含Si-O-P键的减反膜结构及性能影响因素研究

doi:10.3724/SP.J.1077.2014.13416

摘要/Abstract

摘要：

采用SiO₂水溶胶(ACS)为硅源, H₃PO₄为桥联剂, H₂O₂为活化剂在玻璃表面成功制备了一种性能优异的新型减反膜。利用FTIR、XRD、FESEM、TEM、AFM对薄膜结构、形成机理及性能进行了研究, 结果表明, 在成胶过程中, H₂O₂的导入有效修复了SiO₂胶粒的表面羟基, 提高了SiO₂的反应活性; 而在焙烧过程中, H₃PO₄通过其自身脱水形成的偏磷酸链状体分别与SiO₂胶粒及玻璃基底表面的Si-OH进行了脱羟基缩聚, 构架了坚固的Si-O-P网络交联, 最终形成了稳定的磷硅酸盐凝胶网络结构, 提高了成膜质量。当n(H₃PO₄) : n(H₂O₂) : n(EtOH) : n(SiO₂)= 0.49: 0.52: 30: 1时, 制备的SiO₂减反膜在可见光区平均透光率高达98%, 硬度可达6H。

关键词: SiO₂水溶胶, 磷酸, 双氧水, Si-O-P桥键, 减反膜

Abstract:

An antireflective (AR) film was successfully prepared by dip-coating on silica glass substrate. During the preparation, aqueous colloidal silica (ACS) was used as silica source, orthophosphoric acid as adhesion promoting agent and hydrogen peroxide as activating agent. The structure, formation mechanism and performance of the film were investigated by FTIR, XRD, FESEM, TEM and AFM. The hydrogen peroxide in silica sol repairs the surface Si-O^- bonds of colloidal silica particles greatly. As a result, their stabilities and reaction activities are improved. During the heat-treatment of the film, the orthophosphoric acid is firstly transformed into the chain of metaphosphoric acid and subsequently reacted with surface Si-OH from colloidal silica particles and the substrate, resulting in the formation of the numerous Si-O-P cross-linkings and the stable silicophosphate gel structure. When molar ratio of H₃PO₄: H₂O₂: EtOH: SiO₂ is 0.49: 0.52: 30: 1, the average transmittance of the film in the visible light is 98%, and the pencil hardness grade reaches 6H.

Key words: aqueous colloidal silica, orthophosphoric acid, hydrogen peroxide, Si-O-P bonds, antireflective films

中图分类号:

TB34

王燕, 王红宁, 陈若愚. 含Si-O-P键的减反膜结构及性能影响因素研究[J]. 无机材料学报, 2014, 29(6): 639-644.

WANG Yan, WANG Hong-Ning, CHEN Ruo-Yu. Structure of Antireflective Films with Si-O-P Bonds and Impact Factors on Its Performance[J]. Journal of Inorganic Materials, 2014, 29(6): 639-644.

图/表 8

图1 在n(H2O2)﹕n(EtOH)﹕n(SiO2)=0.52﹕30﹕1), n(H3PO4/SiO2)分别为: (a) 0.98, (b) 0.49, (c) 0比例制备的SiO2凝胶的红外光谱图(A)和XRD图谱(B)

Fig. 1 FTIR spectra (A) and XRD patterns (B) of the SiO2 gels with different n(H3PO4/SiO2)(A) a-0, b-0.49, c-0.98; (B) a-0.49, b-0.98

图2 SiO2减反膜形成机理示意图

Fig. 2 Schematic illustration of the formation mechanism for SiO2 antireflective film

表1 在n(H2O2)﹕n(EtOH)﹕n(SiO2)=0.52﹕30﹕1, 以下同n(H3PO4/SiO2)比例制备SiO2凝胶的比表面积和Si-OH含量以及相应SiO2薄膜的铅笔硬度

Table 1 SBET and the Si-OH content of the SiO2 gels with different n(H3PO4)﹕n(H2O2)﹕n(EtOH)﹕n(SiO2)= 0.52﹕30﹕1) and pencil hardness grades of the corresponding SiO2 films

n(H₃PO₄/SiO₂)	0	0.16	0.33	0.49	0.65	0.82	0.98
S_BET/(m²•g^-1)	230.5	76.3	59.6	38.7	21.6	2.1	/
Si-OH content/(bonds•nm^-2)	10.2	7.8	5.6	4.3	3.1	2.3	/
Pencil hardness grade	5B	F	3H	6H	4H	3H	H

图3 在n(H2O2):n(EtOH):n(SiO2)=0.52:30:1, 以下同n(H3PO4/ SiO2)比例制备的SiO2薄膜在可见光区域的平均透光率

Fig. 3 Average transmittance in the visible light of the SiO2 films with different n(H3PO4/SiO2) (n(H2O2/EtOH/SiO2)= 0.52: 30: 1)

图4 经不同修饰比例(n(H2O2/SiO2))改性后的ACS中SiO2胶粒表面的Si-OH含量

Fig. 4 Si-OH content of the SiO2 particles in modified ACS with different n(H2O2/SiO2)

表2 在n(H2O2)﹕n(EtOH)﹕n(SiO2) = 0.49: 30: 1, 以下同n(H3PO4/SiO2)比例制备的SiO2薄膜的硬度及在可见光区的平均透光率

Table 2 Pencil hardness grades and the average transmittance in the visible light of the SiO2 films with different n(H2O2/SiO2) (n(H3PO4/EtOH/SiO2)= 0.49: 30: 1)

n(H₂O₂/SiO₂)	0	0.26	0.39	0.52	0.64	0.77	0.90	1.03
Pencil hardness grade	F	3H	3H	6H	6H	5H	5H	5H
Average transmittance/%	98.0	97.7	98.0	98.0	97.6	97.9	97.8	98.0

图5 SiO2薄膜的表面FESEM照片(a)、横截面FESEM照片(b)、TEM照片(c)和AFM照片(d)

Fig. 5 Surface FESEM (a), cross-sectional FESEM (b), TEM (c) and AFM (d) images of the SiO2 film

图6 SiO2薄膜在可见光区的平均透光率随陈放时间的变化

Fig. 6 Variations of average transmittance in the visible light of SiO2 films with exposure time

参考文献 30

[1]	FURBO S, SHAH L J. Thermal advantages for solar heating systems with a glass cover with antireflection surfaces. Sol. Energy, 2003, 74(6): 513-523.
[2]	ZHANG QIAN, JI RUO-NAN, ZHANG LIANG, et al. Synthesis and properties research of antireflection film for solar cells. Chemical Industry and Engineering Progress, 2012, 31(Sppl.): 347-349.
[3]	NOSTELL P, ROOS A, KARLSSON B. Optical and mechanical properties of Sol-Gel antireflective films for solar energy applications. Thin Solid Films, 1999, 351(1): 170-175.
[4]	WANG QUAN-ZHI, JING XI-LI, MA YI-HENG, et al. Refractive indexes distribution of anti-reflection coatings for high efficiency silicon solar cells. Laser and Infrared, 2011, 41(6): 669-672.
[5]	BAUTISTA M C, MORALES A. Silica antireflective films on glass produced by the Sol-Gel method.. Sol. Energy Mater. Sol.Cells, 2003, 80(2): 217-225.
[6]	BELLEVILLE P F, PRENÉ P, MENNECHEZ F, et al. Sol-Gel antireflective spin-coating process for large-size shielding windows. International symposium on optical science and technology .International Society for Optics and Photonics, 2002, 4804: 69-72.
[7]	RAUT H K, NAIR A S, DINACHALI S S, et al. Porous SiO2 anti-reflective coatings on large-area substrates by electrospinning and their application to solar modules. Sol. Energy Mater. Sol. Cells, 2013, 111: 9-15.
[8]	SHEN JUN, LIU YUAN, LI XIAO-GUANG. Surface modification and contamination resistance of Sol-Gel SiO2 derived. Journal of the Chinese Ceramic Society, 2010, 38(11): 2054-2058.
[9]	MAI X D, JUNE K L, WOO-SIK S, et al. Ultralow-n SiO2 Thin films synthesized using organic nanoparticles template.Bull. Korean Chem. Soc, 2010, 31(12): 3593-3599.
[10]	ZHAO Q N, LIU Y, HOU S H, et al. Preparation and characterization of nano-porous SiO2/TiO2-SiO2 thin films on glass substrates by Sol-Gel method. Key Eng. Mater. , 2013, 531: 651-654.
[11]	XU Y D, PENG CH, XIN CH F, et al. Preparation of silica antireflective films for solar energy application .Mater. Lett, 2013, 94(1): 89-91.
[12]	CHI F T, YAN L H, LV H B, et al. Novel pathways for the preparation of silica antireflective films: improvement in mechanical property. Mater. Lett , 2011, 65: 1095-1097.
[13]	WANG JIAN-WU, BAI YU-CHEN, YAO WEI, et al. Preparation and investigation of SiO2/TiO2 antireflective coatings with self- cle-an--ing and scratch-resistant Properties. Journal of Inorganic Materials, 2011, 26(7): 769-773.
[14]	LI X G, SHEN J. A scratch-resistant and hydrophobic broadband antireflective coating by Sol-Gel method. Thin Solid Films, 2011, 519: 6236-6240.
[15]	WU G M, WANG J, SHEN J, et al. Properties of Sol-Gel derived scratch-resistant nano-porous silica films by a mixed atmosphere treatment. J. Non-Cryst Solids, 2000, 275(3): 169-174.
[16]	WANG J, WU G M, SHEN J, et al. Scratch-resistant improvement of Sol-Gel derived nano-porous silica films. J. Sol-Gel Sci. Technol, 2000, 18: 219-224.
[17]	YE H P, ZHANG X X, ZHANG Y L, et al. Preparation of antireflective coatings with high transmittance and enhanced abrasion- resistance by a base/acid two-step catalyzed Sol-Gel process. Sol. Energy Mater. Sol. Cells, 2011, 95: 2347-2351.
[18]	KOZUKA H, YAMANO A, FUJITA M, et al. Aqueous dip-coating route to dense and porous silica thin films using silica nanocolloids with an aid of polyvinylpyrrolidone. J. Sol-Gel Sci. Technol, 2012, 61: 381-389.
[19]	ZHU JIAN-JUN, YAO JING, LV XIAO-MENG, et al. Synthesis and characterization of superhydrophobic mesoporous silica aerogels by ambient pressure drying .Journal of the Chinese Ceramic Society, 2009, 37(4): 512-515.
[20]	NISHIYAMA N, KAIHARA J, NISHIYAMA Y, et al. Vapor-phase synthesis of mesoporous SiO2-P2O5 thin films. Langmuir, 2007, 23: 4746-4748.
[21]	DAYANAND C, BHIKSHAMAIAH G, JAYA TYAGARAJU V, et al. Review structural investigations of phosphate glasses: a detailed infrared study of the x(PbO)-(1-x)P2O5 vitreous system .J. Mater. Sci, 1996, 31:1945-1967.
[22]	CUI SH, LIU Y, FAN M H, et al. Temperature dependent microstructure of MTES modified hydrophobic .Mater. Lett , 2011, 65: 606-609.
[23]	SALAME I I, BANDOSZ T J. Surface chemistry of activated carbons: combining the results of temperature-programmed desorption, boehm, and potentiometric titrations .J. Colloid Interf. Sci, 2001, 240: 252-258.
[24]	BOEHM H P. Some aspects of the surface chemistry of carbon blacks and other carbons. Carbon, 1994, 32(5): 759-769.
[25]	BOEHM H P. Chemical identification of surface groups. Adv.in Catal., 1966, 16: 179-274.
[26]	OUYANG ZHAO-HUI, WU LIN, LI KONG-BIAO, et al. Surface modification of nano-SiO2 in gas phase. Chemical Industry and Engineering Progress, 2005, 24(11): 1265-1268.
[27]	ISO 15184: 1998, Paints and varnishes: determination of film hardness by pencil test.. ISO, 1998.
[28]	CHEN ZH, WU L Y L, CHWA E, et al. Scratch resistance of brittle thin films on compliant substrates. Mater. Sci. Eng. A, 2008, 493: 292-298.
[29]	DAPUZZO M, ARONNE A, ESPOSITO S, et al. Sol-Gel synthesis of humidity-sensitive P2O5-SiO2 amorphous films .J. Sol-Gel Sci. Technol, 2000, 17: 247-254.
[30]	DUAN XIANG, WANG DE-PING, YAO AI-HUA, et al. Fabrication of hydroxyapatite with three-dimensional pore frame by colloidal template method. Journal of Inorganic Materials, 2009, 24(1): 161-165.