Rb3Hg2(SO4)3Cl新型紫外非线性光学晶体材料

doi:10.15541/jim20220667

无机材料学报 ›› 2023, Vol. 38 ›› Issue (7): 778-784.DOI: 10.15541/jim20220667 CSTR: 32189.14.10.15541/jim20220667

Rb₃Hg₂(SO₄)₃Cl新型紫外非线性光学晶体材料

宋云霞¹(), 韩颖磊², 颜涛²(), 罗敏²()

1.福建工程学院电子电气与物理学院, 福州 350108
2.中国科学院福建物质结构研究所, 光电材料化学与物理重点实验室, 福州 350002

收稿日期:2022-11-09 修回日期:2022-12-27 出版日期:2023-03-15 网络出版日期:2023-03-17
通讯作者: 颜涛, 副研究员. E-mail: yantao@fjirsm.ac.cn;
罗敏, 研究员. E-mail: lm8901@fjirsm.ac.cn
作者简介:宋云霞(1992-), 女, 讲师. E-mail: yxsong@fjut.edu.cn
基金资助:
国家自然科学基金(22222510);国家自然科学基金(21975255);福建省自然科学基金(2021J011080);福建省自然科学基金(2021J01514);福建工程学院科研启动基金(GY-Z20042);中国科学院青年创新促进会(2019303)

New Ultraviolet Nonlinear Optical Crystal Rb₃Hg₂(SO₄)₃Cl

SONG Yunxia¹(), HAN Yinglei², YAN Tao²(), LUO Min²()

1. School of Electronic, Electrical Engineering and Physics, Fujian University of Technology, Fuzhou 350108, China
2. Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China

Received:2022-11-09 Revised:2022-12-27 Published:2023-03-15 Online:2023-03-17
Contact: YAN Tao, associate professor. E-mail: yantao@fjirsm.ac.cn;
LUO Min, professor. E-mail: lm8901@fjirsm.ac.cn
About author:SONG Yunxia (1992-), female, lecturer. E-mail: yxsong@fjut.edu.cn
Supported by:
National Natural Science Foundation of China(22222510);National Natural Science Foundation of China(21975255);Natural Science Foundation of Fujian Province(2021J011080);Natural Science Foundation of Fujian Province(2021J01514);Startup Foundation of Fujian University of Technology(GY-Z20042);Youth Innovation Prmotion Association CAS(2019303)

摘要/Abstract

摘要：

作为实现全固态激光器频率转换功能的关键材料, 紫外非线性光学晶体发挥着不可替代的作用。设计兼具大的非线性光学系数、合适的双折射和宽带隙的紫外非线性光学晶体仍然是该领域亟待攻克的一个难题。由于具有宽的带隙, 硫酸盐已成为紫外非线性光学晶体领域的一个重要研究方向。SO₄四面体基团具有接近非极性的Td对称性, 使其极化率各向异性和二阶极化率较小, 因而对晶体的非线性系数和双折射贡献很小。通常引入畸变程度高的阳离子多面体可以增加晶体的非线性效应和双折射。本工作将易于形成畸变多面体的Hg²⁺离子引入到硫酸盐体系中, 采用高温熔体法合成出新型非线性光学晶体材料Rb₃Hg₂(SO₄)₃Cl。该晶体属于单斜晶系, 空间群为P2₁, 晶胞参数为a=0.78653(2) nm, b=0.97901(2) nm, c=1.00104(3) nm, β=110.95(3), Z=2。其晶体结构由[SO₄]四面体、[HgO₅]和[HgO₄Cl]多面体以角共享的方式连接形成空间网状结构, 而Rb⁺填充在孔洞中。Rb₃Hg₂(SO₄)₃Cl晶体的粉末倍频效应为1.5倍KDP, 且能够在可见光区实现相位匹配。紫外漫反射光谱测试表明, 紫外截止边为251 nm, 对应光学带隙为4.94 eV。利用偏光显微镜确定该晶体在546.1 nm处的双折射为0.04。此外, 第一性原理计算表明, 晶体的非线性系数主要来源于扭曲的[HgO₅]、[HgO₄Cl]和[SO₄]多面体。上述结果表明, Rb₃Hg₂(SO₄)₃Cl是具有潜在应用前景的紫外非线性光学晶体材料。

关键词: 紫外, 汞基硫酸盐, 非线性光学晶体, 晶体结构

Abstract:

Ultraviolet (UV) nonlinear optical (NLO) crystals play an irreplaceable role as the key materials to realize the frequency conversion for all solid state lasers. To date, it is still difficult to design UV NLO crystals with large second harmonic generation (SHG) coefficients, moderate birefringences and wide band gaps. Benefiting from the large band gap, sulfate has become an important research direction of UV NLO crystals. However, since SO₄ is isotropic tetrahedral building units with nearly nonpolar T_d symmetry, it exhibits small microscopic second order polarizability and polarizability anisotropy, which tends to result in a weak SHG effect and small birefringence. In this work, we introduced Hg²⁺ ions that are easy to form distorted polyhedrons into the sulfates, resulting in a new NLO material, Rb₃Hg₂(SO₄)₃Cl. It crystallizes in a monoclinic space group (P2₁) with the lattice parameters a=0.78653(2) nm, b=0.97901(2) nm, c=1.00104(3) nm, and β=110.95(3) (Z=2). Structure of Rb₃Hg₂(SO₄)₃Cl consists of [SO₄] tetrahedra, [HgO₅] and [HgO₄Cl] polyhedral, which connected by a common corner to form a spatial 3D network. All the Rb atoms reside in the cavity of 3D network. The powder SHG measurement proposed by Kurtz and Perry indicates that Rb₃Hg₂(SO₄)₃Cl is a phase-matchable material in the visible region and exhibits a moderate SHG response about 1.5 times that of KH₂PO₄ (KDP). In addition, the UV-Vis-NIR diffuse reflectance spectral measurement indicates that Rb₃Hg₂(SO₄)₃Cl has a short UV cut-off edge of 251 nm, corresponding to the band gap of 4.94 eV. Its polarizing microscope measurement reveals that Rb₃Hg₂(SO₄)₃Cl has a moderate birefringence (The birefringence of Rb₃Hg₂(SO₄)₃Cl crystal at 546.1 nm is 0.04). Moreover, first-principles calculations uncover that the distorted [HgO₅], [HgO₄Cl] and [SO₄] polyhedral are responsible for its SHG effect. Our study shows that Rb₃Hg₂(SO₄)₃Cl may have potential applications as a UV NLO crystal.

Key words: ultraviolet, Hg-based sulfate, nonlinear optical crystal, crystal structure

中图分类号:

TQ174

宋云霞, 韩颖磊, 颜涛, 罗敏. Rb₃Hg₂(SO₄)₃Cl新型紫外非线性光学晶体材料[J]. 无机材料学报, 2023, 38(7): 778-784.

SONG Yunxia, HAN Yinglei, YAN Tao, LUO Min. New Ultraviolet Nonlinear Optical Crystal Rb₃Hg₂(SO₄)₃Cl[J]. Journal of Inorganic Materials, 2023, 38(7): 778-784.

图/表 13

图1 Rb3Hg2(SO4)3Cl样品的X射线粉末衍射图谱(a)及其单晶数据拟合结果(b)

Fig. 1 XRD pattern of (a) Rb3Hg2(SO4)3Cl and its crystal data fitting results (b)

图2 Rb3Hg2(SO4)3Cl的X射线能谱分析图谱

Fig. 2 Energy dispersive X-ray spectrum of Rb3Hg2(SO4)3Cl

图3 Rb3Hg2(SO4)3Cl的热重分析曲线

Fig. 3 TG curve of Rb3Hg2(SO4)3Cl

表1 Rb3Hg2(SO4)3Cl的晶胞参数和结构精修数据

Table 1 Crystal parameters and structure refinements for Rb3Hg2(SO4)3Cl

Parameters	Rb₃Hg₂(SO₄)₃Cl
Mass formula	981.22
Crystal system	Monoclinic
Space group	P2₁
a/nm	0.78653(2)
b/nm	0.97901(2)
c/nm	1.00104(3)
β/(°)	111.095(3)
V/nm³	0.71916(3)
Z	2
ρ(calcd)/(g·cm^-3)	4.531
Temperature/K	293(2)
λ/nm	0.071073
F(000)	864.0
μ/mm^-1	39.701
Rint	0.0304
R/wR (I>2σ(I))	0.0304/0.0703
R/wR (all data)	0.0317/0.0712
GOF on F²	1.023
Largest diff. peak and hole (e/nm^-3)	1.22×10^-3 and -1.76×10^-3

图4 Rb3Hg2(SO4)3Cl的晶体结构

Fig. 4 Crystal structure of Rb3Hg2(SO4)3Cl (a) Coordination environment of S and Hg ions; (b) Stacking of [SO4], [HgO5] and [HgO4Cl] polyhedra within a single cell; (c) Spatial network structure

图5 Rb3Hg2(SO4)3Cl的紫外-可见-近红外漫反射光谱图

Fig. 5 UV-Vis-NIR diffuse reflectance spectrum of Rb3Hg2(SO4)3Cl

图6 Rb3Hg2(SO4)3Cl的双折射测试结果

Fig. 6 Images of Rb3Hg2(SO4)3Cl birefringence (a) Crystals in polarized light; (b) Completed extinction of the crystal with forward compensation; (c) Completed extinction of the crystal with reverse compensation; (d) Thickness of measured crystal

图7 Rb3Hg2(SO4)3Cl的粉末倍频效应与颗粒度的关系

Fig. 7 SHG measurements of Rb3Hg2(SO4)3Cl ground crystals (red) with KDP (black) as a reference

表2 Rb3Hg2(SO4)3Cl的偶极矩

Table 2 Calculated dipole moments of Rb3Hg2(SO4)3Cl

Species	Dipole moment/D
Species	x	y	z	Total
HgO₅(typeⅠ)	1.277	0.673	-0.563	1.549
HgO₅(typeⅡ)	-1.277	0.673	0.563	1.549
∑_Hg-O	0	1.346	0	1.346
HgO₄Cl(typeⅠ)	0.270	3.231	-1.591	3.611
HgO₄Cl(typeⅡ)	-0.262	3.224	1.591	3.605
∑_Hg-O& ∑_Hg-Cl	0.008	6.455	0	6.455
SO₄(typeⅠ)	-0.928	-0.103	2.047	2.250
SO₄(typeⅡ)	-1.177	1.609	0.607	2.084
SO₄(typeⅢ)	1.767	-0.702	-1.505	2.425
SO₄(typeⅣ)	0.928	-0.102	-2.039	2.243
SO₄(typeⅤ)	-1.765	-0.702	1.512	2.428
SO₄(typeⅥ)	1.176	1.611	-0.608	2.085
∑_S-O	0.001	1.611	0.014	1.611

图8 Rb3Hg2(SO4)3Cl的能带结构及态密度分布

Fig. 8 Energy band structures and electronic density distribution of Rb3Hg2(SO4)3Cl (a) Diagram of calculated electronic band structures; (b) Diagrams of calculated PDOS

图9 Rb3Hg2(SO4)3Cl计算的电子密度图

Fig. 9 Calculated electron density diagram of Rb3Hg2(SO4)3Cl

图10 Rb3Hg2(SO4)3Cl计算的非线性光学系数随能量的变化曲线

Fig. 10 Calculated SHG coefficients of Rb3Hg2(SO4)3Cl

图11 计算得到的Rb3Hg2(SO4)3Cl的折射率色散曲线

Fig. 11 Calculated refractive index dispersion curves of Rb3Hg2(SO4)3Cl

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Rb₃Hg₂(SO₄)₃Cl新型紫外非线性光学晶体材料

New Ultraviolet Nonlinear Optical Crystal Rb₃Hg₂(SO₄)₃Cl

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