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Title: Chemical Origin of the Stability Difference between Cu(I)- and Ag(I)-Based Halide Double Perovskites

Abstract

Recently, Cu(I)- and Ag(I)-based halide double perovskites have been proposed as promising candidates for overcoming the toxicity and instability issues inherent within the emerging Pb-based halide perovskite absorbers. However, up to date, only Ag(I)-based halide double perovskites have been experimentally synthesized; there are no reports on successful synthesis of Cu(I)-based analogues. In this study, we show that, owing to the much higher energy level for the Cu 3d10 orbital than for the Ag 4d10 orbital, Cu(I) atoms energetically favor 4-fold coordination, forming [CuX4] tetrahedra (X = halogen), but not 6-fold coordination as required for [CuX6] octahedra. In contrast, Ag(I) atoms can have both 6- and 4-fold coordination’s. Our density functional theory calculations reveal that the synthesis of Cu(I) halide double perovskites may instead lead to products containing [CuX4] tetrahedra, as confirmed by our material synthesis efforts.

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [2]; ORCiD logo [3]
  1. Univ. of Toledo, OH (United States). Wright Center for Photovoltaics Innovation and Commercialization (PVIC); Univ. of Toledo, OH (United States). Dept. of Physics and Astronomy
  2. Duke Univ., Durham, NC (United States). Dept. of Mechanical Engineering and Materials Science, and Dept. of Chemistry
  3. Univ. of Toledo, OH (United States). Wright Center for Photovoltaics Innovation and Commercialization (PVIC)
Publication Date:
Research Org.:
Duke Univ., Durham, NC (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Solar Energy Technologies Office (EE-4S)
OSTI Identifier:
1559770
Alternate Identifier(s):
OSTI ID: 1375986
Grant/Contract Number:  
EE0006712
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie
Additional Journal Information:
Journal Volume: 129; Journal Issue: 40; Journal ID: ISSN 0044-8249
Publisher:
German Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Xiao, Zewen, Du, Ke-Zhao, Meng, Weiwei, Mitzi, David B., and Yan, Yanfa. Chemical Origin of the Stability Difference between Cu(I)- and Ag(I)-Based Halide Double Perovskites. United States: N. p., 2017. Web. doi:10.1002/ange.201705113.
Xiao, Zewen, Du, Ke-Zhao, Meng, Weiwei, Mitzi, David B., & Yan, Yanfa. Chemical Origin of the Stability Difference between Cu(I)- and Ag(I)-Based Halide Double Perovskites. United States. doi:10.1002/ange.201705113.
Xiao, Zewen, Du, Ke-Zhao, Meng, Weiwei, Mitzi, David B., and Yan, Yanfa. Wed . "Chemical Origin of the Stability Difference between Cu(I)- and Ag(I)-Based Halide Double Perovskites". United States. doi:10.1002/ange.201705113. https://www.osti.gov/servlets/purl/1559770.
@article{osti_1559770,
title = {Chemical Origin of the Stability Difference between Cu(I)- and Ag(I)-Based Halide Double Perovskites},
author = {Xiao, Zewen and Du, Ke-Zhao and Meng, Weiwei and Mitzi, David B. and Yan, Yanfa},
abstractNote = {Recently, Cu(I)- and Ag(I)-based halide double perovskites have been proposed as promising candidates for overcoming the toxicity and instability issues inherent within the emerging Pb-based halide perovskite absorbers. However, up to date, only Ag(I)-based halide double perovskites have been experimentally synthesized; there are no reports on successful synthesis of Cu(I)-based analogues. In this study, we show that, owing to the much higher energy level for the Cu 3d10 orbital than for the Ag 4d10 orbital, Cu(I) atoms energetically favor 4-fold coordination, forming [CuX4] tetrahedra (X = halogen), but not 6-fold coordination as required for [CuX6] octahedra. In contrast, Ag(I) atoms can have both 6- and 4-fold coordination’s. Our density functional theory calculations reveal that the synthesis of Cu(I) halide double perovskites may instead lead to products containing [CuX4] tetrahedra, as confirmed by our material synthesis efforts.},
doi = {10.1002/ange.201705113},
journal = {Angewandte Chemie},
number = 40,
volume = 129,
place = {United States},
year = {2017},
month = {8}
}

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