新型紫外非线性光学晶体KNa5Ca5(CO3)8的合成、表征及性能的研究

doi:10.15541/jim20170335

摘要/Abstract

摘要：

采用水热法合成出一种新型碳酸盐非线性光学晶体材料KNa₅Ca₅(CO₃)₈, 该晶体属于六方晶系, 空间群为P63mc, 晶胞参数为a=b=1.00786(4) nm, c=1.26256(8) nm, Z=2。其晶体结构可以看作是由站立的[CO₃]基团连接相邻的两个[CaCO₃]_∞层, 从而沿[010]方向形成了四种不同类型的孔洞, 在这些孔洞中填充着K、Na 和[Na_0.67Ca_0.33]原子。KNa₅Ca₅(CO₃)₈晶体的粉末倍频效应为KDP的1.2倍, 且能够在可见光区实现相位匹配。紫外-可见-近红外漫反射光谱测试结果表明其晶体具有较大的光学带隙, 大概为5.95 eV, 是具有潜在应用前景的紫外非线性光学晶体材料。此外, 第一性原理的计算结果表明, 晶体的非线性系数主要来源于CO₃基团。

关键词: 紫外, 碳酸盐, 非线性光学晶体, 晶体生长

Abstract:

A new carbonate nonlinear optical (NLO) material, KNa₅Ca₅(CO₃)₈, was successfully synthesized by mild hydrothermal method. It crystallizes in hexagonal space group (P63mc) with lattice parameters a=b=1.00786(4) and c=1.26256(8) nm (Z=2). Structure of KNa₅Ca₅(CO₃)₈ can be described as standing-on-edge [CO₃] groups connecting the adjacent inﬁnite [CaCO₃]_∞ layers in the a-b plane to construct a framework with four types of channels running parallel to [010]. K, Na and [Na_0.67Ca_0.33] atoms reside in the tunnels. In the structure, the ?at-lying [CO₃] groups in two successive layers present an opposite orientation. This arrangement is negative for NLO susceptibilities. The macroscopic of SHG effects, however, originated from the standing-on-edge [CO₃] group along c axis. It is regrettable that the standing-on-edge [C3O₃] and [C4O₃] groups are almost arranged oppositely to the c direction, which weakens the SHG contribution from the standing-on-edge [CO₃] groups. Measurement of second harmonic generation (SHG) by the method adapted from Kurtz and Perry indicates that the compound is phase-matchable in visible region and exhibit moderate SHG response about 1.2 times higher than that of KH₂PO₄. In addition, UV-Vis-NIR diffuse reflectance spectral measurements indicate that KNa₅Ca₅(CO₃)₈ has a large optical gap about 5.95 eV. Moreover, first-principles electronic structure calculations show that the CO₃ groups play an important role in the total SHG response. Therefore, our data suggests that the new compound as NLO material may have potential applications in the UV region.

Key words: UV, carbonates, nonlinear optical crystal, crystal growth

中图分类号:

TQ174

陈巧玲, 罗敏, 林晨升. 新型紫外非线性光学晶体KNa₅Ca₅(CO₃)₈的合成、表征及性能的研究[J]. 无机材料学报, 2018, 33(6): 667-672.

CHEN Qiao-Ling, LUO Min, LIN Chen-Sheng. Synthesis, Characterization and Property of a New UV Nonlinear Optical Crystal KNa₅Ca₅(CO₃)₈[J]. Journal of Inorganic Materials, 2018, 33(6): 667-672.

图/表 9

图1 KNa5Ca5(CO3)8的XRD图谱

Fig. 1 XRD patterns of KNa5Ca5(CO3)8

图2 KNa5Ca5(CO3)8的热重分析曲线

Fig. 2 TG diagrams for KNa5Ca5(CO3)8

表1 KNa5Ca5(CO3)8的晶胞参数和结构精修数据

Table 1 Crystal data and structure refinement for KNa5Ca5(CO3)8

Formula	KNa₅Ca₅(CO₃)₈
Formula mass/amu	834.53
Crystal system	Hexagonal
Space group	P63 mc
a/nm	1.00786(4)
c/nm	1.26256(8)
α/(°)	90
γ/(°)	120
V/nm³	1.11066(9)
Z	2
ρ(calcd)(g/cm³)	2.495
Temperature/K	293(2)
λ/nm	0.071073
F (000)	828
μ/mm^-1	3.600
θ/(°)	2.33-27.50
Rint	0.0304
R/wR (I>2σ (I))	0.0620/0.1706
R/wR (all data)	0.0624/0.1710
GOF on F2	1.083
Largest Diff. peak and hole (e/nm^-3)	0.900 and-0.000574

图3 KNa5Ca5(CO3)8的晶体结构

Fig. 3 Crystal structure of KNa5Ca5(CO3)8

表2 KNa5Ca5(CO3)8与CsNa5Ca5(CO3)8的光学性能对比

Table 2 Optical properties of KNa5Ca5(CO3)8 and CsNa5Ca5(CO3)8

Crystal	Band gap/ eV	Nonlinear optical effect (×KDP)	Angle between CO₃group and c axis/(°)
KNa₅Ca₅(CO₃)₈	5.95	1.2	18.92
CsNa₅Ca₅(CO₃)₈	5.92	1.0	16.00

图4 KNa5Ca5(CO3)8粉末样品经过Kubelka-Munk方程转化的吸收光谱

Fig. 4 Diffuse reflectance curve transformed by Kubelka-Munk equation of the powder sample of KNa5Ca5(CO3)8

图5 KNa5Ca5(CO3)8的粉末倍频效应与颗粒度的关系

Fig. 5 SHG measurements of KNa5Ca5(CO3)8 ground crystals (red circle) with KDP (black square) as a reference

图6 KNa5Ca5(CO3)8的能带结构

Fig. 6 Band structure for KNa5Ca5(CO3)8

图7 KNa5Ca5(CO3)8的态密度图

Fig. 7 DOS and PDOS for KNa5Ca5(CO3)8

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新型紫外非线性光学晶体KNa₅Ca₅(CO₃)₈的合成、表征及性能的研究

Synthesis, Characterization and Property of a New UV Nonlinear Optical Crystal KNa₅Ca₅(CO₃)₈

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