银复合的Ge-In-S-CsI硫系玻璃的非线性光学性能研究

doi:10.3724/SP.J.1077.2014.13510

无机材料学报 ›› 2014, Vol. 29 ›› Issue (7): 735-740.DOI: 10.3724/SP.J.1077.2014.13510 CSTR: 32189.14.SP.J.1077.2014.13510

银复合的Ge-In-S-CsI硫系玻璃的非线性光学性能研究

许银生¹, 成俊雯^1,2, 戚嘉妮^1,3, 鲁珊珊³, 鲁克伦⁴, 徐建伟², 邵琦芬², 戴世勋¹

(宁波大学 1. 高等技术研究院红外材料及器件实验室; 2. 信息科学与工程学院; 3. 材料科学与化学工程学院; 4. 科学技术学院, 宁波 315211)

收稿日期:2013-10-06 修回日期:2013-12-27 出版日期:2014-07-20 网络出版日期:2014-06-20
作者简介:许银生(1984-), 男, 讲师. E-mail: xuyinsheng@nbu.edu.cn
基金资助:
国家自然科学基金(61205181);浙江省自然科学基金(LQ12E02003);宁波市自然科学基金(2012A610122);浙江省教育厅科研项目(Y201120457);教育部留学回国人员科研启动基金;宁波大学王宽诚幸福基金

Nonlinear Optical Properties of Silver Composited Ge-In-S-CsI Chalcogenide Glasses

XU Yin-Sheng¹, CHENG Jun-Wen^1,2, QI Jia-Ni^1,3, LU Shan-Shan³, LU Ke-Lun⁴, XU Jian-Wei², SHAO Qi-Fen², DAI Shi-Xun¹

(1. Laboratory of Infrared Materials and Devices, Advanced Technology Research Institute; 2. College of Information Science and Engineering; 3. School of Materials Science and Chemical Engineering; 4. College of Science & Technology, Ningbo University, Ningbo 315211, China)

Received:2013-10-06 Revised:2013-12-27 Published:2014-07-20 Online:2014-06-20
About author:XU Yin-Sheng. E-mail: xuyinsheng@nbu.edu.cn
Supported by:
National Natural Science Foundation of China (61205181);Natural Science Foundation of Zhejiang Province (LQ12E-02003);Natural Science Foundation of Ningbo City (2012A610122);Scientific Research Fund of Zhejiang Provincial Education Department (Y201120457);Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry;K. C. Wong Magna Fund in Ningbo University

摘要/Abstract

摘要：

通过真空熔融淬冷法制备了银复合的70GeS₂-20In₂S₃-10CsI硫系玻璃样品, 利用Z-扫描技术研究了玻璃样品在800 nm处三阶非线性光学性质, 发现引入Ag可提高其折射率n和非线性折射率γ, n从2.204增加至2.4087, γ从23.3×10^-18 m²/W增加到30.5×10^-18m²/W, 此外非线性响应时间从70 fs增加到79 fs。热处理对玻璃的非线性光学性能的影响研究显示, 热处理后样品的γ增加至44.3×10^-18 m²/W, 是As₂Se₃玻璃的两倍多。发现析晶后带隙变小(吸收边红移)导致非线性吸收系数β减小, 使得样品的品质因子提高至3.3。Ag复合的硫系玻璃及玻璃陶瓷非线性折射率大、品质因子高、非线性响应快, 有望用于全关开关等各类非线性光学器件中。

关键词: 银复合, 非线性折射率, 硫系玻璃, Z-扫描, 非线性响应时间

Abstract:

In this study, the Ag doped 70GeS₂-20In₂S₃-10CsI chalcogenide glasses were synthesized by vacuumed melting-quenching technique. The third nonlinear optical properties were studied using Z-Scan technique at 800 nm. After being introduced Ag into the glass, both the linear and nonlinear refraction index γ increased from 2.204 to 2.2087 and from 23.3×10^-18 to 30.5×10^-18 m²/W, respectively. Besides, the nonlinear response time increased from 70 fs to 79 fs. The further heat treatment also enhanced the nonlinear refraction index up to 44.3×10^-18 m²/W, 2 folds higher than that of As₂Se₃. Meanwhile, the nonlinear absorption coefficient β decreased because the bandgap decreased with the thermal heat treatment. However, the highest figure of merit (FOM) is 3.3, which is enough for the nonlinear optics. Large nonlinear refraction index, high FOM, and fast response time ensured that the Ag-composited chalcogenide glass and glass ceramics can find applications in nonlinear optics.

Key words: Ag dopping, nonlinear refractive index, chalcogenide glass, Z-Scan, nonlinear response time

中图分类号:

TQ171

许银生, 成俊雯, 戚嘉妮, 鲁珊珊, 鲁克伦, 徐建伟, 邵琦芬, 戴世勋. 银复合的Ge-In-S-CsI硫系玻璃的非线性光学性能研究[J]. 无机材料学报, 2014, 29(7): 735-740.

XU Yin-Sheng, CHENG Jun-Wen, QI Jia-Ni, LU Shan-Shan, LU Ke-Lun, XU Jian-Wei, SHAO Qi-Fen, DAI Shi-Xun. Nonlinear Optical Properties of Silver Composited Ge-In-S-CsI Chalcogenide Glasses[J]. Journal of Inorganic Materials, 2014, 29(7): 735-740.

图/表 6

表1 样品的线性折射率、三阶非线性参数和非线性响应时间

Table 1 The refractive index, nonlinearity parameters and response time

Glass	Temp.-t/(℃-h)	n(@632.8 nm)	E_g/eV	γ/(×10^-18, m²∙W^-1)	β/(×10^-11, m∙W^-1)	F	Responsetime /fs
G	-	2.204	2.43	23.3	2.09	1.4	70
	350-12	-	2.43	21.6	-	-	-
	380-12	-	2.39	44.3	-	-	-
	380-18	-	2.30	31.6	-	-	-
GAg	-	2.2087	2.46	30.5	1.57	2.4	79
	350-12	-	2.46	31.1	-		-
	380-12	-	1.80	34.3	1.29	3.3	-
Ge₃₅As₁₅Se₅₀^{[18], a}		2.6	1.94^c	24.6	0.5	3.2	-
As₂Se₃^{[19], b}		2.864@1310nm	1.54^c	18	4.5	0.38^c	-
Silica^[20]		-	-	2.73×10^-2	-	-	-

图1 玻璃样品的差热曲线

Fig. 1 DSC curves of G and GAg glasses

图2 样品的在不同热处理下的吸收光谱

Fig. 2 Absorption spectra of glass without (a) or with (b) AgCl addition heat-treatment under different conditions

图3 GAg样品在不同热处理下的XRD图样

Fig. 3 XRD patterns of GAg heat-treated under different conditions

图4 样品G(a)、G-380-18(b)、GAg (c)和GAg-380-12 (d)的Z-扫描闭孔信号(实线为拟合数据, 泵浦激光波长800 nm)

Fig. 4 Closed-aperture Z-Scan curves of samples G (a)、G-380-18 (b)、GAg (c) and GAg-380-12 (d). The red solid lines are theoretical fits

图5 Z-扫描开孔信号, 泵浦激光波长800 nm

Fig. 5 Open aperture Z-Scan curves of the samples at 800 nm

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银复合的Ge-In-S-CsI硫系玻璃的非线性光学性能研究

Nonlinear Optical Properties of Silver Composited Ge-In-S-CsI Chalcogenide Glasses

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