Hexagonal Halide Perovskite Cs2LiInCl6: Cation Ordering, Face-Shared Octahedral Trimers and Mn2+ Luminescence

Bingqi Wang; Pan Liu; Alberto J Fernández-Carrióna; Hui Fu; XiuHui Zhu; Xing Ming; Weixiong You; Zongliang Xiao; Mingxue Tang; Xiuyun Lei; Congling Yin; Xiaojun Kuang

doi:10.1002/asia.202400447

Hexagonal Halide Perovskite Cs2LiInCl6: Cation Ordering, Face-Shared Octahedral Trimers and Mn2+ Luminescence

Chem Asian J. 2024 May 13:e202400447. doi: 10.1002/asia.202400447. Online ahead of print.

Authors

Bingqi Wang¹, Pan Liu², Alberto J Fernández-Carrióna¹, Hui Fu³, XiuHui Zhu², Xing Ming⁴, Weixiong You⁵, Zongliang Xiao⁵, Mingxue Tang⁶, Xiuyun Lei¹, Congling Yin⁷, Xiaojun Kuang⁸

Affiliations

¹ Guilin University of Technology, College of Materials Science and Engineering, CHINA.
² Northwest Industrial Group Co, Northwest Industrial Group Co., Ltd, Xi'an, Shaanxi, CHINA.
³ Peking University, Analytical Instrumentation Center, College of Chemistry and Molecular Engineering, CHINA.
⁴ Guilin University of Technology, College of Science, CHINA.
⁵ JiangXi University of Science and Technology, 5. School of Material Science and Engineering, CHINA.
⁶ Center for High Pressure Science and Technology Advanced Research, Center for High Pressure Science and Technology Advanced Research, CHINA.
⁷ Guilin University of Technology, Materials Science and Engineering, No. 12 Jiangan Road, 541004, Guilin, CHINA.
⁸ Guilin University of Technology, College of Chemistry and Bioengineering, CHINA.

PMID: 38738448
DOI: 10.1002/asia.202400447

Abstract

The In-based double perovskite halides have been widely studied for promising optical-electric applications. The halide hexagonal perovskite Cs2LiInCl6 was isolated using solid-state reactions and investigated using X-ray diffraction and solid-state NMR spectra. The material adopts a 12-layered hexagonal structure (12R) consisting of layered cationic orders driven by the cationic charge difference and has Li+ cations in the terminal site and In3+ in the central site of face-shared octahedron trimers. Such a cationic ordering pattern is stabilized by electrostatic repulsions between the next-nearest neighboring cations in the trimers. The LiCl6 octahedron displays large distortion and is confirmed by 7Li SSNMR in the Cs2LiInCl6. The Cs2LiInCl6 material has a direct bandgap of ~ 4.98 eV. The Cs2LiInCl6: Mn displays redshift luminescence (centered at ~610 - 622 nm) from the substituted Mn2+ emission in octahedron with larger PLQY (17.8%-48%) compared with that of Cs2NaInCl6: Mn2+. The Mn-doped materials show luminescent concentration quenching and thermal quenching. The composition Cs2Li0.99In0.99Mn0.02Cl6 exhibits the highest PL intensity, a maximum PLQY of 48%, and high luminescent retention rate of ~ 86% below 400 K and is suitable for application for pc-LED. These findings contribute to our understanding of the chloride perovskites and hold potential for widespread optical applications.

Keywords: halide perovskite hexagonal perovskite cationic order luminescence Direct bandgap.