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Chemical Origin of the Stability Difference between Copper(I)‐ and Silver(I)‐Based Halide Double Perovskites
Author(s) -
Xiao Zewen,
Du KeZhao,
Meng Weiwei,
Mitzi David B.,
Yan Yanfa
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201705113
Subject(s) - halide , halogen , octahedron , perovskite (structure) , atomic orbital , crystallography , tetrahedron , density functional theory , copper , chemistry , materials science , inorganic chemistry , computational chemistry , crystal structure , physics , metallurgy , electron , alkyl , organic chemistry , quantum mechanics
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.