Sb对GeSbxSe7-x硫系玻璃的结构和物性的影响

doi:10.15541/jim20140097

无机材料学报 ›› 2014, Vol. 29 ›› Issue (11): 1218-1222.DOI: 10.15541/jim20140097 CSTR: 32189.14.10.15541/jim20140097

Sb对GeSb_xSe_7-_x硫系玻璃的结构和物性的影响

魏文猴^1,2, 方亮^1,2, 杨志勇³, 沈祥⁴

(1. 重庆大学机械传动国家重点实验室，重庆400044；2. 重庆大学应用物理系, 重庆 401331; 3. 江苏师范大学物理与电子工程学院, 徐州 221116; 4. 宁波大学高等技术研究院红外材料与器件实验室, 宁波 315211)

收稿日期:2014-03-04 修回日期:2014-05-12 出版日期:2014-11-20 网络出版日期:2014-10-24
作者简介:魏文猴(1985–), 男, 博士研究生. E-mail:wwh732@163.com
基金资助:
国家自然科学基金(61377061,61205207);National Natural Science Foundation of China (61377061,61205207)

Effect of Sb on Structure and Physical Properties of GeSb_xSe_7-_x Chalcogenide Glasses

WEI Wen-Hou^1,2, FANG Liang^1,2, YANG Zhi-Yong³, SHEN Xiang⁴

(1. The State Key Laboratory of Mechanical Transmissions, Chongqing University, Chongqing 400044, China; 2.Department of Applied Physics, Chongqing University, Chongqing 401331, China; 3. School of Physics and Electronic Engineering, Jiangsu Normal University, Xuzhou 221116, China; 4. Laboratory of Infrared Material and Devices, Advanced Technology Research Institute, Ningbo University, Ningbo 315211, China)

Received:2014-03-04 Revised:2014-05-12 Published:2014-11-20 Online:2014-10-24
About author:WEI Wen-Hou. E-mail:wwh732@163.com

摘要/Abstract

摘要：

采用熔融-淬冷法制备了GeSb_xSe_7-_x (x = 0.4、0.8、1.2、1.6、2.0)系列硫系玻璃, 并系统地研究了Sb对玻璃结构和物理性能的影响。拉曼光谱测试结果显示, 随着Sb含量增加, 玻璃结构逐渐从由Se链或Se环主导转变为由交联的SbSe_3/2三角锥结构单元和GeSe_4/2四面体结构单元主导, 玻璃网络交联程度增加。同时, 玻璃的转变温度、密度、弹性模量和折射率都随着Sb含量的增加而增大。透过光谱研究表明, 随着Sb逐渐替换Se原子, 光学带隙逐步减小。

关键词: Ge-Sb-Se, 硫系玻璃, 拉曼光谱, 弹性模量, 折射率, 玻璃转变

Abstract:

GeSb_xSe_7-_x (x = 0.4, 0.8, 1.2, 1.6, 2.0) chalcogenide glasses were prepared by the melt-quenching technique, and the effect of Sb on glass structures and physical properties were systematically investigated. Raman spectra of these glasses show that the glass structure gradually changes from Se chains or Se rings dominated to SbSe_3/2 pyramids and GeSe_4/2 tetrahedra cross-linked, and the degree of cross-linkage of glass network improves with Sb content increase. Meanwhile, the glass transition temperature, density, elastic moduli, and refractive index increase with Sb content increase. The transmittance spectra indicate that replacement of Se with Sb leads to gradually reducing the optical bandgap.

Key words: Ge-Sb-Se, chalcogenide glass, Raman spectrum, elastic moduli, refractive index, glass transition

中图分类号:

TB484

魏文猴, 方亮, 杨志勇, 沈祥. Sb对GeSb_xSe_7-_x硫系玻璃的结构和物性的影响[J]. 无机材料学报, 2014, 29(11): 1218-1222.

WEI Wen-Hou, FANG Liang, YANG Zhi-Yong, SHEN Xiang. Effect of Sb on Structure and Physical Properties of GeSb_xSe_7-_x Chalcogenide Glasses[J]. Journal of Inorganic Materials, 2014, 29(11): 1218-1222.

图/表 6

图1 GeSbxSe7-x玻璃的拉曼光谱图

Fig. 1 Raman spectra of GeSbxSe7-x glasses

图2 GeSbxSe7-x玻璃差示扫描量热曲线

Fig. 2 DSC curves of GeSbxS7-x glasses

图3 GeSbxSe7-x玻璃的密度、剪切弹性模量(Cs)和压缩弹性模量(Cc)

Fig. 3 Density, shear elastic modulus (Cs) and compression elastic modulus (Cc) of GeSbxSe7-x glasses

表1 GeSbxSe7-x的玻璃转变温度(Tg)、密度(ρ)、平均摩尔体积()、剪切弹性模量(Cs)、压缩弹性模量(Cc)、玻璃折射率(n)、直接跃迁光学带隙(Eoptd)和间接跃迁光学带隙(Eopti)

Table 1 Glass transition temperature (Tg), density (ρ), average molar volume (), shear elastic modulus (Cs), compression elastic modulus (Cc), refractive index (n), direct optical band gap (Eoptd) and indirect optical band gap (Eopti) of GeSbxSe7-x glasses

GeSb_xSe_7-_x	T_g / ℃	ρ / (g·cm^-3)	/ (cm³·mol^-1)	C_s/(0.1 GPa)	C_c / (0.1 GPa)	n	E_optd / eV	E_opti / eV
x=0.4	118.9	4.479	17.93	64.346	186.783	2.529	1.64	1.54
x=0.8	139.9	4.613	17.87	66.633	205.459	2.610	1.58	1.47
x=1.2	159.0	4.758	17.78	71.225	228.572	2.702	1.53	1.42
x=1.6	183.1	4.873	17.75	77.619	241.562	2.803	1.47	1.37
x=2.0	243.8	5.009	17.74	82.945	251.312	2.933	1.42	1.32

图4 GeSbxSe7-x玻璃在(a)可见-近红外区域和(b)红外区域的透过光谱

Fig. 4 Transmittance in the region of Vis-NIR (a) and IR (b) of GeSbxSe7-x glasses

图5 GeSbxSe7-x玻璃的(αhν)2和hν(声子能)的关系曲线(a)及(αhν)1/2和hν的关系曲线(b)

Fig. 5 (a) The plots of (αhν)2 vs hν (photon energy) and (b) the plots of (αhν)1/2 vs hν of GeSbxSe7-x glasses

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Sb对GeSb_xSe_7-_x硫系玻璃的结构和物性的影响

Effect of Sb on Structure and Physical Properties of GeSb_xSe_7-_x Chalcogenide Glasses

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Sb对GeSbxSe7-x硫系玻璃的结构和物性的影响

Effect of Sb on Structure and Physical Properties of GeSbxSe7-x Chalcogenide Glasses

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Sb对GeSb_xSe_7-_x硫系玻璃的结构和物性的影响

Effect of Sb on Structure and Physical Properties of GeSb_xSe_7-_x Chalcogenide Glasses