Bismuth-Based Halide Double Perovskite Cs2LiBiCl6: Crystal Structure, Luminescence, and Stability

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 a...

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Autores: Sun, Yanming, Fernández-Carrión, Alberto J., Liu, Yunhui, Yin, Congling, Ming, Xing, Liu, Bo Mei, Wang, Jing, Fu, Hui, Kuang, Xiaojun, Xing, Xianran
Tipo de recurso: artículo
Estado:Versión enviada para evaluación y publicación
Fecha de publicación:2021
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/415418
Acceso en línea:http://hdl.handle.net/10261/415418
https://api.elsevier.com/content/abstract/scopus_id/85112721550
Access Level:acceso abierto
Palabra clave:Halide perovskite
Double perovskite
Luminescence
Stability mechanism
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spelling Bismuth-Based Halide Double Perovskite Cs2LiBiCl6: Crystal Structure, Luminescence, and StabilitySun, YanmingFernández-Carrión, Alberto J.Liu, YunhuiYin, ConglingMing, XingLiu, Bo MeiWang, JingFu, HuiKuang, XiaojunXing, XianranHalide perovskiteDouble perovskiteLuminescenceStability mechanismA 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.The National Science Foundation of China (No. 22090043, 51662013, 21850410458), Guangxi Natural Science Foundation (No. 2019GXNSFGA245006, 2018AD19200, AD19245097), and the Foundation of Guilin University of Technology (No. GUTQDJJ2018115) are acknowledged for the financial support. We thank Prof. Yuanli Liu (Guilin University of Technology) for providing equipment for the luminescence measurement.Peer reviewedAmerican Chemical SocietyNational Natural Science Foundation of ChinaNatural Science Foundation of Guangxi ProvinceFernández-Carrión, A.J. [0000-0001-8320-2828]Ming, Xing [0000-0002-6567-6728]Wang, Jing [0000-0002-1246-991X]Kuang, Xiaojun [0000-0003-2975-9355]Xing, Xianran [0000-0003-0704-8886]202620262021info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Preprintinfo:eu-repo/semantics/submittedVersionapplication/pdfhttp://hdl.handle.net/10261/415418https://api.elsevier.com/content/abstract/scopus_id/85112721550reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Ingléshttps://doi.org/10.1021/acs.chemmater.1c00854Noinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/4154182026-05-22T06:33:51Z
dc.title.none.fl_str_mv Bismuth-Based Halide Double Perovskite Cs2LiBiCl6: Crystal Structure, Luminescence, and Stability
title Bismuth-Based Halide Double Perovskite Cs2LiBiCl6: Crystal Structure, Luminescence, and Stability
spellingShingle Bismuth-Based Halide Double Perovskite Cs2LiBiCl6: Crystal Structure, Luminescence, and Stability
Sun, Yanming
Halide perovskite
Double perovskite
Luminescence
Stability mechanism
title_short Bismuth-Based Halide Double Perovskite Cs2LiBiCl6: Crystal Structure, Luminescence, and Stability
title_full Bismuth-Based Halide Double Perovskite Cs2LiBiCl6: Crystal Structure, Luminescence, and Stability
title_fullStr Bismuth-Based Halide Double Perovskite Cs2LiBiCl6: Crystal Structure, Luminescence, and Stability
title_full_unstemmed Bismuth-Based Halide Double Perovskite Cs2LiBiCl6: Crystal Structure, Luminescence, and Stability
title_sort Bismuth-Based Halide Double Perovskite Cs2LiBiCl6: Crystal Structure, Luminescence, and Stability
dc.creator.none.fl_str_mv Sun, Yanming
Fernández-Carrión, Alberto J.
Liu, Yunhui
Yin, Congling
Ming, Xing
Liu, Bo Mei
Wang, Jing
Fu, Hui
Kuang, Xiaojun
Xing, Xianran
author Sun, Yanming
author_facet Sun, Yanming
Fernández-Carrión, Alberto J.
Liu, Yunhui
Yin, Congling
Ming, Xing
Liu, Bo Mei
Wang, Jing
Fu, Hui
Kuang, Xiaojun
Xing, Xianran
author_role author
author2 Fernández-Carrión, Alberto J.
Liu, Yunhui
Yin, Congling
Ming, Xing
Liu, Bo Mei
Wang, Jing
Fu, Hui
Kuang, Xiaojun
Xing, Xianran
author2_role author
author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv National Natural Science Foundation of China
Natural Science Foundation of Guangxi Province
Fernández-Carrión, A.J. [0000-0001-8320-2828]
Ming, Xing [0000-0002-6567-6728]
Wang, Jing [0000-0002-1246-991X]
Kuang, Xiaojun [0000-0003-2975-9355]
Xing, Xianran [0000-0003-0704-8886]
dc.subject.none.fl_str_mv Halide perovskite
Double perovskite
Luminescence
Stability mechanism
topic Halide perovskite
Double perovskite
Luminescence
Stability mechanism
description 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.
publishDate 2021
dc.date.none.fl_str_mv 2021
2026
2026
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Preprint
info:eu-repo/semantics/submittedVersion
format article
status_str submittedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/415418
https://api.elsevier.com/content/abstract/scopus_id/85112721550
url http://hdl.handle.net/10261/415418
https://api.elsevier.com/content/abstract/scopus_id/85112721550
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv https://doi.org/10.1021/acs.chemmater.1c00854
No
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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