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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

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:
ORCiD logo [1];  [2];  [3]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [1]
  1. Department of Physics and Astronomy and Wright Center for Photovoltaics Innovation and Commercialization, The University of Toledo, Toledo, Ohio 43606, United States
  2. Department of Mechanical Engineering and Materials Science, and Department of Chemistry, Duke University, Durham, North Carolina 27708, United States
  3. Department of Physics and Astronomy and Wright Center for Photovoltaics Innovation and Commercialization, The University of Toledo, Toledo, Ohio 43606, United States; School of Physics and Technology, Center for Electron Microscopy, MOE Key Laboratory of Artificial Micro- and Nano-structures, and Institute for Advanced Studies, Wuhan University, Wuhan 430072, China
  4. School of Physics and Technology, Center for Electron Microscopy, MOE Key Laboratory of Artificial Micro- and Nano-structures, and Institute for Advanced Studies, Wuhan University, Wuhan 430072, China
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center; Duke Univ., Durham, NC (United States)
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. doi:10.1021/jacs.7b02227.
Xiao, Zewen, Du, Ke-Zhao, Meng, Weiwei, Wang, Jianbo, Mitzi, David B., and Yan, Yanfa. Mon . "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. doi: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 = {2017},
month = {4}
}

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