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Bismuth-Based Halide Double Perovskite Cs<sub>2</sub>LiBiCl<sub>6</sub>: Crystal Structure, Luminescence, and Stability

Yanming SunMOE Key Laboratory of New Processing Technology for Nonferrous Metal and Materials, Guangxi Key Laboratory of Optic and Electronic Materials and Devices, College of Materials Science and Engineering, Guilin University of Technology, Guilin 541004, P. R. ChinaAlberto J. Fernández‐CarriónMOE Key Laboratory of New Processing Technology for Nonferrous Metal and Materials, Guangxi Key Laboratory of Optic and Electronic Materials and Devices, College of Materials Science and Engineering, Guilin University of Technology, Guilin 541004, P. R. ChinaYun‐Hui LiuCollege of Science, Guilin University of Technology, Guilin 541004, P. R. ChinaCongling YinMOE Key Laboratory of New Processing Technology for Nonferrous Metal and Materials, Guangxi Key Laboratory of Optic and Electronic Materials and Devices, College of Materials Science and Engineering, Guilin University of Technology, Guilin 541004, P. R. ChinaXing MingCollege of Science, Guilin University of Technology, Guilin 541004, P. R. ChinaBo‐Mei LiuMinistry of Education Key Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry, School of Materials Science and Engineering, Sun Yat-Sen University, Guangzhou 510275, ChinaJing WangMinistry of Education Key Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry, School of Materials Science and Engineering, Sun Yat-Sen University, Guangzhou 510275, ChinaHui FuAnalytical Instrumentation Center, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. ChinaXiaojun KuangMOE Key Laboratory of New Processing Technology for Nonferrous Metal and Materials, Guangxi Key Laboratory of Optic and Electronic Materials and Devices, College of Materials Science and Engineering and College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, P. R. ChinaXianran XingBeijing Advanced Innovation Center for Materials Genome Engineering and Institute of Solid-State Chemistry, University of Science and Technology Beijing, Beijing 100083, China

2021en

ABI

Annotatsiya

A new bismuth-based halide double perovskite Cs2LiBiCl6 was isolated successfully using solid-state reactions. The crystal structure was investigated using X-ray diffraction and complemented by 7Li solid-state nuclear magnetic resonance spectroscopy, which indicated the highly ordered nature of Li and Bi ions in the B sublattice of double perovskite. Compared with the Na analogue, the more moisture-sensitive Cs2LiBiCl6 has a smaller indirect band gap of 3.15(2) eV and red-shift luminescence of around 612 nm as well as stronger intensities at Mn2+ doping. The stability mechanism of Cs2LiBiCl6 was discussed together with that of Cs2NaBiCl6 and their inaccessible Br counterparts based on the tolerance and octahedral factors and density functional theory (DFT) calculations. Owing to the small size of Li+ cations, Cs2LiBiCl6 has low tolerance and octahedral factors close to the boundary between the stable perovskite and nonperovskite compounds, which possess a small decomposition energy and thus easily coexist with other ternary phases. The Br-based compositions of Cs2LiBiBr6 and Cs2NaBiBr6 have even smaller octahedral factors and negative decomposition energies, and therefore their double perovskite polymorphs are destabilized. DFT simulations indicate that the moisture sensitivity of Cs2LiBiCl6 is related to the coordination preference of Li+ due to its smaller size and the steric effect from water molecules, in contrast with the larger Na+ showing a more stable octahedral configuration under the water incorporation. These mechanisms combining the geometry factors and decomposition energies provide new insights into the stability of halide double perovskites.

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DOI: 10.1021/acs.chemmater.1c00854

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