疏水耐环境型SiO2/TiO2/SiO2-TiO2太阳能宽光谱增透膜的制备及性能研究

doi:10.15541/jim20150264

无机材料学报 ›› 2016, Vol. 31 ›› Issue (4): 365-371.DOI: 10.15541/jim20150264 CSTR: 32189.14.10.15541/jim20150264

疏水耐环境型SiO₂/TiO₂/SiO₂-TiO₂太阳能宽光谱增透膜的制备及性能研究

檀满林¹, 张礼杰^{1, 2}, 王晓伟¹, 马清¹, 符冬菊¹, 张维丽¹, 李冬霜¹, 陈建军¹, 张化宇²

(1. 深圳清华大学研究院, 深圳518057; 2. 哈尔滨工业大学深圳研究生院, 深圳518055)

收稿日期:2015-06-04 修回日期:2015-08-31 出版日期:2016-04-20 网络出版日期:2016-03-25
基金资助:
深圳市科技计划项目(CXZZ20150323160924557);广东省科技计划项目(2014A010106004);国家自然科学基金(51302150)

Hydrophobic and Environment-resistant Properties of SiO₂/TiO₂/SiO₂-TiO₂ Multilayer Antireflective Films in Wide Solar Spectra Range

TAN Man-Lin¹, ZHANG Li-Jie^1,2, WANG Xiao-Wei¹, MA Qing¹, FU Dong-Ju¹, ZHANG Wei-Li¹, LI Dong-Shuang¹, CHEN Jian-Jun¹, ZHANG Hua-Yu²

(1. Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057, China; 2. Harbin Institute of Technology Shenzhen Graduate School, Shenzhen 518055, China)

Received:2015-06-04 Revised:2015-08-31 Published:2016-04-20 Online:2016-03-25
Supported by:
Shenzhen Science and Technology Plan (CXZZ20150323160924557);Science and Technology Planning Projecf of Guangdong Province, China (2014A010106004);Natinal Natural Science Foundation of China (51302150)

摘要/Abstract

摘要：

利用TFCcal设计软件构建膜系结构, 采用溶胶-凝胶工艺和提拉法在超白玻璃上制备出厚度精确可控的宽光谱、高增透型SiO₂/TiO₂/SiO₂-TiO₂减反膜, 同时结合甲基三乙氧基硅烷(MTES)改性碱催化的SiO₂溶胶, 通过提拉法一次制备出高透过率疏水型薄膜。研究表明, 高增透型三层宽光谱减反膜的理论膜层厚度依次为: 80.9 nm(内层SiO₂-TiO₂)、125.0 nm(中间层TiO₂)、95.5 nm(外层SiO₂), 其在400~700 nm可见光范围内平均透过率实际可高达97.03%以上。多层膜经过退火处理后, 膜面的水接触角高达131.5°, 同时陈化两个月以后的多层膜透过率仅下降0.143%, 表明制备的SiO₂/TiO₂/ SiO₂-TiO₂多层减反膜具有优良的疏水和耐环境性能。

关键词: 增透膜, 疏水型, 耐环境, 宽光谱

Abstract:

In the help of coatings optimization design using TFCcal program, wide spectrum antireflective SiO₂/ TiO₂/SiO₂-TiO₂multilayer films with thickness precisely controlled were prepared on low iron glass using sol gel process and Czochralski method. The thickness of above layers were separately set as 80.9 nm (SiO₂-TiO₂, inner layer), 125.0 nm (TiO₂, inter-layer) and 95.5 nm (SiO₂, outer layer) according to the results of calculation. A high transmission and highly hydrophobic film was prepared by Czochralski method combined with methyl triethoxysilane (MTES) SiO₂ modified base-catalyzed sol. The average optical transmittance could reach 97.03% in the wavelength range of 400-700 nm. After annealing treatment, the surface water contact angles were almost around 131.5°. Furthermore, the optical transmittance only reduced 0.143% after aging for two months, showing that the prepared SiO₂/TiO₂/SiO₂-TiO₂ multilayer antireflective films had excellent hydrophobic and environment resistant properties.

Key words: antireflective films, hydrophobic, environment resistant, wide spectrum

中图分类号:

TB321

檀满林, 张礼杰, 王晓伟, 马清, 符冬菊, 张维丽, 李冬霜, 陈建军, 张化宇. 疏水耐环境型SiO₂/TiO₂/SiO₂-TiO₂太阳能宽光谱增透膜的制备及性能研究[J]. 无机材料学报, 2016, 31(4): 365-371.

TAN Man-Lin, ZHANG Li-Jie, WANG Xiao-Wei, MA Qing, FU Dong-Ju, ZHANG Wei-Li, LI Dong-Shuang, CHEN Jian-Jun, ZHANG Hua-Yu. Hydrophobic and Environment-resistant Properties of SiO₂/TiO₂/SiO₂-TiO₂ Multilayer Antireflective Films in Wide Solar Spectra Range[J]. Journal of Inorganic Materials, 2016, 31(4): 365-371.

图/表 11

表1 膜层理论结构参数

Table 1 Calculated parameters of optimized multilayer antireflective film

Refractive index		Layer thickness／nm
Glass	1.52	-
SiO₂-TiO₂	1.71	80.5
TiO₂	2.20	125.0
SiO₂	1.44	95.5

图1 三层减反射膜理论反射率曲线

Fig. 1 Calculated reflectivity curve of triple-layer antireflective film

图2 TiO2含量对TiO2-SiO2薄膜折射率的影响

Fig. 2 Effect of TiO2 content on the refractive index of TiO2-SiO2 film

图3 TiO2层不同提拉速度制备的三层膜透过率

Fig. 3 Transmittance of triple-layer antireflective film with TiO2 layer prepared at different pulling rates (a) 380 mm/min; (b) 400 mm/min; (c) 420 mm/min; (d) 440 mm/min; (e) 460 mm/min; (f) 480 mm/min

图4 SiO2层不同提拉速度制备的三层膜的透过率

Fig. 4 Transmittances of triple-layer antireflective films with SiO2 layer prepared at different pulling rates (a) 380 mm/min; (b) 400 mm/min; (c) 420 mm/min; (d) 440 mm/min; (e) 460 mm/min; (f) 480 mm/min

表2 SiO2/TiO2/ SiO2-TiO2三层减反射膜理论和实验参数

Table 2 Calculated and experimental parameters of SiO2/TiO2/ SiO2-TiO2 triple-layer antireflective film

	Calculated		Experimental
	Refractive index	Layer thickness/nm	Refractive index	Layer thickness/nm	Pulling rate/ (nm·min^-1)
Glass	1.52	—	1.52	—	—
SiO₂-TiO₂	1.70	80.9	1.70	72	190
TiO₂	2.20	125.0	2.20	127	420
SiO₂	1.44	95.5	1.44	96	190

图5 最佳工艺参数下三层膜透过率曲线

Fig. 5 Transmittance curve of triple-layer antireflective film with optimized process parameters

图6 SiO2/TiO2/SiO2-TiO2多层膜截面SEM照片

Fig. 6 Sectional image of SiO2/TiO2/SiO2-TiO2 multiplayer antireflective film

图7 不同MTES掺杂比制备的SiO2薄膜表面接触角的影响

Fig. 7 Surface water contact angles of SiO2 films prepared with different MTES doping ratios

图8 不同MTES掺杂比制备的SiO2薄膜红外光谱

Fig. 8 Infrared spectra of SiO2 films prepared with different MTES doping ratios (a) 0; (b) 10mol%; (c) 20mol%; (d) 30mol%; (e) 40mol%; (f) 50mol%

图9 超白玻璃与三层疏水膜耐候性测试前后透射率曲线

Fig. 9 Transmittances of low-ion glass and triple-layer antireflective films after environment resistant test a1) glass, a2) glass without cleaning, a3) glass after cleaning, b1) triple-layer film, b2) triple-layer film without cleaning, b3) triple-layer film after cleaning

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疏水耐环境型SiO₂/TiO₂/SiO₂-TiO₂太阳能宽光谱增透膜的制备及性能研究

Hydrophobic and Environment-resistant Properties of SiO₂/TiO₂/SiO₂-TiO₂ Multilayer Antireflective Films in Wide Solar Spectra Range

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