Quaternary sulfide Ba6Zn6ZrS14: synthesis, crystal structure, band structure, and multiband physical properties

Xian Zhang; Jianqiao He; Wei Chen; Ketian Zhang; Chong Zheng; Junliang Sun; Fuhui Liao; Jianhua Lin; Fuqiang Huang

doi:10.1002/chem.201304525

Quaternary sulfide Ba6Zn6ZrS14: synthesis, crystal structure, band structure, and multiband physical properties

Chemistry. 2014 May 12;20(20):5977-82. doi: 10.1002/chem.201304525. Epub 2014 Apr 3.

Authors

Xian Zhang¹, Jianqiao He, Wei Chen, Ketian Zhang, Chong Zheng, Junliang Sun, Fuhui Liao, Jianhua Lin, Fuqiang Huang

Affiliation

¹ Beijing National Laboratory for Molecular Sciences and State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (P.R. China), Fax: (+86) 10-62758225.

PMID: 24700506
DOI: 10.1002/chem.201304525

Abstract

Ba6Zn6ZrS14 was synthesized by a traditional salt-melt method with KI as flux. The pale yellow crystals of Ba6Zn6ZrS14 crystallize in the tetragonal space group I4/mcm with a=16.3481 (4) Å and c=9.7221(6) Å. The structure features unique one-dimensional parallel [Zn6S9](6-) and [ZrS5](6-) straight chains. The D2h-symmetric [Zn6S9](6-) cluster serves as the building block of the [Zn6S9](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 D4h crystal field. The multiband nature of Ba6Zn6ZrS14 also results in photocatalytic activity under visible-light irradiation and three band-edge emissions.

Keywords: electronic structure; solid-state structures; sulfides; zinc; zirconium.