CN1016104B - Anti-corrosion double-layer antireflection film - Google Patents
Anti-corrosion double-layer antireflection filmInfo
- Publication number
- CN1016104B CN1016104B CN89106212A CN89106212A CN1016104B CN 1016104 B CN1016104 B CN 1016104B CN 89106212 A CN89106212 A CN 89106212A CN 89106212 A CN89106212 A CN 89106212A CN 1016104 B CN1016104 B CN 1016104B
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- Prior art keywords
- hfo
- film
- layer
- reflection
- weight ratio
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- 238000005260 corrosion Methods 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 229910052745 lead Inorganic materials 0.000 claims abstract description 7
- 229910052788 barium Inorganic materials 0.000 claims abstract description 6
- 239000011521 glass Substances 0.000 claims description 15
- 230000007797 corrosion Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000005304 optical glass Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- 238000002054 transplantation Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 13
- 230000008021 deposition Effects 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Glass Compositions (AREA)
- Surface Treatment Of Optical Elements (AREA)
Abstract
本发明公开了一种防蚀双层减反射膜，其特征是采用HfO2或Y2O3或94-80%重量比的HfO2与6-20%重量比的Y2O3作为高折射率的多层减反射膜。采用本发明可避免与含Pb，Ba，Cd成分的光学玻璃发生化学反应而腐蚀膜层坚硬牢固，光学特性稳定，重复性好，制备工艺简单，容易移植，HfO2，Y2O3材料价廉易于从市场获得。The invention discloses an anti-corrosion double-layer anti-reflection film, which is characterized in that HfO 2 or Y 2 O 3 or HfO 2 with a weight ratio of 94-80% and Y 2 O 3 with a weight ratio of 6-20% are used as the high refraction film. High rate multilayer anti-reflection coating. Adopting the present invention can avoid chemical reaction with optical glass containing Pb, Ba, and Cd, and the corroded film layer is hard and firm, with stable optical properties, good repeatability, simple preparation process, and easy transplantation. HfO 2 , Y 2 O 3 material prices Cheap and easy to obtain from the market.
Description
本发明涉及光学中的多层减反射膜，尤其涉及防蚀双层减反射膜。The invention relates to a multi-layer anti-reflection film in optics, in particular to an anti-corrosion double-layer anti-reflection film.
任何光学和激光仪器都离不开减反射膜。否则将因透过光能量低，背景杂散光强而使仪器无法工作。Any optical and laser instruments are inseparable from anti-reflection coatings. Otherwise, the instrument will not be able to work due to the low energy of the transmitted light and the strong background stray light.
传统的减反射膜都是单层MgF2，它的效率比较低，对折射率为1.52的KK9玻璃，单面反射率在可见光区只能从4.2%下降到1.8%左右。因此，近些年来，要求用双层或多层膜来取代单层膜，因为它们可使可见光区的残余反射率降低到0.3%以下。Traditional anti-reflection coatings are single-layer MgF 2 , and its efficiency is relatively low. For KK 9 glass with a refractive index of 1.52, the single-sided reflectance can only drop from 4.2% to about 1.8% in the visible light region. Therefore, in recent years, it is required to replace the single-layer film with a double-layer or multi-layer film, because they can reduce the residual reflectance in the visible light region to below 0.3%.
减反射膜内层常用高折射率的氧化物膜（如ZrO2、TiO2、Ta2O3等），但是这些材料与含Pb、Cd、Ba的光学玻璃（包括BaK、ZK、LaK、KF、QF、F、BaF、ZBaF、ZF等绝大部分玻璃）会发生化学反应。如折射率为1.9的材料通常利用ZrO2，而折射率为2.3的材料常选用TiO2和Ta2O3。这些材料在加热蒸发过程中会发生分解，因而在膜层中存在着金属离子或低价氧化物离子，这些离子与玻璃中的Pb、Cd、Ba等离子发生交换，并与空气中的水汽、CO2等反应生成酸性碳酸化合物或碱性氢氧化物，使玻璃产生腐蚀而失透。Oxide films with high refractive index (such as ZrO 2 , TiO 2 , Ta 2 O 3 , etc.) , QF, F, BaF, ZBaF, ZF and most other glasses) chemical reactions will occur. For example, the material with a refractive index of 1.9 usually uses ZrO 2 , while the material with a refractive index of 2.3 usually uses TiO 2 and Ta 2 O 3 . These materials will decompose during the heating and evaporation process, so there are metal ions or low-valent oxide ions in the film layer, these ions exchange with Pb, Cd, Ba ions in the glass, and with water vapor, CO 2 and other reactions generate acidic carbonates or alkaline hydroxides, causing corrosion and devitrification of the glass.
本发明的目的是为克服上述腐蚀现象，提供一种防腐双层减反射膜，在不增加任何工艺复杂性的前提下避免了玻璃的失透现象，从而获得低反射的优质减反射膜。The object of the present invention is to overcome the above-mentioned corrosion phenomenon and provide an anti-corrosion double-layer anti-reflection film, which avoids devitrification of the glass without increasing any process complexity, thereby obtaining a high-quality anti-reflection film with low reflection.
本发明的特征是：对含Pb、Ba、Cd成份占优势的无机光学玻璃采用HfO2或Y2O3或94-80%重量比的HfO2与6-20%重量比的Y2O3作为高折射率的双层减反射膜。这些材料为高温热压材料，纯度优于99%。The feature of the present invention is: HfO 2 or Y 2 O 3 or HfO 2 with a weight ratio of 94-80% and Y 2 O 3 with a weight ratio of 6-20% are used for the inorganic optical glass containing Pb, Ba, and Cd. As a high refractive index double-layer anti-reflection coating. These materials are high-temperature hot-pressed materials with a purity better than 99%.
双层减反射膜的膜系设计常为玻璃上的第一层半波长（λ2/2）厚度的高折射率材料和1/4波长（λ0/4）厚度的低折射率材料，其折射率分别为1.9和1.38。或者采用任意厚度膜系，玻璃上的第一层高折射率膜和第二层低折射率膜的厚度随玻璃折射率而变，其折射率分别为2.3和1.38。为了使反射色重复出现墨绿色，第二层λ0/4膜采用SiO2和MgF2合成膜，其厚度比约为1∶2，使W型曲线的中间凸峰控制在0.6%左右的反射率。由于含Pb、Ba、Cd成分的玻璃，其折射率一般都比较高，故一般用双层膜就可满足减反射要求。The film system design of the double-layer anti-reflection film is usually a high refractive index material with a thickness of half wavelength (λ 2 /2) and a low refractive index material with a thickness of 1/4 wavelength (λ 0 /4) on the glass. The refractive indices are 1.9 and 1.38, respectively. Or adopt any thickness film system, the thicknesses of the first high-refractive index film and the second low-refractive index film on the glass vary with the refractive index of the glass, and the refractive indices are 2.3 and 1.38 respectively. In order to make the reflection color appear dark green repeatedly, the second layer of λ 0 /4 film is made of SiO 2 and MgF 2 composite film, and its thickness ratio is about 1:2, so that the middle convex peak of the W-shaped curve is controlled at about 0.6% reflection Rate. Since the refractive index of glass containing Pb, Ba, and Cd is generally relatively high, a double-layer film can generally meet the anti-reflection requirements.
镀膜的制备工艺过程如下：将玻璃用酒精，乙醚清洁，擦干，放入真空室抽气。并将玻璃烘烤加热至180℃，当真空度达2×10-5乇时，对HfO2或Y2O3或HfO2与Y2O3混合料进行除气。电子枪除气功率为：电压5.5KV，电流从20mA逐渐上升至100mA，并使真空度不低于5×10-5乇。除气后即可开始蒸发，蒸发功率为：电压5.8KW，电流100mA。淀积速率用石英晶体频率计监控。并维持在3～4A/S范围内。在镀完半波厚的HfO2膜后，增加加热功率，将玻璃加热到230℃左右，接着蒸发SiO2，淀积速率为4nm/S，淀积厚度为1/3×1/4λ0，然后继续蒸发MgF2。用钼舟电阻加热将材料预熔，待完全熔解后，打开挡板控制淀积速率为5nm/S，并补足厚度到1/4λ0。The preparation process of the coating film is as follows: clean the glass with alcohol and ether, dry it, and put it into a vacuum chamber to pump air. And the glass is baked and heated to 180°C. When the vacuum reaches 2×10 -5 Torr, the HfO 2 or Y 2 O 3 or the mixture of HfO 2 and Y 2 O 3 is degassed. The degassing power of the electron gun is: the voltage is 5.5KV, the current is gradually increased from 20mA to 100mA, and the vacuum degree is not lower than 5×10 -5 Torr. Evaporation can start after degassing, the evaporation power is: voltage 5.8KW, current 100mA. The deposition rate was monitored with a quartz crystal frequency meter. And maintain it in the range of 3~4A/S. After plating the half-wave thickness HfO 2 film, increase the heating power, heat the glass to about 230°C, then evaporate SiO 2 , the deposition rate is 4nm/S, and the deposition thickness is 1/3×1/4λ 0 , Evaporation of MgF2 was then continued. The material was pre-melted by resistance heating with a molybdenum boat. After it was completely melted, the baffle was opened to control the deposition rate to 5nm/s, and the thickness was added to 1/4λ 0 .
实践证明含Pb、Ba、Cd的玻璃品种：PK2，BaK1-9，ZK1-20，LaK1-3，KF1-3，QF1-5，F1-13，TF3，BaK1-8，ZBaF1-5，ZF1-7，均不能应用ZrO2，TiO2和Ta2O5，必须采用HfO2或Y2O3或HfO2或Y2O3的混合料作为高折射率的双层减反射膜。Practice has proved that glass varieties containing Pb, Ba, and Cd: PK 2 , BaK 1-9 , ZK 1-20 , LaK 1-3 , KF 1-3 , QF 1-5 , F 1-13 , TF 3 , BaK 1 -8 , ZBaF 1-5 , ZF 1-7 , can not use ZrO 2 , TiO 2 and Ta 2 O 5 , must use the mixture of HfO 2 or Y 2 O 3 or HfO 2 or Y 2 O 3 as high refraction High rate double-layer anti-reflection coating.
采用本发明镀制的双层减反射膜可避免与含Pb、Ba、Cd成分的光学玻璃发生化学反应而发雾，膜层坚硬牢固，光学特性稳定，重复性好，避免ZrO2的折射率非均匀性而使膜层特性变差的缺点，制备工艺简单，容易移植，HfO2，Y2O3材料价廉易于从市场获得。The double-layer anti-reflection film plated by the present invention can avoid chemical reaction with optical glass containing Pb, Ba, and Cd to cause fogging . The disadvantage of non-uniformity makes the characteristics of the film layer worse, the preparation process is simple, easy to transplant, and the HfO 2 and Y 2 O 3 materials are cheap and easy to obtain from the market.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89106212A CN1016104B (en) | 1989-07-25 | 1989-07-25 | Anti-corrosion double-layer antireflection film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89106212A CN1016104B (en) | 1989-07-25 | 1989-07-25 | Anti-corrosion double-layer antireflection film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1049059A CN1049059A (en) | 1991-02-06 |
| CN1016104B true CN1016104B (en) | 1992-04-01 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89106212A Expired CN1016104B (en) | 1989-07-25 | 1989-07-25 | Anti-corrosion double-layer antireflection film |
Country Status (1)
| Country | Link |
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| CN (1) | CN1016104B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4926504B2 (en) * | 2006-03-08 | 2012-05-09 | 浜松ホトニクス株式会社 | Photocathode, electron tube provided with the photocathode, and method for producing photocathode |
| CN100447583C (en) * | 2007-03-30 | 2008-12-31 | 厦门大学 | Double-layer anti-reflection film for ultraviolet light detector and preparation method thereof |
| CN110359016A (en) * | 2019-03-19 | 2019-10-22 | 长春理工大学 | A kind of high-reflecting film and preparation method thereof |
-
1989
- 1989-07-25 CN CN89106212A patent/CN1016104B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN1049059A (en) | 1991-02-06 |
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