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Title: 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:
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), 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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Works referencing / citing this record:

Highly Efficient Blue-Emitting Bi-Doped Cs 2 SnCl 6 Perovskite Variant: Photoluminescence Induced by Impurity Doping
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Thermodynamic Stability Landscape of Halide Double Perovskites via High-Throughput Computing and Machine Learning
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From Lead Halide Perovskites to Lead‐Free Metal Halide Perovskites and Perovskite Derivatives
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Lead-Free Highly Efficient Blue-Emitting Cs 3 Cu 2 I 5 with 0D Electronic Structure
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Structural and Functional Diversity in Lead‐Free Halide Perovskite Materials
journal, April 2019


Machine Learning Stability and Bandgaps of Lead‐Free Perovskites for Photovoltaics
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Progress of Lead‐Free Halide Double Perovskites
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A Supported Bismuth Halide Perovskite Photocatalyst for Selective Aliphatic and Aromatic C–H Bond Activation
journal, January 2020


Low-Bandgap Cs 4 CuSb 2 Cl 12 Layered Double Perovskite: Synthesis, Reversible Thermal Changes, and Magnetic Interaction
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Ag/In lead‐free double perovskites
journal, February 2020


0D Cs 3 Cu 2 X 5 (X = I, Br, and Cl) Nanocrystals: Colloidal Syntheses and Optical Properties
journal, December 2019


Perovskite Solar Absorbers: Materials by Design
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Lead‐Free Double Perovskites for Perovskite Solar Cells
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Distinct green electroluminescence from lead-free CsCuBr 2 halide micro-crosses
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CsAg 2 Sb 2 I 9 solar cells
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Initiation and future prospects of colloidal metal halide double-perovskite nanocrystals: Cs 2 AgBiX 6 (X = Cl, Br, I)
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Lead-free double perovskites Cs 2 InCuCl 6 and (CH 3 NH 3 ) 2 InCuCl 6 : electronic, optical, and electrical properties
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Recent progress in Pb-free stable inorganic double halide perovskites
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Mechanochemical synthesis of the lead-free double perovskite Cs 2 [AgIn]Br 6 and its optical properties
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Investigation of AgInS2/ZnS Quantum Dots by Magnetic Circular Dichroism Spectroscopy
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A Supported Bismuth Halide Perovskite Photocatalyst for Selective Aliphatic and Aromatic C–H Bond Activation
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