Intrinsic Instability of Cs 2 In(I)M(III)X 6 (M = Bi, Sb; X = Halogen) Double Perovskites: A Combined Density Functional Theory and Experimental Study
Abstract
Recently, there has been substantial interest in developing double-B-cation halide perovskites, which hold the potential to overcome the toxicity and instability issues inherent within emerging lead halide-based solar absorber materials. Among all double perovskites investigated, In(I)-based Cs2InBiCl6 and Cs2InSbCl6 have been proposed as promising thin-film photovoltaic absorber candidates, with computational examination predicting suitable materials properties, including direct bandgap and small effective masses for both electrons and holes. In this study, we report the intrinsic instability of Cs2In(I)M(III)X6 (M = Bi, Sb; X = halogen) double perovskites by a combination of density functional theory and experimental study. Our results suggest that the In(I)-based double perovskites are unstable against oxidation into In(III)-based compounds. Further, the results show the need to consider reduction–oxidation (redox) chemistry when predicting stability of new prospective electronic materials, especially when less common oxidation states are involved.
- Authors:
-
[1];
[4];
[2];
[1]
- Univ. of Toledo, OH (United States). Wright Center for Photovoltaics Innovation and Commercialization (PVIC)
- Duke Univ., Durham, NC (United States). Dept. of Mechanical Engineering and Materials Science, and Dept. of Chemistry
- Wuhan Univ., Wuhan (China). School of Physics and Technology, Center for Electron Microscopy, MOE Key Laboratory of Artificial Micro- and Nano-structures, and Inst. for Advanced Studies; Univ. of Toledo, OH (United States). Wright Center for Photovoltaics Innovation and Commercialization (PVIC)
- Wuhan Univ., Wuhan (China). School of Physics and Technology, Center for Electron Microscopy, MOE Key Laboratory of Artificial Micro- and Nano-structures, and Inst. for Advanced Studies
- Publication Date:
- Research Org.:
- Duke Univ., Durham, NC (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- OSTI Identifier:
- 1559768
- Alternate Identifier(s):
- OSTI ID: 1488933
- Grant/Contract Number:
- EE0006712; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 139; Journal Issue: 17; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Xiao, Zewen, Du, Ke-Zhao, Meng, Weiwei, Wang, Jianbo, Mitzi, David B., and Yan, Yanfa. Intrinsic Instability of Cs 2 In(I)M(III)X 6 (M = Bi, Sb; X = Halogen) Double Perovskites: A Combined Density Functional Theory and Experimental Study. United States: N. p., 2017.
Web. doi:10.1021/jacs.7b02227.
Xiao, Zewen, Du, Ke-Zhao, Meng, Weiwei, Wang, Jianbo, Mitzi, David B., & Yan, Yanfa. Intrinsic Instability of Cs 2 In(I)M(III)X 6 (M = Bi, Sb; X = Halogen) Double Perovskites: A Combined Density Functional Theory and Experimental Study. United States. https://doi.org/10.1021/jacs.7b02227
Xiao, Zewen, Du, Ke-Zhao, Meng, Weiwei, Wang, Jianbo, Mitzi, David B., and Yan, Yanfa. Tue .
"Intrinsic Instability of Cs 2 In(I)M(III)X 6 (M = Bi, Sb; X = Halogen) Double Perovskites: A Combined Density Functional Theory and Experimental Study". United States. https://doi.org/10.1021/jacs.7b02227. https://www.osti.gov/servlets/purl/1559768.
@article{osti_1559768,
title = {Intrinsic Instability of Cs 2 In(I)M(III)X 6 (M = Bi, Sb; X = Halogen) Double Perovskites: A Combined Density Functional Theory and Experimental Study},
author = {Xiao, Zewen and Du, Ke-Zhao and Meng, Weiwei and Wang, Jianbo and Mitzi, David B. and Yan, Yanfa},
abstractNote = {Recently, there has been substantial interest in developing double-B-cation halide perovskites, which hold the potential to overcome the toxicity and instability issues inherent within emerging lead halide-based solar absorber materials. Among all double perovskites investigated, In(I)-based Cs2InBiCl6 and Cs2InSbCl6 have been proposed as promising thin-film photovoltaic absorber candidates, with computational examination predicting suitable materials properties, including direct bandgap and small effective masses for both electrons and holes. In this study, we report the intrinsic instability of Cs2In(I)M(III)X6 (M = Bi, Sb; X = halogen) double perovskites by a combination of density functional theory and experimental study. Our results suggest that the In(I)-based double perovskites are unstable against oxidation into In(III)-based compounds. Further, the results show the need to consider reduction–oxidation (redox) chemistry when predicting stability of new prospective electronic materials, especially when less common oxidation states are involved.},
doi = {10.1021/jacs.7b02227},
journal = {Journal of the American Chemical Society},
number = 17,
volume = 139,
place = {United States},
year = {Tue Apr 18 00:00:00 EDT 2017},
month = {Tue Apr 18 00:00:00 EDT 2017}
}
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