一系列新型红外非线性光学半导体，ZnY6Si2S14、Al(x)Dy3(Si(y)Al(1 - y))S7以及Al0.33Sm3SiS7。

A series of new infrared NLO semiconductors, ZnY6Si2S14, Al(x)Dy3(Si(y)Al(1-y))S7, and Al0.33Sm3SiS7.

作者信息

Guo Sheng-Ping, Guo Guo-Cong, Wang Ming-Sheng, Zou Jian-Ping, Xu Gang, Wang Guo-Jian, Long Xi-Fa, Huang Jin-Shun

机构信息

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, PR China.

出版信息

Inorg Chem. 2009 Aug 3;48(15):7059-65. doi: 10.1021/ic802443n.

DOI:10.1021/ic802443n

PMID:19588902

Abstract

Four new quaternary isostructural rare-earth thiosilicates, ZnY(6)Si(2)S(14) (1), Al(0.50)Dy(3)(Si(0.50)Al(0.50))S(7) (2), Al(0.38)Dy(3)(Si(0.85)Al(0.15))S(7) (3), and Al(0.33)Sm(3)SiS(7) (4), crystallized in the chiral and polar space group P6(3), have been prepared by a facile synthetic routine. Compounds 1-3 show strong second harmonic generation effects at 2.1 um with the intensities of 1, 2, and 3 being about 2, 2, and 1 times that of KTP (KTiOPO(4)), respectively. The calculated band structure of 1 implies that the optical absorptions of BLn(6)M(2)Q(14) and ALn(3)MQ(7) family compounds are mainly ascribed to the charge transitions from Q-p to Ln-4f (4d for Y) states. Compounds 2-4 exhibit antiferromagnetic-like interactions.

摘要

通过一种简便的合成方法制备了四种新的同构四元稀土硫代硅酸盐，即ZnY₆Si₂S₁₄（1）、Al₀.₅₀Dy₃(Si₀.₅₀Al₀.₅₀)S₇（2）、Al₀.₃₈Dy₃(Si₀.₈₅Al₀.₁₅)S₇（3）和Al₀.₃₃Sm₃SiS₇（4），它们在手性极性空间群P6₃中结晶。化合物1 - 3在2.1μm处表现出强烈的二次谐波产生效应，其强度分别约为KTP（KTiOPO₄）的2倍、2倍和1倍。对1的计算能带结构表明，BLn₆M₂Q₁₄和ALn₃MQ₇族化合物的光吸收主要归因于从Q - p到Ln - 4f（Y为4d）态的电荷跃迁。化合物2 - 4表现出类反铁磁相互作用。