NH3/HTMS气相法改性SiO2增透膜的耐环境稳定性

doi:10.15541/jim20180033

无机材料学报 ›› 2018, Vol. 33 ›› Issue (11): 1219-1224.DOI: 10.15541/jim20180033 CSTR: 32189.14.10.15541/jim20180033

NH₃/HTMS气相法改性SiO₂增透膜的耐环境稳定性

赵慧月¹, 王晓栋¹, 冯建斌², 刘源², 黄吉辰², 沈军¹

1. 同济大学物理科学与工程学院, 上海市特殊人工微结构材料与技术重点实验室, 上海 200092;
2. 上海理工大学理学院, 上海 200093

收稿日期:2018-01-29 修回日期:2018-04-10 出版日期:2018-11-16 网络出版日期:2018-10-20
作者简介:赵慧月(1994-), 女, 硕士研究生. E-mail: huiyuezhao@foxmail.com
基金资助:
国家重点研发计划“纳米科技”重点专项(2017YFA0204600);国家自然科学基金(11874288);上海市教育发展基金会和上海市教育委员会“晨光计划”(14CG19);中央高校基本科研业务专项资金

Environmental Stable SiO₂Antireflective Coating Modified via NH₃/HTMS Vapor Phase Treatment

ZHAO Hui-Yue¹, WANG Xiao-Dong¹, FENG Jian-Bin², LIU Yuan², HUANG Ji-Chen², SHEN Jun¹

1. Shanghai Key Laboratory of Special Artificial Microstructure Materials and Technology, School of Physics Science and Engineering, Tongji University, Shanghai 200092, China;
2. College of Science, University of Shanghai for Science and Technology, Shanghai 200093, China

Received:2018-01-29 Revised:2018-04-10 Published:2018-11-16 Online:2018-10-20
About author:ZHAO Hui-Yue. E-mail: huiyuezhao@foxmail.com
Supported by:
National Key Research and Development Program of China (2017YFA0204600);National Natural Science Foundation of China (11874288);“Chen Guang” Project Supported by Shanghai Municipal Education Commission and Shanghai Education Development Foundation (14CG19);Fundamental Research Funds for the Central Universities

摘要/Abstract

摘要：

溶胶-凝胶法制备的二氧化硅增透膜因具有极低的折射率与较高的激光损伤阈值而被广泛应用于高功率激光系统中。但是, 激光系统工作环境中的水汽及挥发性有机污染物极易污染薄膜。本研究以正硅酸四乙酯为前驱体, 氨水为催化剂, 乙醇为溶剂制备了碱性催化的单分散SiO₂溶胶。采用提拉法在BK7玻璃基板表面镀制了SiO₂薄膜, 并对薄膜进行氨水气氛以及HTMS气氛联合处理改性。改性后的薄膜表现出了极佳的耐环境稳定性, 在高湿环境下放置2个月后膜层峰值透过率仅下降0.03%, 在低真空二甲基硅油污染环境下放置2个月后透过率光谱几乎无变化。NH₃/HTMS气相法联合处理可以有效延长SiO₂增透膜在高功率激光系统中的工作寿命。

关键词: 溶胶-凝胶, 耐环境稳定性, 增透膜, 气氛处理

Abstract:

Sol-Gel derived silica antireflective coatings have been widely used in high power laser system because of their ultra-low refractive index and high laser damage threshold. However, water vapor and volatile organic compounds in the laser system contaminate these coatings and reduce their antireflective efficiency and laser damage resistance. In this work, environmental stable SiO₂ antireflective coating was prepared by vapor phase treatment of ammonia and HTMS. Monodisperse colloidal silica sol was synthesized by Sol-Gel method using tetraethylorthosilicate (TEOS) as precursor, ammonia as catalyst, and ethanol as solvent. The silica coatings were then deposited on the BK7 glass using dip-coating method. Ammonia vapor phase treatment and HTMS vapor phase treatment were combined to improve the environmental stability of the antireflective coating. The peak transmittance of the BK7 glass coated with the modified coating decreased only 0.03% after being exposed in the humid environment for 2 m. Meanwhile, the transmittance curve of the BK7 glass coated with modified coating had almost no change after being placed under low vacuum condition with oil pollutants for 2 m, indicating that the coating modified via combined vapor phase treatment of ammonia and HTMS possessed an excellent environmental stable performance. Therefore, the combination of ammonia and HTMS vapor phase treatment is effective to improve the working life of SiO₂ antireflective coating in high power laser system.

Key words: Sol-Gel, environmental stability, antireflective coating, vapor phase treatment

中图分类号:

O484

赵慧月, 王晓栋, 冯建斌, 刘源, 黄吉辰, 沈军. NH₃/HTMS气相法改性SiO₂增透膜的耐环境稳定性[J]. 无机材料学报, 2018, 33(11): 1219-1224.

ZHAO Hui-Yue, WANG Xiao-Dong, FENG Jian-Bin, LIU Yuan, HUANG Ji-Chen, SHEN Jun. Environmental Stable SiO₂Antireflective Coating Modified via NH₃/HTMS Vapor Phase Treatment[J]. Journal of Inorganic Materials, 2018, 33(11): 1219-1224.

图/表 6

图1 二氧化硅薄膜的氨水(a)和HTMS(b)气氛处理示意图

Fig. 1 Diagram of SiO2 coating modified via (a) ammonia vapor phase treatment and (b) HTMS vapor phase treatment

图2 二氧化硅薄膜的氨水(a)和HTMS(b)气氛处理原理示意图

Fig. 2 Schematic diagram of SiO2 coating modified via (a) ammonia vapor phase treatment and (b) HTMS vapor phase treatment

图3 未经气氛处理(Base-SiO2)、氨水气氛处理6 h(NH3-6h-SiO2)以及NH3/HTMS气氛联合处理(NH3-6h-HTMS-12h-SiO2)的薄膜样品红外光谱图

Fig. 3 FT-IR spectra of unmodified SiO2 coating (Base-SiO2), SiO2 coating modified via ammonia vapor phase treatment (NH3-6h-SiO2) and NH3/HTMS vapor phase treatment (NH3-6h-HTMS-12h-SiO2)

图4 未经气氛处理(a)、氨水气氛处理6 h(b)以及NH3/HTMS气氛联合处理(c)的薄膜样品SEM表面与截面照片

Fig. 4 SEM surface and cross-section images of unmodified SiO2 coating (a), SiO2 coating modified via ammonia vapor phase treatment (b) and NH3/HTMS vapor phase treatment (c)

图5 未经气氛处理(Base-SiO2)、氨水气氛处理6 h(NH3-6h-SiO2)以及经过NH3和HTMS气氛联合处理的薄膜样品(NH3-6h-HTMS-12h-SiO2)的透过率光谱图(a)及其折射率光谱图(b)

Fig. 5 (a) Transmittance spectra and (b) refractive index spectra of unmodified SiO2 coating (Base-SiO2), SiO2 coating modified via ammonia vapor phase treatment (NH3-6h-SiO2) and NH3/HTMS vapor phase treatment (NH3-6h-HTMS-12h-SiO2)

图6 潮湿环境下(a)未经处理的和(b)NH3/HTMS气氛联合处理的二氧化硅薄膜透过率光谱图; 低真空二甲基硅油环境下(c)未处理的和(d) NH3/HTMS气氛联合处理的二氧化硅薄膜透过率光谱图

Fig. 6 Transmittance spectra of (a) unmodified SiO2 coating and (b) SiO2 coating modified via NH3/HTMS vapor phase treatment after being exposed in the humid environment; Transmittance spectra of (c) unmodified SiO2 coating and (d) SiO2 coating modified via NH3/HTMS vapor phase treatment after being placed under low vacuum condition with oil pollutants

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NH₃/HTMS气相法改性SiO₂增透膜的耐环境稳定性

Environmental Stable SiO₂Antireflective Coating Modified via NH₃/HTMS Vapor Phase Treatment

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