Ge-Sb-Se硫系玻璃的折射率和热光系数

杨安平; 王雨伟; 张少伟; 李兴隆; 杨志杰; 李耀程; 杨志勇

doi:10.7498/aps.68.20181869

摘要

Ge-Sb-Se硫系玻璃被认为是极佳的红外传输材料和有潜力的非线性光学材料.在光学设计中，玻璃的线性折射率（n）及其热光系数（ζ）是关键技术参数.以预测和调控Ge-Sb-Se玻璃的n和ζ为目的，考察了玻璃的n，ζ，密度（d）和体积膨胀系数（β）与化学参数dSe和拓扑网络结构参数<r>的内在联系.研究发现，玻璃的n随d的增加而增大；ζ随β的增大而近似线性减小；β随dSe的减小或<r>的增大而减小；当Ge含量固定时，d随dSe的减小或<r>的增大而增大，当Sb含量固定时，d在dSe=0时具有最小值.基于实测d和n，拟合获得了Ge，Sb和Se元素在2–12 μm波段的摩尔折射度（R_i），分别为R_Ge=10.16–10.50 cm³/mol，R_Sb=16.71–17.08 cm³/mol和R_Se=11.15–11.21 cm³/mol，根据d和R_i计算得到的n与实测值的偏差小于1%.基于实测ζ和β，拟合得到了Ge，Sb和Se元素在2–12 μm波段的摩尔折射度温度系数（φ_i），分别为φ_Ge=21.1–22.6 ppm/K，φ_Sb=7.2–8.4 ppm/K和φ_Se=90.2–94.2 ppm/K，根据β和φ_i计算得到的ζ与实测值的偏差小于6 ppm/K.

关键词:

Abstract

Ge-Sb-Se chalcogenide glass is environmentally friendly, and has wide infrared transmitting window, high optical nonlinearity, as well as good mechanical property. These make it a good material for infrared transmission and nonlinear optics. In optical designs, the refractive index (n) and thermo-optic coefficient (ζ) of the glass are key technical parameters. In order to predict and tailor the n and ζ of Ge-Sb-Se glass, compositions with different chemical and topological features are prepared, their n, ζ, density (d) and volume expansion coefficient (β) are measured, and the composition dependence of the parameters is systematically investigated. The chemical feature of the glass is quantified by the percentage deviation of the composition from the stoichiometric ratio and denoted as dSe. The topological feature is represented by the mean coordination number <r> of each atom in the composition. It is shown that the n of Ge-Sb-Se glass increases with d increasing; the ζ decreases almost linearly with β increasing; and the β decreases with dSe decreasing or <r> increasing. When the Ge content is fixed, the d increases with dSe decreasing or <r> increasing; when the Sb concentration is fixed, the d has a minimum value at dSe=0. Based on the measured d and n, the molar refractivity (R_i) of Ge, Sb and Se elements in a spectral range of 2-12 μm are calculated. The obtained value of R_Ge is in a range of 10.16-10.50 cm³/mol, R_Sd in a range of 16.71-17.08 cm³/mol, and R_Se in a range of 11.15-11.21 cm³/mol. When the R_i and d are used to compute n of any composition, the discrepancy between the calculated value and the measured one is less than 1%. According to the measured ζ and β, the thermal coefficients of the molar refractivity (φ_i) of Ge, Sb, and Se elements in a wavelength region of 2-12 μm are computed. The optimal value of φ_Ge is in a range of 21.1-22.6 ppm/K, φ_Sb in a range of 7.2-8.4 ppm/K, and φ_Se in a range of 90.2-94.2 ppm/K. When the φ_i and β are used to compute ζ of any composition, the discrepancy between the calculated value and the measured value is less than 6 ppm/K.

Keywords:

作者及机构信息

1. 江苏师范大学物理与电子工程学院, 江苏省先进激光材料与器件重点实验室, 徐州 221116;

2. 上海航天控制技术研究所, 上海 201109

Authors and contacts

1. Jiangsu Key Laboratory of Advanced Laser Materials and Devices, School of Physics and Electronic Engineering, Jiangsu Normal University, Xuzhou 221116, China;

2. Shanghai Aerospace Control Technology Institute, Shanghai 201109, China

参考文献

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[8]	Dai S X, Wang Y Y, Pen X F, Zhang P Q, Wang X S, Xu Y S 2018 Appl. Sci. Basel 8 707
[9]	Bernier M, Fortin V, Caron N, El-Amraoui M, Messaddeq Y, Vallee R 2013 Opt. Lett. 38 127
[10]	Kabakova I, Pant R, Winful H, Eggleton B 2014 J. Nonlinear Opt. Phys. Mater. 23 1450001
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[12]	Zhang X Y, Chen F F, Zhang X H, Ji W 2018 Chin. Phys. B 27 084208
[13]	Gleason B, Richardson K, Sisken L, Smith C 2016 Int. J. Appl. Glass Sci. 7 374
[14]	Wang T, Gulbiten O, Wang R, Yang Z, Smith A, Luther-Davies B, Lucas P 2014 J. Phys. Chem. B 118 1436
[15]	Wang Y W, Qi S S, Yang Z Y, Wang R P, Yang A P, Lucas P 2017 J. Non-Cryst. Solids 459 88
[16]	Thorpe M F 1983 J. Non-Cryst. Solids 57 355
[17]	Woollam J A, Johs B D, Herzinger C M, Hilfiker J N, Synowicki R A, Bungay C L 1999 Proc. SPIE CR72 3
[18]	Prod'homme L 1960 Phys. Chem. Glasses 1 119
[19]	Wei W H, Wang R P, Shen X, Fang L, Luther-Davies B 2013 J. Phys. Chem. C 117 16571
[20]	Han X, Tao H, Gong L, Wang X, Zhao X, Yue Y 2014 J. Non-Cryst. Solids 391 117
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施引文献

[1]	Zhang X H, Guimond Y, Bellec Y 2003 J. Non-Cryst. Solids 326 519
[2]	Cha D, Kim H, Hwang Y, Jeong J, Kim J 2012 Appl. Opt. 51 5649
[3]	Qi S S, Zhang B, Zhai C C, Li Y C, Yang A P, Yu Y, Tang D Y, Yang Z Y, Luther-Davies B 2017 Opt. Express 25 26148
[4]	Adam J L, Zhang X H 2014 Chalcogenide Glasses: Preparation, Properties and Applications (Oxford: Woodhead Publishing) pp438-470
[5]	Singh V, Lin P, Patel N, Lin H, Li L, Zou Y, Deng F, Ni C, Hu J, Giammarco J, Soliani A, Zdyrko B, Luzinov I, Novak S, Novak J, Wachtel P, Danto S, Musgraves J, Richardson K, Kimerling L, Agarwal A 2014 Sci. Technol. Adv. Mater. 15 014603
[6]	Ma P, Choi D, Yu Y, Yang Z Y, Vu K, Thach N, Mitchell A, Luther-Davies B, Madden S 2015 Opt. Express 23 19969
[7]	Yan T Y, Shen X, Wang R P, Wang G X, Dai S X, Xu T F, Nie Q H 2017 Chin. Phys. B 26 024213
[8]	Dai S X, Wang Y Y, Pen X F, Zhang P Q, Wang X S, Xu Y S 2018 Appl. Sci. Basel 8 707
[9]	Bernier M, Fortin V, Caron N, El-Amraoui M, Messaddeq Y, Vallee R 2013 Opt. Lett. 38 127
[10]	Kabakova I, Pant R, Winful H, Eggleton B 2014 J. Nonlinear Opt. Phys. Mater. 23 1450001
[11]	Zhang B, Yu Y, Zhai C C, Qi S S, Wang Y W, Yang A P, Gai X, Wang R P, Yang Z Y, Luther-Davies B 2016 J. Am. Ceram. Soc. 99 2565
[12]	Zhang X Y, Chen F F, Zhang X H, Ji W 2018 Chin. Phys. B 27 084208
[13]	Gleason B, Richardson K, Sisken L, Smith C 2016 Int. J. Appl. Glass Sci. 7 374
[14]	Wang T, Gulbiten O, Wang R, Yang Z, Smith A, Luther-Davies B, Lucas P 2014 J. Phys. Chem. B 118 1436
[15]	Wang Y W, Qi S S, Yang Z Y, Wang R P, Yang A P, Lucas P 2017 J. Non-Cryst. Solids 459 88
[16]	Thorpe M F 1983 J. Non-Cryst. Solids 57 355
[17]	Woollam J A, Johs B D, Herzinger C M, Hilfiker J N, Synowicki R A, Bungay C L 1999 Proc. SPIE CR72 3
[18]	Prod'homme L 1960 Phys. Chem. Glasses 1 119
[19]	Wei W H, Wang R P, Shen X, Fang L, Luther-Davies B 2013 J. Phys. Chem. C 117 16571
[20]	Han X, Tao H, Gong L, Wang X, Zhao X, Yue Y 2014 J. Non-Cryst. Solids 391 117
[21]	Feltz A 1993 Amorphous Inorganic Materials and Glasses (Weinheim: VCH) pp46-258

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