S取代Se对Ge11.5As24Se64.5–xSx玻璃结构及光学性质的影响

许思维; 杨晓宁; 杨大鑫; 王训四; 沈祥

doi:10.7498/aps.70.20210536

摘要

本文制备了硫系玻璃Ge_11.5As₂₄Se_64.5–xS_x (x = 0, 16.125%, 32.25%, 48.375%和64.5%)并研究了其光学性质, 目的在于筛选可用于光学器件的最佳组分. 通过测试该系列玻璃的激光损伤阈值、折射率、三阶非线性折射率以及吸收光谱, 结果发现, 玻璃中的Se被S原子逐渐替代后, 玻璃的线性和三阶非线性折射率逐渐降低, 玻璃光学带隙和激光损伤阈值不断升高. 我们进一步利用拉曼散射光谱和高分辨率X射线光电子能谱研究导致这些物理性能变化的结构起源, 通过分析玻璃中不同结构单元的演变过程, 发现在这些玻璃网络结构中均以异极键(Ge—Se/S, As—Se/S)为主, 且相对于Se而言, Ge和As优先与S结合成键. 随着玻璃结构中S/Se比例的增加, 与Se相关的化学键(Ge—Se, As—Se和Se—Se)数量逐渐减少, S相关化学键(Ge—S, As—S和S—S)数量逐渐增加, 但这对玻璃的拓扑结构几乎没有影响. 由此可以断定引起玻璃物理性质变化的主要原因是玻璃结构体系中各个化学键强度之间的差异.

关键词:

硫系玻璃 /
结构 /
光学性质

Abstract

In this paper, chalcogenide glasses Ge_11.5As₂₄Se_64.5–xS_x (x = 0, 16.125%, 32.25%, 48.375% and 64.5%) are prepared and their optical properties are studied in order to select the best components for the use in optical devices. The values of laser damage threshold, refractive index, and third-order nonlinear refractive index, as well as the absorption spectra of the glasses are measured. The results show that the linear and third-order nonlinear refractive indices of the glass decrease gradually, the glass optical band gap increases gradually, and the laser damage threshold increases continuously after the high threshold component S atoms have been introduced gradually. We further investigate the structural origins of these changes in physical properties by Raman scattering spectra and high resolution X-ray photoelectron spectroscopy. By analyzing the evolution process of different structural units in the glass, it is found that the heteropolar bonds (Ge—Se/S, As—Se/S) are dominant in these glass network structures, and compared with Se, and that Ge and As prefer to bond with S. As the ratio of S/Se increases, the number of chemical bonds related to Se (Ge—Se, As—Se and Se—Se) decreases gradually, while the number of chemical bonds related to Se (Ge—S, As—S and S—S) increases gradually, which has little effect on the change of the topological structure of glass. It can be concluded that the main reason for the change of physical properties of glass is the difference of the strength between chemical bonds in the glass structural system.

Keywords:

作者及机构信息

1.
湖南文理学院数理学院, 常德　415000

2.
宁波大学高等技术研究院, 浙江省光电探测材料及器件重点实验室, 宁波　315211

通信作者: 许思维, xusiwei1227@163.com

基金项目: 国家自然科学基金(批准号: 62004067, 11847159)、湖南省自然科学基金(批准号: 2019JJ50410)和湖南省教育厅科学研究项目(批准号: 18C0744)资助的课题

Authors and contacts

1.
College of Mathematics and Physics, Hunan University of Arts and Science, Changde 415000, China

2.
Key Laboratory of Photoelectric Materials and Devices of Zhejiang Province, The Research Institute of Advanced Technologies, Ningbo University, Ningbo 315211, China

Corresponding author: Xu Si-Wei, xusiwei1227@163.com

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 62004067, 11847159), the Natural Science Foundation of Hunan Province, China (Grant No. 2019JJ50410), and the Research Foundation of Education Bureau of Hunan Province, China (Grant No. 18C0744)

文章全文

参考文献

[1]	Wang R P 2014 Amorphous Chalcogenides: Advances and Applications (Singapore: Pan Stanford Publisher) pp97−118
[2]	Tanaka K, Shimakawa K 2011 Amorphous Chalcogenide Semiconductors and Related Materials (New York: Springer International Publishing) pp118−122
[3]	Niu L, Chen Y M, Shen X, Xu T F 2020 Chin. Phys. B 29 087803 Google Scholar
[4]	许思维, 王丽, 沈祥 2015 物理学报 64 223302 Google Scholar Xu S W, Wang L, Shen X 2015 Acta Phys. Sin. 64 223302 Google Scholar
[5]	Xu S W, Wang R P, Yang Z Y, Wang L, Luther-Davies B 2016 Chin. Phys. B 25 057105 Google Scholar
[6]	乔北京, 陈飞飞, 黄益聪, 戴世勋, 聂秋华, 徐铁峰 2015 物理学报 64 154216 Google Scholar Qiao B J, Chen F F, Huang Y C, Dai S X, Nie Q H, Xu T F 2015 Acta Phys. Sin. 64 154216 Google Scholar
[7]	Eggleton B J, Luther-Davies B, Richardson K 2011 Nat. Photonics 5 141 Google Scholar
[8]	Ren J, Lu X S, Lin C G, Jain R K 2020 Opt. Express 28 21522 Google Scholar
[9]	Wang R P, Bulla D, Smith A, Wang T, Luther-Davies B 2011 J. Appl. Phys. 109 023517 Google Scholar
[10]	Lin H T, Song Y, Huang Y Z, Kita D, Deckoff-Jones S, Wang K Q, Li L, Li J Y, Zheng H Y, Luo Z Q, Wang H Z, Novak S, Yadav A, Huang C C, Shiue R J, Englund D, Gu T, Hewak D, Richardson K, Kong J, Hu J J 2017 Nat. Photonics 11 798 Google Scholar
[11]	Wang L L, Zeng J H, Zhu L, Yang D D, Zhang Q, Zhang P Q, Wang X S, Dai S X 2018 Appl. Opt. 57 10044 Google Scholar
[12]	田康振, 胡永胜, 任和, 祁思胜, 杨安平, 冯宪, 杨志勇 2021 物理学报 70 047801 Google Scholar Tian K Z, Hu Y S, Ren H, Qi S S, Yang A P, Feng X, Yang Z Y 2021 Acta Phys. Sin. 70 047801 Google Scholar
[13]	Choi D Y, Madden S, Rode A, Wang R P, Luther-Davies B 2007 Appl. Phys. Lett. 91 011115 Google Scholar
[14]	Wang T, Gai X, Wei W H, Wang R P, Yang Z Y, Shen X, Madden S, Luther-Davies B 2014 Opt. Mater. Express 4 1011 Google Scholar
[15]	Wang T, Gulbiten O, Wang R P, Yang Z Y, Smith A, Luther-Davies B, Lucas P 2014 J. Phys. Chem. B 118 1436 Google Scholar
[16]	Wang R P, Yan K L, Yang Z Y, Luther-Davies B 2015 J. Non-Cryst. Solids 427 16 Google Scholar
[17]	Kotsalas I P, Papadimitriou D, Raptis C, Vlcek M, Frumar M 1998 J. Non-Cryst. Solids 226 85 Google Scholar
[18]	Wang R P, Smith A, Luther-Davies B, Kokkonen H, Jackson I 2009 J. Appl. Phys. 105 056109 Google Scholar
[19]	Cernosek Z, Cernoskova E, Todorov R, Holubova J 2020 J. Solid State Chem. 291 121599 Google Scholar
[20]	Wang R P, Smith A, Prasad A, Choi D Y, Luther-Davies B 2009 J. Appl. Phys. 106 043520 Google Scholar
[21]	Yang G, Bureau B, Rouxel T, Gueguen Y, Gulbiten O, Roiland C, Soignard E, Yarger J L, Troles J, Sangleboeuf J C, Lucas P 2010 Phys. Rev. B 82 195206 Google Scholar
[22]	徐航, 彭雪峰, 戴世勋, 徐栋, 张培晴, 许银生, 李杏, 聂秋华 2016 物理学报 65 154207 Google Scholar Xu H, Peng X F, Dai S X, Xu D, Zhang P Q, Xu Y S, Li X, Nie Q H 2016 Acta Phys. Sin. 65 154207 Google Scholar
[23]	Jackson K, Briley A, Grossman S, Porezag D V, Pederson M R 1999 Phys. Rev. B 60 14985 Google Scholar
[24]	Mei Q, Saienga J, Schrooten J, Meyer B, Martin S W 2003 J. Non-Cryst. Solids 324 264 Google Scholar
[25]	Zhang Y, Xu Y S, You C Y, Xu D, Tang J Z, Zhang P Q, Dai S X 2017 Opt. Express 25 8886 Google Scholar
[26]	Frumarova B, Nemec P, Frumar M, Oswald J, Vlcek M 1999 J. Non-Cryst. Solids 256-257 266 Google Scholar
[27]	Kotsalas I P, Papadimitriou D, Raptis C, Vlcek M, Frumar M 1998 Journal of Non-Cryst. Solids 226 85
[28]	Rana A, Singh B P, Sharma R 2019 J. Non-Cryst. Solids 523 119597 Google Scholar
[29]	Musgraves J D, Wachtel P, Gleason B, Richardson K 2014 J. Non-Cryst. Solids 386 61 Google Scholar
[30]	Nefedov V I 1988 X-Ray Photoelectron Spectroscopy of Solid Surfaces (Boca Raton: CRC Press) pp97−128
[31]	Wang R P, Choi D Y, Rode A V, Madden S J, Luther-Davies B 2007 J. Appl. Phys. 101 113517 Google Scholar
[32]	Xu S W, Wang R P, Luther-Davies B, Kovalskiy A, Miller A C, Jain H 2014 J. Appl. Phys. 115 083518 Google Scholar
[33]	Luo Y R 2007 Comprehensive Handbook of Chemical Bond Energies (Boca Raton: CRC Press) pp431−488
[34]	Kovalskiy A, Jain H, Miller A C, Golovchak R Y, Shpotyuk O I 2006 J. Phys. Chem. B 110 22930 Google Scholar
[35]	Opletal G, Drumm D W, Wang R P, Russo S P 2014 J. Phys. Chem. A 118 4790 Google Scholar
[36]	Li Q L, Wang R P, Xu F, Wang X S, Yang Z Y, Gai X 2020 Opt. Mater. Express 10 1413 Google Scholar
[37]	Lu X S, Li J H, Yang L, Zhang R N, Zhang Y D, Ren J, Galca A C, Secu M, Farrell G, Wang P F 2020 J. Non-Cryst. Solids 528 119757 Google Scholar

施引文献

图 1 Ge_11.5As₂₄Se_64.5–xS_x玻璃制备的流程图

Fig. 1. Flow chart of Ge_11.5As₂₄Se_64.5–xS_x glasses fabrication.

下载: 全尺寸图片幻灯片

图 2 Ge_11.5As₂₄Se_64.5–xS_x玻璃的拉曼散射光谱分峰拟合图

Fig. 2. Raman scattering spectra of Ge_11.5As₂₄Se_64.5–xS_x glasses and their decompositions.

下载: 全尺寸图片幻灯片

图 3 (a) Ge_11.5As₂₄Se_64.5–xS_x 玻璃的S2p 的XPS分解; (b) Ge_11.5As₂₄Se_64.5–xS_x 玻璃的Se3d 的XPS分解

Fig. 3. (a) S2p spectra of Ge_11.5As₂₄Se_64.5–xS_x glasses and their decompositions; (b) Se3d spectra of Ge_11.5As₂₄Se_64.5–xS_x glasses and their decompositions.

下载: 全尺寸图片幻灯片

图 4 (a) Ge_11.5As₂₄Se_64.5–xS_x 玻璃的Ge3d 的XPS分解; (b) Ge_11.5As₂₄Se_64.5–xS_x 玻璃的As3d 的XPS分解

Fig. 4. (a) Ge3d spectra of Ge_11.5As₂₄Se_64.5–xS_x glasses and their decompositions; (b) As3d spectra of Ge_11.5As₂₄Se_64.5–xS_x glasses and their decompositions.

下载: 全尺寸图片幻灯片

表 1 Ge_11.5As₂₄Se_64.5–xS_x的组分与光学参数(n, I_th, E_g和n₂)

Table 1. Compositions and optical parameters (n, I_th, E_g and n₂) of Ge_11.5As₂₄Se_64.5–xS_x glasses.

Ge_11.5As₂₄ Se_64.5–xS_x	n	I_th/(W·cm^–2)	E_g/eV	n₂/(10^–14 W·cm^–2)
x = 0	2.639	3.95 × 10⁵	1.859	7.411
x = 16.125	2.546	14.78 × 10⁵	1.898	5.498
x = 32.25	2.451	21.40 × 10⁵	1.979	3.679
x = 48.375	2.378	35.29 × 10⁵	2.069	2.751
x = 64.5	2.261	—	2.347	2.187

下载: 导出CSV

表 2 拉曼散射光谱分峰拟合中各个结构单元的相对比例

Table 2. Relative ratio of the different structural units derived from the decomposed Raman scattering spectra.

	Ge Se_4/2 (CS) /%	Ge Se_4/2 (ES) /%	As Se_3/2/%	Se-Se/%	As-Se/%	As S_3/2/%	Ge S_4/2 (CS)/%	Ge S_4/2 (ES)/%	As-S/%	S-S/%
Ge_11.5As₂₄Se_64.5	14.79	7.52	45.36	9.28	23.05	0	0	0	0	0
Ge_11.5As₂₄Se_48.375S_16.125	10.24	6.97	36.36	6.27	21.57	5.96	2.35	7.63	2.65	0
Ge_11.5As₂₄Se_32.25S_32.25	4.98	4.63	25.65	2.09	19.08	16.26	9.47	11.92	5.61	0.31
Ge_11.5As₂₄Se_16.125S_48.375	0.94	2.20	13.92	0.58	16.84	26.16	11.94	19.16	7.47	0.79
Ge_11.5As₂₄S_64.5	0	0	0	0	0	41.64	14.55	29.21	13.52	1.08

下载: 导出CSV

表 3 Ge_11.5As₂₄Se_64.5–xS_x 玻璃的Ge3d, As3d, Se3d 和S2p 的XPS的拟合参数

Table 3. The fitting parameters for the decomposed Ge3d, As3d, Se3d and S2p spectra of Ge_11.5As₂₄Se_64.5–xS_x glasses.

		Structural unit
		Se-Se- Ge/As	As/Ge-Se-Ge/As	S-S- Ge/As	As/Ge-S-Ge/As	AsSe/S_3/2	As-As- related structure	GeSe/S_4/2	Ge-Ge- related structure
Ge_11.5As₂₄Se_64.5	BE/eV	54.9	54.5	—	—	43.0	—	31.3	—
	FWHM/eV	1.11	1.13			1.03		1.01
	Content/%	18	82			100		100
Ge_11.5As₂₄ Se_48.375S_16.125	BE/eV	55.0	54.6	—	162.1	42.9	—	31.3	—
	FWHM/ eV	1.10	1.18		1.12	1.03		1.10
	Content/%	13	87		100	100		100
Ge_11.5As₂₄ Se_32.25S_32.25	BE/eV	54.9	54.5	162.4	162.1	43.0	—	31.4	—
	FWHM/ eV	1.09	1.11	1.21	1.23	1.15		1.04
	Content/%	11	89	6	94	100		100
Ge_11.5As₂₄ Se_16.125S_48.375	BE/eV	55.0	54.6	162.3	162.0	42.9	—	31.2	—
	FWHM/ eV	1.11	1.14	1.25	1.11	1.11		1.14
	Content/%	8	92	12	88	100		100
Ge_11.5As₂₄S_64.5	BE/eV	—	—	162.3	162.1	42.8	—	31.3	—
	FWHM/ eV			1.21	1.12	1.03		1.09
	Content/%			16	84	100		100

下载: 导出CSV

[1]	Wang R P 2014 Amorphous Chalcogenides: Advances and Applications (Singapore: Pan Stanford Publisher) pp97−118
[2]	Tanaka K, Shimakawa K 2011 Amorphous Chalcogenide Semiconductors and Related Materials (New York: Springer International Publishing) pp118−122
[3]	Niu L, Chen Y M, Shen X, Xu T F 2020 Chin. Phys. B 29 087803 Google Scholar
[4]	许思维, 王丽, 沈祥 2015 物理学报 64 223302 Google Scholar Xu S W, Wang L, Shen X 2015 Acta Phys. Sin. 64 223302 Google Scholar
[5]	Xu S W, Wang R P, Yang Z Y, Wang L, Luther-Davies B 2016 Chin. Phys. B 25 057105 Google Scholar
[6]	乔北京, 陈飞飞, 黄益聪, 戴世勋, 聂秋华, 徐铁峰 2015 物理学报 64 154216 Google Scholar Qiao B J, Chen F F, Huang Y C, Dai S X, Nie Q H, Xu T F 2015 Acta Phys. Sin. 64 154216 Google Scholar
[7]	Eggleton B J, Luther-Davies B, Richardson K 2011 Nat. Photonics 5 141 Google Scholar
[8]	Ren J, Lu X S, Lin C G, Jain R K 2020 Opt. Express 28 21522 Google Scholar
[9]	Wang R P, Bulla D, Smith A, Wang T, Luther-Davies B 2011 J. Appl. Phys. 109 023517 Google Scholar
[10]	Lin H T, Song Y, Huang Y Z, Kita D, Deckoff-Jones S, Wang K Q, Li L, Li J Y, Zheng H Y, Luo Z Q, Wang H Z, Novak S, Yadav A, Huang C C, Shiue R J, Englund D, Gu T, Hewak D, Richardson K, Kong J, Hu J J 2017 Nat. Photonics 11 798 Google Scholar
[11]	Wang L L, Zeng J H, Zhu L, Yang D D, Zhang Q, Zhang P Q, Wang X S, Dai S X 2018 Appl. Opt. 57 10044 Google Scholar
[12]	田康振, 胡永胜, 任和, 祁思胜, 杨安平, 冯宪, 杨志勇 2021 物理学报 70 047801 Google Scholar Tian K Z, Hu Y S, Ren H, Qi S S, Yang A P, Feng X, Yang Z Y 2021 Acta Phys. Sin. 70 047801 Google Scholar
[13]	Choi D Y, Madden S, Rode A, Wang R P, Luther-Davies B 2007 Appl. Phys. Lett. 91 011115 Google Scholar
[14]	Wang T, Gai X, Wei W H, Wang R P, Yang Z Y, Shen X, Madden S, Luther-Davies B 2014 Opt. Mater. Express 4 1011 Google Scholar
[15]	Wang T, Gulbiten O, Wang R P, Yang Z Y, Smith A, Luther-Davies B, Lucas P 2014 J. Phys. Chem. B 118 1436 Google Scholar
[16]	Wang R P, Yan K L, Yang Z Y, Luther-Davies B 2015 J. Non-Cryst. Solids 427 16 Google Scholar
[17]	Kotsalas I P, Papadimitriou D, Raptis C, Vlcek M, Frumar M 1998 J. Non-Cryst. Solids 226 85 Google Scholar
[18]	Wang R P, Smith A, Luther-Davies B, Kokkonen H, Jackson I 2009 J. Appl. Phys. 105 056109 Google Scholar
[19]	Cernosek Z, Cernoskova E, Todorov R, Holubova J 2020 J. Solid State Chem. 291 121599 Google Scholar
[20]	Wang R P, Smith A, Prasad A, Choi D Y, Luther-Davies B 2009 J. Appl. Phys. 106 043520 Google Scholar
[21]	Yang G, Bureau B, Rouxel T, Gueguen Y, Gulbiten O, Roiland C, Soignard E, Yarger J L, Troles J, Sangleboeuf J C, Lucas P 2010 Phys. Rev. B 82 195206 Google Scholar
[22]	徐航, 彭雪峰, 戴世勋, 徐栋, 张培晴, 许银生, 李杏, 聂秋华 2016 物理学报 65 154207 Google Scholar Xu H, Peng X F, Dai S X, Xu D, Zhang P Q, Xu Y S, Li X, Nie Q H 2016 Acta Phys. Sin. 65 154207 Google Scholar
[23]	Jackson K, Briley A, Grossman S, Porezag D V, Pederson M R 1999 Phys. Rev. B 60 14985 Google Scholar
[24]	Mei Q, Saienga J, Schrooten J, Meyer B, Martin S W 2003 J. Non-Cryst. Solids 324 264 Google Scholar
[25]	Zhang Y, Xu Y S, You C Y, Xu D, Tang J Z, Zhang P Q, Dai S X 2017 Opt. Express 25 8886 Google Scholar
[26]	Frumarova B, Nemec P, Frumar M, Oswald J, Vlcek M 1999 J. Non-Cryst. Solids 256-257 266 Google Scholar
[27]	Kotsalas I P, Papadimitriou D, Raptis C, Vlcek M, Frumar M 1998 Journal of Non-Cryst. Solids 226 85
[28]	Rana A, Singh B P, Sharma R 2019 J. Non-Cryst. Solids 523 119597 Google Scholar
[29]	Musgraves J D, Wachtel P, Gleason B, Richardson K 2014 J. Non-Cryst. Solids 386 61 Google Scholar
[30]	Nefedov V I 1988 X-Ray Photoelectron Spectroscopy of Solid Surfaces (Boca Raton: CRC Press) pp97−128
[31]	Wang R P, Choi D Y, Rode A V, Madden S J, Luther-Davies B 2007 J. Appl. Phys. 101 113517 Google Scholar
[32]	Xu S W, Wang R P, Luther-Davies B, Kovalskiy A, Miller A C, Jain H 2014 J. Appl. Phys. 115 083518 Google Scholar
[33]	Luo Y R 2007 Comprehensive Handbook of Chemical Bond Energies (Boca Raton: CRC Press) pp431−488
[34]	Kovalskiy A, Jain H, Miller A C, Golovchak R Y, Shpotyuk O I 2006 J. Phys. Chem. B 110 22930 Google Scholar
[35]	Opletal G, Drumm D W, Wang R P, Russo S P 2014 J. Phys. Chem. A 118 4790 Google Scholar
[36]	Li Q L, Wang R P, Xu F, Wang X S, Yang Z Y, Gai X 2020 Opt. Mater. Express 10 1413 Google Scholar
[37]	Lu X S, Li J H, Yang L, Zhang R N, Zhang Y D, Ren J, Galca A C, Secu M, Farrell G, Wang P F 2020 J. Non-Cryst. Solids 528 119757 Google Scholar

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S取代Se对Ge_11.5As₂₄Se_64.5–xS_x玻璃结构及光学性质的影响