal bonding motif in the cubic phase, and they contribute to another phase transition of CsSnBr3 at 60 K. Our findings elucidate the fundamental origin of anharmonicities in halide perovskites and provide the crucial link between chemical composition and optoelectronic properties, opening opportunities for lead-free and solution-processable photovoltaics.
- Authors:
-
[1];
[2];
[3];
[4];
[5];
[3];
[1];
[2]
- Department of Chemistry, University of Pennsylvania, Philadelphia, USA
- Department of Chemical and Biological Physics, Weizmann Institute of Science, Rehovot 76100, Israel
- Department of Chemistry, Northwestern University, Evanston, USA
- Max Planck Institute for Solid State Research, Stuttgart 70569, Germany
- Department of Materials Science and Technology, University of Crete, Voutes Campus, Heraklion 70013, Greece
- Publication Date:
- Research Org.:
- Univ. of California, Santa Barbara, CA (United States); Northwestern Univ., Evanston, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Alexander von Humboldt Foundation; US Department of the Navy, Office of Naval Research (ONR)
- OSTI Identifier:
- 1798926
- Alternate Identifier(s):
- OSTI ID: 1870316
- Grant/Contract Number:
- FG02- 07ER46431; AC02-05CH11231; SC0012541; FG02-07ER46431; 2016650; N00014-20-1-2701
- Resource Type:
- Published Article
- Journal Name:
- Materials Advances
- Additional Journal Information:
- Journal Name: Materials Advances Journal Volume: 2 Journal Issue: 14; Journal ID: ISSN 2633-5409
- Publisher:
- Royal Society of Chemistry (RSC)
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Gao, Lingyuan, Yadgarov, Lena, Sharma, Rituraj, Korobko, Roman, McCall, Kyle M., Fabini, Douglas H., Stoumpos, Constantinos C., Kanatzidis, Mercouri G., Rappe, Andrew M., and Yaffe, Omer. Metal cation s lone-pairs increase octahedral tilting instabilities in halide perovskites. United Kingdom: N. p., 2021.
Web. doi:10.1039/D1MA00288K.
Gao, Lingyuan, Yadgarov, Lena, Sharma, Rituraj, Korobko, Roman, McCall, Kyle M., Fabini, Douglas H., Stoumpos, Constantinos C., Kanatzidis, Mercouri G., Rappe, Andrew M., & Yaffe, Omer. Metal cation s lone-pairs increase octahedral tilting instabilities in halide perovskites. United Kingdom. https://doi.org/10.1039/D1MA00288K
Gao, Lingyuan, Yadgarov, Lena, Sharma, Rituraj, Korobko, Roman, McCall, Kyle M., Fabini, Douglas H., Stoumpos, Constantinos C., Kanatzidis, Mercouri G., Rappe, Andrew M., and Yaffe, Omer. Tue .
"Metal cation s lone-pairs increase octahedral tilting instabilities in halide perovskites". United Kingdom. https://doi.org/10.1039/D1MA00288K.
@article{osti_1798926,
title = {Metal cation s lone-pairs increase octahedral tilting instabilities in halide perovskites},
author = {Gao, Lingyuan and Yadgarov, Lena and Sharma, Rituraj and Korobko, Roman and McCall, Kyle M. and Fabini, Douglas H. and Stoumpos, Constantinos C. and Kanatzidis, Mercouri G. and Rappe, Andrew M. and Yaffe, Omer},
abstractNote = {Halide perovskites exhibit beneficial opto-electronic properties (e.g. long carrier lifetimes and low defect densities), and their dynamic structural instabilities and anharmonic thermal fluctuations are directly implicated in these properties. In this work, we combine in-depth analysis of Raman spectroscopy and ab initio calculations to uncover the critical roles of Group 14 M2+ (M = Pb, Sn, Ge) metal cation s orbital lone pairs in the dynamic instabilities of CsMBr3 and particularly in governing the octahedral tilting. Previous studies concluded that the lone-pair stereochemical activity primarily leads to the off-centering motion of the metal cation, and the tilting is usually ascribed to ionic size effects. Here, we show that the lone-pair stereochemical activity contributes to strong octahedral tilting instabilities that induce liquid-like behavior in all examined crystals, which underlies the robustness of halide perovskites to charged defects. In addition, the lone-pairs induce a local, molecule-like behavior of the Ge2+ with a pyramidal bonding motif in the cubic phase, and they contribute to another phase transition of CsSnBr3 at 60 K. Our findings elucidate the fundamental origin of anharmonicities in halide perovskites and provide the crucial link between chemical composition and optoelectronic properties, opening opportunities for lead-free and solution-processable photovoltaics.},
doi = {10.1039/D1MA00288K},
journal = {Materials Advances},
number = 14,
volume = 2,
place = {United Kingdom},
year = {Tue Jul 20 00:00:00 EDT 2021},
month = {Tue Jul 20 00:00:00 EDT 2021}
}
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