Chemical Origin of the Stability Difference between Cu(I)- and Ag(I)-Based Halide Double Perovskites
Abstract
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. Here we show that, owing to the much higher energy level for the Cu 3d 10 orbitals than for the Ag 4d 10 orbitals, Cu I atoms energetically favor 4‐fold coordination, forming [CuX 4 ] tetrahedra (X=halogen), but not 6‐fold coordination as required for [CuX 6 ] octahedra. In contrast, Ag I atoms can have both 6‐ and 4‐fold coordinations. Our density functional theory calculations reveal that the synthesis of Cu I halide double perovskites may instead lead to non‐perovskites containing [CuX 4 ] tetrahedra, as confirmed by our material synthesis efforts.
- Authors:
-
- 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
- Duke Univ., Durham, NC (United States). Dept. of Mechanical Engineering and Materials Science, and Dept. of Chemistry
- 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), Renewable Power Office. Solar Energy Technologies Office
- OSTI Identifier:
- 1559770
- Alternate Identifier(s):
- OSTI ID: 1375986
- Grant/Contract Number:
- EE0006712
- Resource Type:
- Journal Article: 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. https://doi.org/10.1002/ange.201705113
Xiao, Zewen, Du, Ke-Zhao, Meng, Weiwei, Mitzi, David B., and Yan, Yanfa. 2017.
"Chemical Origin of the Stability Difference between Cu(I)- and Ag(I)-Based Halide Double Perovskites". United States. https://doi.org/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 = {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. Here we show that, owing to the much higher energy level for the Cu 3d 10 orbitals than for the Ag 4d 10 orbitals, Cu I atoms energetically favor 4‐fold coordination, forming [CuX 4 ] tetrahedra (X=halogen), but not 6‐fold coordination as required for [CuX 6 ] octahedra. In contrast, Ag I atoms can have both 6‐ and 4‐fold coordinations. Our density functional theory calculations reveal that the synthesis of Cu I halide double perovskites may instead lead to non‐perovskites containing [CuX 4 ] tetrahedra, as confirmed by our material synthesis efforts.},
doi = {10.1002/ange.201705113},
url = {https://www.osti.gov/biblio/1559770},
journal = {Angewandte Chemie},
issn = {0044-8249},
number = 40,
volume = 129,
place = {United States},
year = {Wed Aug 23 00:00:00 EDT 2017},
month = {Wed Aug 23 00:00:00 EDT 2017}
}
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