TiO2掺杂Ge-Sn-Se微晶玻璃的结构与光学特性研究

doi:10.15541/jim20150191

摘要/Abstract

摘要：

通过热熔融法将作为成核剂的TiO₂引入Ge-Sn-Se三元体系的硫系玻璃中, 并对玻璃样品进行不同时间的热处理。实验结果表明, 热处理能够使TiO₂掺杂Ge-Sn-Se玻璃析出SnSe₂六方晶体与GeSe₂单斜晶体, 并且随着热处理时间的延长, 透明样品的短波吸收边发生了红移, 光学带隙减小, Urbach能量增加, 说明玻璃中缺陷组织的数量在增加。通过Z扫描方法获得了各个样品在通信波长1550 nm下的三阶非线性参数, 研究了热处理时间对TiO₂掺杂Ge-Sn-Se玻璃光学非线性性能的影响。结果表明: 玻璃内部在热处理后析出的纳米级晶体具有很强的局域场效应, 能够极大地增加玻璃的三阶非线性, 样品的非线性折射率n₂最高达到5.75×10^-16 m²/W, 热处理3 h的样品同时具有较高非线性折射率和较高品质因子, 是一种性能优良的非线性光学材料。

关键词: 玻璃陶瓷, 非线性光学, 硫系玻璃, 红外和拉曼光谱

Abstract:

TiO₂manifested as nucleating agent was introduced in Ge-Sn-Se ternary chalcogenide glass by heat-melt method. Then the samples were heat-treated for different time. The experiment results indicated that heat treatment process can lead to the precipitation of GeSe₂ monoclinic crystals and SnSe₂ hexagonal crystals in the TiO₂doped Ge-Sn-Se glass with the heat treatment time increasing. The variety of UV cut-off wavelength, optical band gap and Urbach energy revealed that the number of defect units in glass-ceramic samples increased with the increment of heat treatment time. The third-order optical nonlinearity of all samples was measured by Z-scan technology at 1550 nm. The results showed that the formation of nano-crystals in glass-ceramic samples can improve the third-order nonlinear refraction index significantly due to the strong local field effect. The largest value of nonlinear refraction index reached 5.75×10^-16 m²/W, and the sample heat-treated for 3 h was considered as a high-quality nonlinear optical material for its high nonlinear refraction index as well as high figure of merit.

Key words: glass-ceramic, nonlinear optics, chalcogenide glass, infrared and Raman spectra

中图分类号:

TQ174

乔北京, 陈飞飞, 聂秋华, 戴世勋, 黄益聪. TiO₂掺杂Ge-Sn-Se微晶玻璃的结构与光学特性研究[J]. 无机材料学报, 2015, 30(11): 1189-1194.

QIAO Bei-Jing, CHEN Fei-Fei, NIE Qiu-Hua, DAI Shi-Xun, HUANG Yi-Cong. Structure and Third-order Optical Nonlinearity Performance of Ge-Sn-Se Doped TiO₂Glass-ceramics at 1550 nm[J]. Journal of Inorganic Materials, 2015, 30(11): 1189-1194.

图/表 8

图1 经270℃热处理不同时间TiO2掺杂Ge-Sn-Se玻璃样品的XRD图谱

Fig. 1 XRD patterns of samples after heat-treatment at 270℃ for different time

图2 热处理不同时间TiO2掺杂Ge-Sn-Se玻璃样品的拉曼光谱图

Fig. 2 Raman spectra of TiO2 doped Ge-Sn-Se samples heat- treated for different time Inset is the variation of integrated area from 170 to 210 cm-1 with heat- treatment time

图3 基质玻璃和玻璃陶瓷样品的吸收光谱

Fig. 3 Absorption spectra of host and glass-ceramic samples Inset is enlarged absorption edge from 707 nm to 721 nm

图 4 不同热处理时间TiO2掺杂的Ge-Sn-Se玻璃样品的Tauc曲线

Fig. 4 Tauc curves and optical band gap Eopg of TiO2 doped Ge-Sn-Se samples affer heat-treatment for different time Inset is variety tendency of Eopgwith heat treatment time

图5 不同热处理时间的TiO2掺杂Ge-Sn-Se硫系玻璃样品的Urbach 能量

Fig. 5 Urbach energy of TiO2 doped Ge-Sn-Se samples affer heat-treatment for different time

表1 不同热处理时间TiO2掺杂Ge-Sn-Se玻璃样品的密度、光学带隙和三阶非线性参数

Table 1 Physical properties and nonlinearity parameters of TiO2 doped Ge-Sn-Se glass-ceramic samples

NO.	Density/(g·cm^-3) (±0.001)	E_opg/ eV(±0.001)	E_e/ eV(±0.001)	n₂/ (10^-17m²·W^-1)(±10%)	β/ (10^-12 m·W^-1)(±10%)	FOM (±20%)
GSS-Ti-0	4.492	1.667	0.082	5.59	2.22	16.25
GSS-Ti-3	4.479	1.659	0.087	23.36	4.01	37.58
GSS-Ti-6	4.475	1.652	0.099	57.50	93.73	3.96
GSS-Ti-12	4.451	1.634	0.100	49.24	110.27	2.88
GSS-Ti-18	4.367	--	--	--	--	--
GSS-Ti-30	4.360	--	--	--	--	--
As₂Se₃	--	--	--	1.22	1.20	13.12

图6 不同热处理时间样品的傅里叶远红外透过光谱

Fig. 6 FTIR of samples after heat-treatment for different time

图7 不同热处理时间TiO2掺杂的Ge-Sn-Se玻璃样品的闭孔z扫描曲线(a)和开孔z扫描曲线(b)

Fig. 7 Closed-aperture Z-scan curves (a) and open-aperture Z-scan curves (b) of TiO2 doped Ge-Sn-Se glass-ceramic samples

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TiO₂掺杂Ge-Sn-Se微晶玻璃的结构与光学特性研究

Structure and Third-order Optical Nonlinearity Performance of Ge-Sn-Se Doped TiO₂Glass-ceramics at 1550 nm

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