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Design of Mixed‐Cation Tri‐Layered Pb‐Free Halide Perovskites for Optoelectronic Applications
Author(s) -
Liu Zhun,
Zhao Xingang,
Zunger Alex,
Zhang Lijun
Publication year - 2019
Publication title -
advanced electronic materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.25
H-Index - 56
ISSN - 2199-160X
DOI - 10.1002/aelm.201900234
Subject(s) - halide , perovskite (structure) , octahedron , materials science , crystallography , electronic structure , crystal structure , inorganic chemistry , computational chemistry , chemistry
To eliminate the toxic Pb 2+ cation in hybrid halide perovskites, M′ 3+ cations of Bi/Sb‐based layered halide perovskites are being increasingly investigated for optoelectronic applications. However, such M′ 3+ trivalent cations constrain the face‐sharing bioctahedral or the bi‐layered perovskites required to meet the charge neutrality condition. This usually gives rise to oversized indirect bandgaps and inferior carrier transport. Recent experiment suggested a mixed‐cation tri‐layered halide perovskite can be obtained by sandwiching a [Cu 2+ X 6 ] 4− layer between Sb 3+ perovskite bilayers along the polar [111] planes with cation ordering. A material design of mixed‐cation <111>‐oriented tri‐layered Pb‐free halide perovskite A 4 MM′ 2 X 12 is studied by a computational screening of various combinations of M 2+ cations (e.g., Zn 2+ , Sn 2+ ) and M′ 3+ cations (e.g., Bi 3+ , Sb 3+ ). The thermodynamic stability of the candidate materials is systemically evaluated with respect to potential decomposition pathways and a series of stable compounds is synthesized. These results further indicate the chemical trend of electronic structure and how octahedral tilting coupling with charge ordering affects electronic properties. A protocol for engineering A 4 MM′ 2 X 12 perovskites with optimized structures and electronic properties by exploiting octahedral tilting coupling with charge ordering in the polar <111> layered perovskites is established.