Synthesis, Crystal Structure, and Optical Properties of Noncentrosymmetric Na2ZnSnS4

Jianqiao He; Yangwu Guo; Wenjuan Huang; Xian Zhang; Jiyong Yao; Tianyou Zhai; Fuqiang Huang

doi:10.1021/acs.inorgchem.8b01025

Synthesis, Crystal Structure, and Optical Properties of Noncentrosymmetric Na₂ZnSnS₄

Inorg Chem. 2018 Aug 20;57(16):9918-9924. doi: 10.1021/acs.inorgchem.8b01025. Epub 2018 Aug 3.

Authors

Jianqiao He^{1

2}, Yangwu Guo^{2

3}, Wenjuan Huang⁴, Xian Zhang⁵, Jiyong Yao³, Tianyou Zhai⁴, Fuqiang Huang^{1

5}

Affiliations

¹ State Key Laboratory of High Performance Ceramics and Superfine Microstructure , Shanghai Institute of Ceramics, Chinese Academy of Sciences , Shanghai 200050 , P. R. China.
² University of Chinese Academy of Sciences , 19 Yuquan Road , Beijing 100049 , P. R. China.
³ Center for Crystal Research and Development, Technical Institute of Physics and Chemistry , Chinese Academy of Sciences , Beijing 100190 , P. R. China.
⁴ State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Engineering , Huazhong University of Science and Technology (HUST) , Wuhan 430074 , P. R. China.
⁵ 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 , 202 Chengfu Road , Beijing 100871 , P. R. China.

PMID: 30074388
DOI: 10.1021/acs.inorgchem.8b01025

Abstract

A new chalcogenide Na₂ZnSnS₄ has been successfully synthesized by using Na₂S₂ as reactive flux. Na₂ZnSnS₄ crystallizes in the tetragonal system with space group of I4̅. Its cell parameters are a = 6.4835(6) Å and c = 9.134(1) Å. The structure is a derivative of AgGaS₂, in which the Ag⁺ ions are replaced by Na⁺ ions and the Ga³⁺ ions are replaced by Zn²⁺ and Sn⁴⁺ ions. All three cations are in seriously distorted tetrahedral geometry with a distortion factor (η = c/ a) of 1.4. Optical measurements show that the Na₂ZnSnS₄ powder sample has a large transparent range from 0.8 to 25 μm and a wide band gap of 3.1 eV. It exhibits large second-harmonic generation intensity of 0.9 × AgGaS₂ in the grain size range from 41 to 74 μm. First-principles calculation results reveal that the valence band maximum and conduction band minimum are mainly composed of S 3p, Zn 3d orbitals and Sn 5s, S 3p orbitals, respectively.