CN110484869B - Mildew-proof and damp-proof optical film and preparation method thereof - Google Patents
Mildew-proof and damp-proof optical film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a damp-proof and mildew-proof optical film, which comprises a substrate, a high-density antireflection film system main body, a hard wear-resistant protective layer, a first hydrophobic film layer and a second hydrophobic film layer, wherein the high-density antireflection film system main body, the hard wear-resistant protective layer, the first hydrophobic film layer and the second hydrophobic film layer are sequentially evaporated on the substrate in a vacuum environment; also discloses a preparation process method thereof; the invention has the typical characteristics of high transmittance of the optical window after film coating, smooth and wear-resistant surface, good moisture-proof and mildew-proof performance, and easy transplantation of the preparation process. The invention can effectively solve the difficult problems of moisture and mildew resistance in the practical application process of the optical lens, and can be widely applied to the technical fields of military and civil photoelectrons such as military photoelectric equipment, precise optical instruments, outdoor monitoring cameras and the like in a high-humidity environment.
Description
Technical Field
The invention belongs to the technical field of optical films, and particularly relates to a high-transmittance damp-proof and mildew-proof optical film applied to protective windows of glass, optical crystals and the like, and a preparation method thereof.
Background
In various harsh environmental conditions, mold growth and moisture erosion are one of the important factors that cause corrosion and destruction of the protective window of the optoelectronic device. In fact, mildew on the surface of the optical window is essentially the result of destructive chemical corrosion, which cannot be removed once dense mildew stains are formed, and which directly affects the optical performance of the system and the service life of the optical window over time.
Research shows that the mold can continuously secrete corrosive toxins during the growth process of glass or optical crystals. However, conventional antireflection films are not subjected to long-term chronic corrosion of such secretions because of insufficient compactness and often more dot nodule defects inside the film layer. In addition, the mold also propagates by ejecting its spores, with a jumping expansion. These are among the reasons why mould proofing of optical instruments is difficult. In nature, molds usually grow as hyphae and propagate as spores. The mould prefers acidic environment and is aerobic, the optimum growth temperature is 25-35 ℃, and the relative humidity is 70-100%. As long as the available carbon source, nitrogen source and other nutrients (such as oil stain, sweat stain, dust, finger print on the surface) have proper temperature and high relative humidity, sufficient oxygen supply can ensure that a great deal of mould grows.
On the other hand, for an antireflection film prepared by conventional electron beam thermal evaporation, the moisture absorption phenomenon often starts from the nodule defects on the film surface (such as dust, rough spots, pits, scratches or polishing residual particles), and gradually develops in the film layer with poor compactness (such as a low refractive index layer) in the transverse direction and gradually penetrates to the depth. Based on the characteristics, the appearance of moisture absorption spots can be observed in the whole moisture absorption process, the spots are gradually enlarged and connected into a piece, and finally, a uniform moisture absorption layer is formed.
In fact, moisture attack and mold growth can also promote each other, thereby accelerating irreversible corrosion damage to the film layer and even to the optical window substrate. At present, the literature reports that a plurality of methods for preventing moisture and mildew of photoelectric equipment exist, and the types of related organic reagents are complete, but no effective solution exists at home and abroad for preventing moisture and mildew of an optical protection window.
Therefore, for the optical protection window, it is necessary to develop a new film structure to overcome the above defects and ensure that the optical window has good optical performance and moisture and mold resistance, and finally, the engineering application is realized.
Disclosure of Invention
In view of the shortcomings of the prior art, it is an object of the present invention to provide a high transmittance moisture and mold resistant optical film for use in an optical window.
The technical scheme adopted by the invention for solving the technical problems is as follows: a damp-proof and mildew-proof optical film comprises a substrate, a high-density antireflection film system main body, a hard wear-resistant protective layer, a first hydrophobic film layer and a second hydrophobic film layer, wherein the high-density antireflection film system main body, the hard wear-resistant protective layer, the first hydrophobic film layer and the second hydrophobic film layer are sequentially vapor-plated on the substrate; the substrate is glass, sapphire, zinc sulfide or silicon chip which is made of the same material as the optical window; the high-compactness antireflection film system main body is formed by combining a plurality of high-refractive-index film layers and low-refractive-index film layers, and the hard wear-resistant protective layer is Ta with the physical thickness of more than or equal to 150nm and the purity of more than or equal to 99.9 percent2O5Or HfO2Or Y2O3Or SiO2The high-compactness antireflection film system main body and the hard wear-resistant protective layer are an integral body formed by electron beam thermal evaporation; the hydrophobic film is made of fluorine-containing organic siloxane material.
The high-refractive-index film layer of the dampproof and mildewproof optical film is TiO2The film layer with low refractive index is SiO2。
The high-compactness antireflection film system main body, the hard wear-resistant protective layer, the first hydrophobic film layer and the second hydrophobic film layer are an integral body formed by electron beam thermal evaporation.
The invention also aims to provide a preparation process method of the moistureproof and mildewproof optical film for the optical window.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a damp-proof and mildew-proof optical film mainly comprises the following steps:
1) firstly, roughly wiping the substrate by using polishing solution once to remove surface corrosion stripes so as to form a fresh pollution-free surface to be coated, then cleaning the substrate for many times by using an anhydrous mixed organic solution, wiping off residues after polishing, and then checking the surface finish of the substrate by using a haar method;
2) placing qualified substrate in vacuum chamber, and making background vacuum be up to 1.5X 10-3Pa and below, simultaneously baking the substrate at the temperature of 170-250 ℃, ensuring that the heat penetration time is not less than 1 hour, starting an ion source to perform ion beam directional etching cleaning on the surface of the substrate for 3-10 minutes, wherein the working gas is high-purity argon, and the etched physical thickness is 30-80 nm;
3) adjusting the technological parameters of the ion source, and alternately evaporating TiO on the substrate by adopting electron beam evaporation according to the structural requirement of a designed multilayer antireflection film system2Film layer and SiO2A film layer to complete the evaporation of the multilayer antireflection film system; wherein the TiO is2The deposition rate of the film layer is 0.2nm/s, the oxygen flow is 25sccm, and the ion source parameters are set to be 130V/50A; SiO 22The deposition rate of the film layer is 0.5nm/s, the oxygen flow is 5sccm, and the ion source parameters are set to be 140V/50A;
4) adjusting ion source process parameters, setting the ion source parameters to be 135V/50A, setting the deposition rate to be 0.2-0.5 nm/s, continuously filling oxygen with the flow rate of 5sccm, bombarding the surface of the high-density antireflection film system main body, evaporating a hard wear-resistant layer on the high-density antireflection film system main body, after film coating is completed, adjusting the ion source parameters to be 140V/55A, continuously bombarding the surface of the hard wear-resistant layer for 3-5 minutes, and ensuring that the etched physical thickness value is 10-20 nm and the surface molecular activity of the hard wear-resistant layer is enhanced;
5) turning off the ion source, and vacuumizing to 1.0 × 10-3The baking temperature is reduced to 120-150 ℃ below Pa, then an evaporation baffle is opened in advance, the surface scanning amplitude of an electron beam is adjusted to cover the whole evaporation crucible, an evaporation source is opened, the emission current is set to be 3-10 mA, and the baffle and the electron beam evaporation source are immediately closed until the deposition rate is reduced to zero again, so that the plating of the first hydrophobic film layer is completed, and the first hydrophobic film layer with the physical thickness of 5-10 nm is obtained;
6) keeping the substrate baking state for 10-30 minutes, and finishing the plating of the second hydrophobic film layer according to the step 5);
7) setting the baking temperature of the substrate to be 120-140 ℃ and the time to be not less than 20 minutes; and continuously vacuumizing until the temperature of the substrate is gradually reduced to be below 80 ℃, opening the evaporation chamber to take the workpiece, and detecting the surface quality of the film layer.
Further, the vacuum chamber in the step 2) is a clean evaporation chamber of a film coating machine, vacuumizing is performed, the lens is heated, the support is started to rotate, the baking temperature is 180 ℃, the lens is heated thoroughly, and the heating time is not less than 85 minutes.
Furthermore, the ion source process parameters are adjusted to continuously bombard the surface of the coated layer after the evaporation of each layer in the step 3) is finished, so that the ion beam directional polishing effect is achieved until the evaporation of the next layer is started, and the treatment is beneficial to further reducing the nodule defects of the coated layer.
Furthermore, before vapor deposition, the steps 3) are respectively carried out with pre-melting degassing fully so as to avoid generating nodule defects due to sputtering in the evaporation process; after the film coating is finished, the temperature is kept for no less than 20 minutes under the vacuum condition, and then the temperature is naturally reduced to be below 80 ℃ to discharge the parts.
Further, the deposition rate in the step 4) is 0.4nm/s, and the physical thickness value etched away is 20 nm.
Further, the emission current in the step 5) is about 5mA, and the physical thickness of the plated first hydrophobic film layer is 60 nm; the physical thickness of the second hydrophobic film layer in the step 6) is 8 nm.
Further, the baking temperature in the step 7) is 130 ℃, and the heat preservation time is 30 minutes.
In summary, the invention has the advantages that:
the ion beam is adopted to directionally etch the surface of the substrate, so that organic pollutants on the surface of the substrate are effectively removed, surface molecules (or atoms) are activated, and residual defect seeds on the surface of the substrate are eliminated, thereby effectively improving the adhesive force of the film layer on the substrate and the film forming quality.
By optimizing the technological parameters of the ion source in the coating process and introducing the ion beam directional etching process after coating, various raised nodule defects formed in the coated layer and on the surface of the coated layer can be effectively removed or reduced, so that the further growth of the nodule defects in the subsequent film layer is inhibited. Meanwhile, the ion beam directional etching process after plating can also play a role in activating the surface molecules of the plated film layer, which is favorable for inhibiting the subsequent film layer from generating a columnar structure to a certain extent due to preferential production at the raised defect point, so that the compactness of the high-compactness anti-reflection film system main body and the hard wear-resistant protection layer in the invention is obviously improved, and the moisture and mildew resistance of the whole film system is further favorably improved. In addition, in order to reduce various nodule defects formed in the film deposition process, the effect of enhancing ion beam bombardment is also equivalent to controlling the deposition rate of each layer of film at a lower level, which is also favorable for improving the compactness of the film layer.
By successively evaporating a fluorine-containing organosiloxane (CF) hydrophobic film layer for two times and performing high-temperature curing treatment after plating, the shadow effect formed by protruding nodulation defects in the hydrophobic film material molecule deposition process is effectively avoided, so that the film layer can uniformly and compactly cover the hard wear-resistant protective layer, and the firmness is good. Meanwhile, after the hydrophobic film is coated at each time, high-temperature baking and curing treatment is respectively carried out, so that the firmness and the hardness of the hydrophobic film are further improved.
The preparation process is based on common vacuum coating equipment, and the related process method is easy to transplant, so that the protective antireflection film of the optical window has excellent physical properties such as moisture resistance, mildew resistance and the like while having good optical performance. On the other hand, the preparation method of the medium thin film with low defect and high density and the hydrophobic film has wide guiding significance in the preparation of other optical film systems.
Drawings
FIG. 1 is a block diagram of a moisture and mold resistant optical film system of the present invention;
FIG. 2 is a graph showing transmittance curves before and after an experiment of a sample of the moisture-and mold-resistant optical film of the present invention;
FIG. 3 is a diagram showing the hydrophobic effect on the surface of the sample of the moisture-proof and mold-proof optical film of the present invention.
The figures are numbered: 1-substrate, 2-high compact anti-reflection film system body, 3-hard wear-resistant protective layer, 4-first hydrophobic film layer, 5-second hydrophobic film layer.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1
The invention relates to a damp-proof and mildew-proof optical film which is realized on a Laibao SYRUSpro1110 type vacuum film plating machine; the apparatus is equipped with an APSII plasma source, an electron beam evaporation system, an IC5 film thickness monitor, and the like.
Referring to fig. 1 to 3, the invention discloses a high-transmittance damp-proof and mildew-proof optical film, which comprises a substrate 1, and a high-density antireflection film system main body 2, a hard wear-resistant protective layer 3, a first hydrophobic film layer 4 and a second hydrophobic film layer 5 which are sequentially evaporated on the substrate 1; the substrate 1 is made of glass, sapphire, zinc sulfide or silicon wafers which are made of the same materials as the optical window, so that the substrate 1 can be laid on the optical window to form a whole with the optical window, and the optical window can be used as the substrate 1 to be sequentially evaporated with other film layers; the high-density antireflection film system main body 2 is formed by combining a plurality of high-refractive-index film layers and low-refractive-index film layers, the high-density antireflection film system main body 2 and the hard wear-resistant protective layer 3 are an integral body formed by electron beam thermal evaporation, and the hard wear-resistant protective layer 3 is Ta with the physical thickness of more than or equal to 150nm and the purity of more than or equal to 99.9 percent2O5Or HfO2Or Y2O3Or SiO2(ii) a The hydrophobic membrane is made of fluorine-containing organic siloxane materials, wherein the first hydrophobic layer 4 and the second hydrophobic layer 5 are evaporated and plated twice by adopting an electron beam thermal evaporation mode, high-temperature baking and curing treatment is carried out in the middle, the baking temperature is 120-150 ℃, and the heat preservation time is 15-30 minutes.
Further, the first hydrophobic film layer 4 and the second hydrophobic film layer 5 are also integrated with the high-density antireflection film system main body 2 and the hard wear-resistant protection layer 3, and the influence on the transmission spectrum performance can be ignored only because the two hydrophobic film layers are too thin.
The material of the hard wear-resistant protective layer 3 in the invention has high surface energy, and is preferably SiO2The film material is favorable for improving the firmness of a subsequent hydrophobic film layer, so that good adhesive force can be formed between the film material and the molecules of the hydrophobic film deposited subsequently, and if other materials are selected, a SiO layer is recommended to be coated before the hydrophobic film is deposited2And a transition layer.
The high-refractivity film layer can adopt TiO2The film layer with low refractive index can be SiO2The high-density anti-reflection film system main body 2 is used as a multi-layer anti-reflection film system, and can be made into 2-10 layers.
The test result shows that the surface of the optical film is smooth and compact, and the optical film can pass the mould test level 1 standard specified by GJB150.10A-2009 at one time, and can play a good role in preventing moisture and mildew.
Example 2
High-efficiency antireflection film with moisture-proof and mildew-proof functions and coated on K9 glass optical window
. The technical requirements are as follows:
incident angle of 0-300. The coating sample piece passes the high-low temperature, constant humidity and heat, adhesive force and heavy friction tests specified by GJB2485-1995 at one time. Meanwhile, the compound also can withstand the mould test specified by GJB150.10A-2009.
Firstly, the membrane system structure is optimally designed according to the technical requirements, and the result is as follows:
wherein, the material of the hard wear-resistant protective layer 3 is selected to be SiO2And a-f are respectively the physical thicknesses of the film layers, and M1 and M2 are fluorine silicon-based organic hydrophobic film layers, and the physical thicknesses of the film layers are both 6.0 nm. The physical thicknesses of other film layers are as follows:
a-70.25nm；b-82.66nm；c-137.15nm；d-270.01nm。
the preparation process is implemented as follows:
1) preparation work: firstly, the substrate 1 is roughly wiped once by using special polishing solution, then the substrate is cleaned by using anhydrous (mixed) organic solution, then whether the surface smoothness of the substrate 1 meets the requirements is checked by using a Hash method, the substrate is placed into a cleaned evaporation chamber of a film coating machine after the surface smoothness is qualified, the substrate is vacuumized and heated, a support is started to rotate, the heating temperature is set to be 180 ℃, and the substrate is thoroughly heated for 85 minutes.
2) Ion beam etching and cleaning: when the background vacuum of 1.5X 10 is reached-3When Pa is needed, an ion source is started to carry out ion bombardment on the surface of the substrate 1, and the working gas is high-purity argon (99.99%). Setting parameters: the energy of the ion beam and the beam current are 160V/55A, and the duration is 8 minutes; the physical thickness of the etch was about 35 nm.
3) Adjusting the technological parameters of an ion source, and alternately evaporating high-refractive-index film TiO on a K9 substrate by adopting electron beam evaporation2And SiO2The physical thickness of the film layer is performed according to the design result of the film system. Wherein, TiO2The deposition rate of the film layer is 0.2nm/s, the oxygen flow is 25sccm, and the ion source parameters are set as follows: 130V/50A; SiO 22The deposition rate of the film layer was 0.5nm/s, the oxygen flow was set to 5sccm, and the ion source parameters were set as: 140V/50A. Before evaporation, the pre-melting degassing is fully carried out respectively so as to avoid generating nodule defects due to splashing in the evaporation process.
4) Plating a hard wear-resistant layer: the ion source parameters were set at 135V/50A, the deposition rate was 0.4nm/s, and the oxygen flow was 5 sccm. After the film coating is finished, the ion source parameter is adjusted to be 140V/55A, the surface of the hard wear-resistant layer is continuously bombarded, and the etched physical thickness value is 20 nm. The etching away of the hard wear-resistant protective layer 3 after plating is about 20nm, mainly considering the physical thickness compensation of the hydrophobic film layer.
5) Plating a first hydrophobic film layer: turning off the ion source, and vacuumizing to 1.0 × 10-3Pa below and the baking temperature is reduced to 135 ℃, and then an electron gun evaporation baffle is opened in advance. Adjusting the surface scanning amplitude of the electron beam to cover the whole evaporation crucible, opening the evaporation source and setting the emission current5mA, until the deposition rate is reduced to zero again, the baffle plate and the electron beam evaporation source are closed immediately. The film thickness monitor showed that the physical thickness of the first hydrophobic film layer was 6.0 nm.
6) And (3) keeping the substrate baking state for 10-30 minutes, and finishing the plating of the second hydrophobic film layer according to the step 5). The film thickness monitor showed that the physical thickness of the second hydrophobic film layer was 8nm (the physical thickness of the hydrophobic film layer may be different each time until evaporation was completed).
7) Setting the baking temperature of the substrate at 130 ℃ and the heat preservation time for 30 minutes.
And continuously vacuumizing until the temperature of the substrate is gradually reduced to be below 80 ℃, opening the evaporation chamber to take the workpiece, and detecting the surface quality of the film layer.
According to the invention, the compactness of the high-compactness anti-reflection film system main body and the hard wear-resistant protection layer is obviously improved and the nodule defects in the film layer are obviously reduced by adjusting the energy of charged ions and the beam density in the film deposition process and introducing the ion beam directional polishing process after plating; by sequentially evaporating the fluorine-containing organosiloxane (CF) hydrophobic film layer for two times and performing high-temperature curing treatment after plating, the film layer can be uniformly and compactly covered on the hard wear-resistant protective layer, the firmness is good, and the formation of a columnar cavity structure due to preferential growth in the rapid deposition process of hydrophobic film material molecules is avoided.
On the other hand, the surface of the substrate is firstly cleaned by ion beam directional etching before the film evaporation layer is coated, so that organic pollutants on the surface of the substrate are effectively stripped and surface molecules (or atoms) are activated, which is beneficial to radically inhibiting the nodule defect on the background of the substrate and remarkably improving the firmness between the film layer and the glass substrate. In the process, the range of the etching physical thickness is 30-80 nm.
The above-described embodiments are merely illustrative of the principles and effects of the present invention, and some embodiments may be applied, and it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the inventive concept of the present invention, and these embodiments are within the scope of the present invention.
Claims (8)
1. A moisture and mold resistant optical film, comprising: comprises a substrate (1), and a high-density anti-reflection film system main body (2), a hard wear-resistant protective layer (3), a first hydrophobic film layer (4) and a second hydrophobic film layer (5) which are sequentially evaporated on the substrate (1); the substrate (1) is glass, sapphire, zinc sulfide or silicon wafer; the high-compactness antireflection film system main body (2) is formed by combining a plurality of high-refractive-index film layers and low-refractive-index film layers, wherein the high-refractive-index film layers are TiO2The low refractive index film layer is SiO2The hard wear-resistant protective layer (3) is Ta with the physical thickness of more than or equal to 150nm and the purity of more than or equal to 99.9 percent2O5Or HfO2Or Y2O3Or SiO2The high-density antireflection film system main body (2), the hard wear-resistant protective layer (3), the first hydrophobic film layer (4) and the second hydrophobic film layer (5) are an integral body formed by electron beam thermal evaporation; the hydrophobic film is made of fluorine-containing organic siloxane material.
2. A method of making a moisture and mold resistant optical film as defined in claim 1, comprising the steps of:
1) firstly, roughly wiping the substrate (1) by using polishing solution, then cleaning the substrate (1) for multiple times by using anhydrous organic solution, and then checking the surface finish of the substrate (1) by using a Hash method;
2) placing the qualified substrate (1) in a vacuum chamber, and the background vacuum reaches 1.5 multiplied by 10-3Pa, simultaneously baking the substrate (1) at the temperature of 170-250 ℃, enabling the thermal penetration time to be not less than 1 hour, starting an ion source to perform ion beam directional etching cleaning on the surface of the substrate (1), lasting for 3-10 minutes, using high-purity argon as working gas, and etching off the substrate with the physical thickness of 30-80 nm;
3) adjusting the technological parameters of the ion source, and alternately evaporating TiO on the substrate (1) by adopting electron beam evaporation2Film layer and SiO2A film layer; wherein the TiO is2The deposition rate of the film layer is 0.2nm/s, the oxygen flow is 25sccm, and the ion source parameters are set to be 130V/50A; SiO 22Deposition rate of film 0.5nm/s, oxygen flowThe amount is 5sccm, and the ion source parameters are set to 140V/50A;
4) setting ion source parameters to be 135V/50A, setting the deposition rate to be 0.2-0.5 nm/s, continuously filling oxygen with the flow rate of 5sccm, bombarding the surface of the high-density antireflection film system main body (2), vapor-plating a hard wear-resistant protection layer (3) on the high-density antireflection film system main body (2), adjusting the ion source parameters to be 140V/55A, continuously bombarding the surface of the hard wear-resistant protection layer (3), lasting for 3-5 minutes, and etching to obtain the physical thickness of 10-20 nm;
5) turning off the ion source, and vacuumizing to 1.0 × 10-3The baking temperature is reduced to 120-150 ℃ below Pa, an evaporation baffle is opened in advance, the surface scanning amplitude of the electron beam is adjusted to cover the whole evaporation crucible, an evaporation source is opened, the emission current is set to be 3-10 mA, and the baffle and the electron beam evaporation source are immediately closed until the deposition rate is reduced to zero again, so that a first hydrophobic film layer (4) with the physical thickness of 5-10 nm is obtained;
6) keeping the baking state for 10-30 minutes, and finishing plating of the second hydrophobic film layer (5) according to the step 5);
7) setting the baking temperature to be 120-140 ℃ and the time to be not less than 20 minutes; continuously pumping high vacuum until the temperature of the substrate (1) is gradually reduced to be below 80 ℃, and opening the evaporation chamber to take out the parts.
3. The method for preparing a moisture-proof and mildew-proof optical film as claimed in claim 2, wherein the vacuum chamber in step 2) is a clean evaporation chamber of a film plating machine, the baking temperature is 180 ℃ and the baking time is not less than 85 minutes.
4. The method for preparing a moisture-proof and mildew-proof optical film as claimed in claim 2, wherein the ion source process parameters are adjusted to continuously bombard the surface of the coated layer after the evaporation of each layer in the step 3) is finished until the evaporation of the next layer is started.
5. The method for preparing a moisture-proof and mildew-proof optical film as claimed in claim 2, wherein, pre-melting degassing is respectively carried out before the evaporation in the step 3); after the film coating is finished, the temperature is kept for no less than 20 minutes under the vacuum condition, and then the temperature is naturally reduced to be below 80 ℃ to discharge the parts.
6. The method for preparing a moisture-proof and mold-proof optical film as claimed in claim 2, wherein the deposition rate in step 4) is 0.4nm/s and the physical thickness etched away is 20 nm.
7. The method for preparing the moisture-proof and mildew-proof optical film as claimed in claim 2, wherein the emission current in the step 5) is about 5mA, the physical thickness of the plated first hydrophobic film layer (4) is 6nm, and the physical thickness of the second hydrophobic film layer (5) in the step 6) is 8 nm.
8. The method for preparing a moisture-proof and mildew-proof optical film as claimed in claim 2, wherein the baking temperature in the step 7) is 130 ℃, and the temperature is kept for 30 minutes.
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| CN111485203A (en) * | 2020-05-19 | 2020-08-04 | 中国科学院光电技术研究所 | Preparation method for improving optical performance of optical film |
| CN112458409B (en) * | 2020-11-25 | 2023-01-10 | 湖北久之洋红外系统股份有限公司 | Preparation method of underwater pressure-resistant optical window antireflection film |
| CN112458400B (en) * | 2020-11-25 | 2023-01-03 | 湖北久之洋红外系统股份有限公司 | Preparation method of sand-proof, damp-proof and mildew-proof composite antireflection film for window |
| CN113532695B (en) * | 2021-08-14 | 2024-04-19 | 中建材玻璃新材料研究院集团有限公司 | Tin bath physical simulation method suitable for float glass |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10115711A (en) * | 1996-10-09 | 1998-05-06 | Nikon Corp | Production of optical thin film |
| CN101435888A (en) * | 2007-11-16 | 2009-05-20 | 爱普生拓优科梦株式会社 | Optical multilayer filter, method of manufacturing the same, and electronic apparatus |
| CN101550533A (en) * | 2009-05-07 | 2009-10-07 | 厦门美澜光电科技有限公司 | Antistatic optical substrate preparation method |
| CN102747328A (en) * | 2012-06-27 | 2012-10-24 | 同济大学 | Coating method capable of improving laser induced damage threshold of high-reflectivity film |
| CN104087933A (en) * | 2014-07-10 | 2014-10-08 | 深圳市东丽华科技有限公司 | Film coating method and film coating device |
| CN104090312A (en) * | 2014-07-30 | 2014-10-08 | 中国船舶重工集团公司第七一七研究所 | Infrared metal reflecting film with high adhesive force and manufacturing method thereof |
| CN109182969A (en) * | 2018-08-30 | 2019-01-11 | 湖北久之洋红外系统股份有限公司 | The preparation method of medium-wave infrared optics horniness protective film |
| CN109182972A (en) * | 2018-08-30 | 2019-01-11 | 华中光电技术研究所（中国船舶重工集团有限公司第七七研究所） | Multispectral hard anti-reflection film of large-size sapphire substrate and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5169163B2 (en) * | 2006-12-01 | 2013-03-27 | 旭硝子株式会社 | Method for finishing a pre-polished glass substrate surface |
| CN101962769B (en) * | 2010-10-08 | 2012-05-23 | 中国航空工业集团公司北京航空制造工程研究所 | Method for preparing hydrophobic film on surface of material |
| CN203732856U (en) * | 2013-11-08 | 2014-07-23 | 朱诗艺 | Camera antibiotic mildewproof filter |
-
2019
- 2019-07-11 CN CN201910626627.0A patent/CN110484869B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10115711A (en) * | 1996-10-09 | 1998-05-06 | Nikon Corp | Production of optical thin film |
| CN101435888A (en) * | 2007-11-16 | 2009-05-20 | 爱普生拓优科梦株式会社 | Optical multilayer filter, method of manufacturing the same, and electronic apparatus |
| CN101550533A (en) * | 2009-05-07 | 2009-10-07 | 厦门美澜光电科技有限公司 | Antistatic optical substrate preparation method |
| CN102747328A (en) * | 2012-06-27 | 2012-10-24 | 同济大学 | Coating method capable of improving laser induced damage threshold of high-reflectivity film |
| CN104087933A (en) * | 2014-07-10 | 2014-10-08 | 深圳市东丽华科技有限公司 | Film coating method and film coating device |
| CN104090312A (en) * | 2014-07-30 | 2014-10-08 | 中国船舶重工集团公司第七一七研究所 | Infrared metal reflecting film with high adhesive force and manufacturing method thereof |
| CN109182969A (en) * | 2018-08-30 | 2019-01-11 | 湖北久之洋红外系统股份有限公司 | The preparation method of medium-wave infrared optics horniness protective film |
| CN109182972A (en) * | 2018-08-30 | 2019-01-11 | 华中光电技术研究所（中国船舶重工集团有限公司第七七研究所） | Multispectral hard anti-reflection film of large-size sapphire substrate and preparation method thereof |
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