CN1084481C - Process for preparing zirconium oxide-silicon oxide film with high resistance to laser damage and high reflectivity - Google Patents
Process for preparing zirconium oxide-silicon oxide film with high resistance to laser damage and high reflectivity Download PDFInfo
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- 238000002310 reflectometry Methods 0.000 title description 5
- 238000004519 manufacturing process Methods 0.000 title description 2
- AXFLWPUWMOTLEY-UHFFFAOYSA-N oxosilicon(2+) oxygen(2-) zirconium(4+) Chemical compound [Si+2]=O.[O-2].[Zr+4].[O-2].[O-2] AXFLWPUWMOTLEY-UHFFFAOYSA-N 0.000 title 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 40
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011521 glass Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 230000005499 meniscus Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 230000002431 foraging effect Effects 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000007747 plating Methods 0.000 abstract description 2
- 229910004298 SiO 2 Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 15
- 230000003287 optical effect Effects 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- AGMNAIOLVWYHRE-UHFFFAOYSA-N [O-2].[Th+4].[Si+2]=O.[O-2].[O-2] Chemical compound [O-2].[Th+4].[Si+2]=O.[O-2].[O-2] AGMNAIOLVWYHRE-UHFFFAOYSA-N 0.000 description 1
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- FMLYSTGQBVZCGN-UHFFFAOYSA-N oxosilicon(2+) oxygen(2-) titanium(4+) Chemical compound [O-2].[Ti+4].[Si+2]=O.[O-2].[O-2] FMLYSTGQBVZCGN-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Surface Treatment Of Glass (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
一种氧化锆/氧化硅系高抗激光损伤高反膜的制备方法，在玻璃基底上用化学镀膜法交替制备数层氧化锆(ZrO2)和氧化硅(SiO2)膜层。氧化锆(ZrO2)溶胶镀膜液制备方法为：以正丙醇锆Zr(O-nC3H7)4为前驱体，在碱性或中性催化条件下，加入一定量的二甘醇(DEG)，搅拌均匀后，按一定比例加入水和无水乙醇，混合后充分搅拌，然后装入密闭容器中在适当的温度下进行陈化。本发明制备过程简单、方便，膜层达到高反所需的层数减少，膜层的耐激光损伤阈值在5～25J/cm2(1064nm，3ns)。The invention relates to a preparation method of a zirconia/silicon oxide system highly resistant to laser damage and high reflection. Several layers of zirconia (ZrO 2 ) and silicon oxide (SiO 2 ) film layers are alternately prepared on a glass substrate by chemical plating. The preparation method of zirconia (ZrO 2 ) sol coating solution is as follows: using zirconium n-propoxide Zr(O-nC 3 H 7 ) 4 as a precursor, adding a certain amount of diethylene glycol ( DEG), after stirring evenly, add water and absolute ethanol in a certain proportion, mix and stir thoroughly, then put it into a closed container and age it at an appropriate temperature. The preparation process of the invention is simple and convenient, the number of layers required for the film layer to achieve high reflection is reduced, and the laser damage resistance threshold of the film layer is 5-25J/cm 2 (1064nm, 3ns).
Description
本发明属于一种高反膜的制备方法，具体地说涉及一种氧化锆/氧化硅系高抗激光损伤高反膜的制备方法。The invention belongs to a preparation method of a high-reflection film, in particular to a preparation method of a zirconia/silicon oxide system highly resistant to laser damage and a high-reflection film.
制作高反膜通常采用物理真空镀膜和溶胶—凝胶化学镀膜。The production of high reflection film usually adopts physical vacuum coating and sol-gel chemical coating.
物理真空镀膜是将无机材料在真空室中高温蒸发，然后在电场的作用下沉积到玻璃基片上形成镀层，因其设备复杂、造价昂贵，所镀膜层不够均匀、不易控制膜层的微观结构，以及抗激光损伤阈值不高等难以克服的缺点，实际应用受到限制。Physical vacuum coating is to evaporate inorganic materials at high temperature in a vacuum chamber, and then deposit them on a glass substrate under the action of an electric field to form a coating. Because of the complexity of the equipment and high cost, the coating layer is not uniform enough and it is difficult to control the microstructure of the film layer. And the insurmountable shortcomings such as the low laser damage threshold, the practical application is limited.
溶胶—凝胶法化学镀膜是用预先配制好的胶体，通过旋转、提拉或弯液面镀膜等过程获得膜层。研究人员(国际光学工程会议文集Vol.2114，232；Vol.2253，764)选用几种不同的物质作为高折射率材料，氧化硅作为低折射率材料，用溶胶—凝胶法制备了高反膜。其中氧化钍—氧化硅在光学性能和损伤阈值两方面都能满足要求，但不安全；氧化钛—氧化硅体系给出良好的光学性能，但是没有高的损伤阈值；氧化铝—氧化硅体系可以满足损伤阈值的要求，但是氧化铝的折射率只有1.44，与氧化硅折射率1.22相比不算太大，要达到较好的光学性能则需要镀很多层膜。目前研究的焦点正逐步转向氧化锆/氧化硅体系，其中氧化锆溶胶多采用无机合成方法，据文献(国际光学工程会议文集Vol.2253，764报导，其抗激光损伤阈值为8J/cm2(1064nm，3ns)，但制备过程非常繁琐、影响因素多，不易控制。采用有机氧化锆溶胶制备高反膜虽有少量报导，但没有抗激光损伤方面的应用。The sol-gel chemical coating is to use the pre-prepared colloid to obtain the film layer through the process of rotation, pulling or meniscus coating. Researchers (Proceedings of the International Conference on Optical Engineering Vol.2114, 232; Vol.2253, 764) selected several different substances as high-refractive-index materials, and silicon oxide as low-refractive-index materials. membrane. Among them, thorium oxide-silicon oxide can meet the requirements in both optical properties and damage threshold, but it is not safe; titanium oxide-silicon oxide system gives good optical properties, but does not have a high damage threshold; aluminum oxide-silicon oxide system can It meets the requirements of the damage threshold, but the refractive index of aluminum oxide is only 1.44, which is not too large compared with the refractive index of silicon oxide of 1.22. To achieve better optical performance, many layers of films need to be coated. The current research focus is gradually shifting to the zirconia/silicon oxide system, in which zirconia sol is mostly synthesized by inorganic methods. According to the literature (International Optical Engineering Conference Proceedings Vol.2253, 764 report, its resistance to laser damage threshold is 8J/cm 2 1064nm, 3ns), but the preparation process is very cumbersome, with many influencing factors, and it is not easy to control. Although there are a few reports on the preparation of high-reflection films by using organic zirconia sol, there is no application in the aspect of anti-laser damage.
本发明的发明目的是提供一种具有制备过程简单、容易控制的氧化锆/氧化硅系高抗激光损伤高反膜的制备方法。The object of the present invention is to provide a method for preparing a zirconia/silicon oxide-based high resistance to laser damage and high reflection film with a simple preparation process and easy control.
本发明的目的是这样实现的：这种膜层由玻璃基底上用化学镀膜法交替制备的数层氧化锆和氧化硅膜层组成。本方法所用氧化锆溶胶镀膜液特征在于用二甘醇控制正丙醇锆的水解，直接在有机溶剂中一步合成溶胶，另外向体系中加入一定量的聚乙烯吡咯烷酮将氧化锆孔道填充起来，不仅使膜层的折光率增大，反射效果增强，膜层达到高反所需的层数有所减少，而且，还可以使膜层的耐激光损伤阈值大大提高。The object of the present invention is achieved like this: this film layer is made up of several layers of zirconium oxide and silicon oxide film layers alternately prepared by chemical plating method on the glass substrate. The zirconia sol coating solution used in this method is characterized in that diethylene glycol is used to control the hydrolysis of zirconium n-propoxide, and the sol is directly synthesized in an organic solvent in one step, and a certain amount of polyvinylpyrrolidone is added to the system to fill the zirconia pores, not only The refractive index of the film layer is increased, the reflection effect is enhanced, the number of layers required for the film layer to achieve high reflection is reduced, and the laser damage resistance threshold of the film layer can be greatly increased.
本发明的制备方法如下：The preparation method of the present invention is as follows:
1.氧化锆溶胶镀膜液的制备：以正丙醇锆为前驱体，在碱性或中性催化条件下，加入稳定剂、高分子添加剂，搅拌均匀后，加入水和无水乙醇，混合后充分搅拌，然后装入密闭容器中在0-60℃下进行陈化15-100天；1. Preparation of zirconia sol coating solution: use zirconium n-propoxide as the precursor, add stabilizer and polymer additives under alkaline or neutral catalytic conditions, stir evenly, add water and absolute ethanol, mix Stir well, then put it into a closed container and age at 0-60°C for 15-100 days;
氧化锆溶胶的原料摩尔比为：The raw material molar ratio of zirconia sol is:
正丙醇锆∶无水乙醇∶水∶二甘醇∶聚乙烯吡咯烷酮∶氨水＝1∶86-172∶1-2.78∶0.53-2.97∶2.0×10-5-2.0×10-3∶0-0.15；Zirconium n-propoxide: absolute ethanol: water: diethylene glycol: polyvinylpyrrolidone: ammonia water=1:86-172:1-2.78:0.53-2.97:2.0×10 -5 -2.0×10 -3 :0-0.15 ;
所述的稳定剂为二甘醇，所述的高分子添加剂为聚乙烯吡咯烷酮。The stabilizer is diethylene glycol, and the polymer additive is polyvinylpyrrolidone.
2.制备氧化硅溶胶镀膜液的方法为：以正硅酸甲酯或正硅酸乙酯为前驱体，在碱性或酸性催化条件下，按一定比例加入水和无水乙醇，混和后充分搅拌，然后装入密闭容器中在适当温度下进行陈化，具体地制备方法见中国发明专利，申请号98106504.X；2. The method for preparing the silica sol coating solution is as follows: use methyl orthosilicate or ethyl orthosilicate as the precursor, under alkaline or acidic catalytic conditions, add water and absolute ethanol in a certain proportion, mix fully Stir, and then put it into a closed container for aging at an appropriate temperature. For the specific preparation method, please refer to the Chinese invention patent, application number 98106504.X;
3.高反膜的制备：在玻璃基底上采用旋转法或提拉法以及弯液面法交替制备氧化锆和氧化硅膜层；3. Preparation of high-reflection film: Alternately prepare zirconia and silicon oxide film layers on the glass substrate by rotating method or pulling method and meniscus method;
本发明与现有技术相比具有如下优点：Compared with the prior art, the present invention has the following advantages:
1.由于用二甘醇控制正丙醇锆的水解，直接在有机溶剂中一步合成溶胶所以制备过程简单方便。1. Since diethylene glycol is used to control the hydrolysis of zirconium n-propoxide, and the sol is directly synthesized in one step in an organic solvent, the preparation process is simple and convenient.
2.由于加入聚乙烯吡咯烷酮，将氧化锆孔道填充起来，不仅可以使膜层的折光率增大，反射效果增强，膜层达到高反所需的层数有所减少，而且还可以使膜层的耐激光损伤阈值大大提高，抗激光损伤阈值为：5～25J/cm2(1064nm，3ns)。2. Due to the addition of polyvinylpyrrolidone to fill the zirconia pores, not only the refractive index of the film layer can be increased, the reflection effect can be enhanced, the number of layers required for the film layer to achieve high reflection is reduced, and the film layer can also be made The laser damage resistance threshold is greatly improved, and the laser damage resistance threshold is: 5~25J/cm 2 (1064nm, 3ns).
3.原料易得，成本低。3. The raw material is easy to obtain and the cost is low.
本发明的实施例如下：Embodiments of the present invention are as follows:
实施例1Example 1
将0.01mol正丙醇锆、0.0053mol二甘醇、2.77×10-7聚乙烯吡咯烷酮(平均分子量360000)和0.86mol乙醇混合并搅拌10分钟后，再加入0.0083mol水、1.38×10-3氨水并继续搅拌1小时，然后转入聚四氟乙烯密闭容器中，在室温下陈化20天后，与氧化硅溶胶交替镀制高反膜。在1064nm处反射率≥98％，抗激光损伤阈值高于15J/cm2(1064nm，3ns)。Mix 0.01mol zirconium n-propoxide, 0.0053mol diethylene glycol, 2.77×10 -7 polyvinylpyrrolidone (average molecular weight 360000) and 0.86mol ethanol and stir for 10 minutes, then add 0.0083mol water and 1.38×10 -3 ammonia water And continue to stir for 1 hour, then transfer to a polytetrafluoroethylene airtight container, after aging at room temperature for 20 days, and alternately plate high reflection film with silica sol. The reflectivity at 1064nm is ≥98%, and the anti-laser damage threshold is higher than 15J/cm 2 (1064nm, 3ns).
实施例2Example 2
将0.01mol正丙醇锆、0.0106mol二甘醇和1.20mol乙醇混合并搅拌10分钟后，再加入0.0166mol水、1.38×10-3氨水并继续搅拌1小时，然后转入聚四氟乙烯密闭容器中，在室温下陈化12天后加入5.54×10-7聚乙烯吡咯烷酮(平均分子量360000)，待完全溶解并充分摇匀后与氧化硅溶胶交替镀制高反膜。在1064nm处反射率≥98％，抗激光损伤阈值高于15J/cm2(1064nm，3ns)。Mix 0.01mol zirconium n-propoxide, 0.0106mol diethylene glycol and 1.20mol ethanol and stir for 10 minutes, then add 0.0166mol water, 1.38×10 -3 ammonia water and continue stirring for 1 hour, then transfer to a closed polytetrafluoroethylene container After aging for 12 days at room temperature, add 5.54×10 -7 polyvinylpyrrolidone (average molecular weight: 360,000), and after it is completely dissolved and shaken well, it is alternately plated with silica sol to form a high reflection film. The reflectivity at 1064nm is ≥98%, and the anti-laser damage threshold is higher than 15J/cm 2 (1064nm, 3ns).
实施例3Example 3
将0.01mol正丙醇锆、0.0297mol二甘醇、1.00×10-6聚乙烯吡咯烷酮(平均分子量200000)和1.72mol乙醇混合并搅拌10分钟后，再加入0.0278mol水并继续搅拌1小时，然后转入聚四氟乙烯密闭容器中，在室温下陈化80天后与氧化硅溶胶交替镀制高反膜。在1064nm处反射率≥98％，抗激光损伤阈值高于15J/cm2(1064nm，3ns)。0.01mol zirconium n-propoxide, 0.0297mol diethylene glycol, 1.00×10 -6 polyvinylpyrrolidone (average molecular weight 200000) and 1.72mol ethanol were mixed and stirred for 10 minutes, then 0.0278mol water was added and stirred for 1 hour, then Transfer to a polytetrafluoroethylene airtight container, and after aging for 80 days at room temperature, it is alternately plated with silica sol to form a high-reflection film. The reflectivity at 1064nm is ≥98%, and the anti-laser damage threshold is higher than 15J/cm 2 (1064nm, 3ns).
实施例4Example 4
将0.01mol正丙醇锆、0.0297mol二甘醇、2.00×10-5聚乙烯吡咯烷酮(平均分子量30000)和0.86mol乙醇混合并搅拌10分钟后，再加入0.0194mol水并继续搅拌1小时，然后转入聚四氟乙烯密闭容器中，在室温下陈化60天后与氧化硅溶胶交替镀制高反膜。在1064nm处反射率≥98％，抗激光损伤阈值高于15J/cm2(1064nm，3ns)。0.01mol zirconium n-propoxide, 0.0297mol diethylene glycol, 2.00×10 -5 polyvinylpyrrolidone (average molecular weight 30000) and 0.86mol ethanol were mixed and stirred for 10 minutes, then 0.0194mol water was added and stirred for 1 hour, then Transfer to a polytetrafluoroethylene airtight container, and after aging for 60 days at room temperature, it is alternately plated with silica sol to form a high-reflection film. The reflectivity at 1064nm is ≥98%, and the anti-laser damage threshold is higher than 15J/cm 2 (1064nm, 3ns).
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| CN109851231A (en) * | 2019-01-24 | 2019-06-07 | 福建工程学院 | A kind of anti-reflection, anti-laser damage glass and preparation method thereof |
| CN113671609B (en) * | 2021-07-27 | 2023-08-04 | 上海灵曼信息科技有限公司 | A kind of high laser damage threshold film and preparation method thereof |
| CN114477192B (en) * | 2021-12-17 | 2023-03-03 | 山东科缘新材料科技有限公司 | Silicon-zirconium composite sol, and preparation method and application thereof |
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1998
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