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Quaternary Sulfide Ba 6 Zn 6 ZrS 14 : Synthesis, Crystal Structure, Band Structure, and Multiband Physical Properties
Author(s) -
Zhang Xian,
He Jianqiao,
Chen Wei,
Zhang Ketian,
Zheng Chong,
Sun Junliang,
Liao Fuhui,
Lin Jianhua,
Huang Fuqiang
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201304525
Subject(s) - tetragonal crystal system , crystallography , photoluminescence , absorption (acoustics) , crystal structure , materials science , absorption edge , electronic band structure , cluster (spacecraft) , flux method , zinc , crystal (programming language) , photocatalysis , band gap , analytical chemistry (journal) , chemistry , single crystal , condensed matter physics , physics , optoelectronics , biochemistry , metallurgy , computer science , programming language , composite material , catalysis , chromatography
Ba 6 Zn 6 ZrS 14 was synthesized by a traditional salt‐melt method with KI as flux. The pale yellow crystals of Ba 6 Zn 6 ZrS 14 crystallize in the tetragonal space group I 4/ mcm with a =16.3481 (4) Å and c =9.7221(6) Å. The structure features unique one‐dimensional parallel [Zn 6 S 9 ] 6− and [ZrS 5 ] 6− straight chains. The D 2 h ‐symmetric [Zn 6 S 9 ] 6− cluster serves as the building block of the [Zn 6 S 9 ] 6− chains. A powder sample was investigated by X‐ray diffraction, optical absorption, and photoluminescence measurements. The compound shows multiple‐absorption character with three optical absorption edges around 1.78, 2.50, and 2.65 eV, respectively, which are perfectly consistent with the results of first‐principles calculations. Analysis of the density of states further revealed that the three optical absorption bands are attributable to the three S(3p 6 )→Zr(4d 0 ) transitions due to the splitting of the Zr 4d orbitals in the D 4 h crystal field. The multiband nature of Ba 6 Zn 6 ZrS 14 also results in photocatalytic activity under visible‐light irradiation and three band‐edge emissions.