CN108349792A - Complex optics coating and its manufacturing method（Modification） - Google Patents
Complex optics coating and its manufacturing method（Modification） Download PDFInfo
- Publication number
- CN108349792A CN108349792A CN201580082993.4A CN201580082993A CN108349792A CN 108349792 A CN108349792 A CN 108349792A CN 201580082993 A CN201580082993 A CN 201580082993A CN 108349792 A CN108349792 A CN 108349792A
- Authority
- CN
- China
- Prior art keywords
- coating
- layer
- complex optics
- protective
- manufacturing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/38—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal at least one coating being a coating of an organic material
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/73—Anti-reflective coatings with specific characteristics
- C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Laminated Bodies (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The present invention relates to the surface treatments of the substrate carried out by applying coating, in particular to thin film technique.The object of the present invention is to provide a kind of simple and reliable optical coating and its production technology with superior availability, which is suitble to mass produce with low cost.It is listed to solve the problems, such as the adhesive phase of 5 to 200nm modification the thickness formed made of amorphous substance, between anti-reflection coating and protective coating in including the complex optics coating of the multi-layer anti-reflection coating and protective coating that are formed by the alternating layer with high index and low refractive index.Additionally provide two kinds of modifications of the method for producing the complex optics coating.
Description
The present invention relates to the substrate surface process carried out by applying coating, i.e. thin film technique.It is anti-it can be used to prepare
Reflectance coating, resisting influences device (such as mobile phone, music player, e-book, tablet computer, computer, ATM, airport
Check-in equipment, etc.) display surface and various Optical devices camera lenses surface pollution and external corrosion corrode.
Anti-reflection coating is the single-layer or multi-layer optical texture in optical system surface, is changed since the reflection of generation incident light is reduced
The transmissivity of kind optical system.The coating is possible to improve picture contrast and clarity, especially when device is exposed to direct projection
When sunlight.Surface with anti-reflection coating needs processing with caution, because they are easily damaged.Anti-reflective coating layer surface
Pollutant, such as oil, grease or dust, can interfere the light reflection for applying layer function and dramatically increasing polluted surface；In addition, with
The passage of time, these pollutants can destroy anti-reflection coating.In order to keep the optical property of anti-reflection coating, should will protect
Coating, which is coated on its surface, to be influenced to protected from external corrosion and allows the easy clean to inevitable pollutant.
However, protective layer must not interfere the function of anti-reflection coating.
It is mobile phone, music player, e-book, tablet computer, notes using the target market positioning of this type coating
The touch screen of this computer (these are the consumer electronics of large-scale production).Therefore, high processing performance is before being used for research and development
State the Compulsory Feature of the painting layer manufacturing method of the touch screen of device.
For claimed both coating and its manufacturing method, similar coating and method are known, are described in
In U.S. Patent No. 8817376 disclosed on 08 26th, 2014.On the transparent substrate this publication describe coating
Optical coating is applied by being formed on its surface silica film and being coated with the organic hydrophobic protection of fluoro on the film successively
The multi-layer anti-reflection coating composition of layer.
Manufacturing method according to the optical coating of referenced patents is as follows：Multilayer is resisted using ion auxiliary electron beam evaporation method
Reflectance coating coats on the transparent substrate, forms silicon oxide film in coating surface using identical method, and will using evaporation source
Hydrophobic protective coating film is coated on silicon oxide film.During optical coating is formed, all process units should be mounted on one
In a vacuum chamber, and sample should be fixed between them on the dome of rotation.
The shortcomings that optical coating and its manufacturing method of referenced patents, is as follows：
The hydrophobic performance of coating is poor：It is about 75 ° that contact angle is moistened after 6000 wear-out periods, shows protective coating
Partial destruction, however its physical property must provide at least 100 ° of moistening contact angle；
There is the defect caused by pollution in the coating formed, because the alternating of the layer with different mechanical performances leads to material
Material is removed from tool；
Processing performance is low, due to the fast dust-removing of indoor tool, also because of anti-reflective coating layer component and hydrophobic protective coating
Fluoro organic component, service cleaning procedure between the vacuum equipment runtime must shorten to reduce the defect of coating.
Claimed optical coating and its manufacturing method, immediate coating and method are described in 04 month 2014
In U. S. application the 2014113083rd disclosed in 24 days.This publication describe coating being resisted by multilayer on the transparent substrate
The optical coating of reflectance coating composition.Stabilized protective organic at elevated temperatures, is applied on optical coating.
Here, anti-reflection coating can by with high index (1.7≤n≤3.0), mean refractive index (1.6≤n≤1.7) and
The alternating layer of low refractive index (1.3≤n≤1.6) forms, and the number of these layers and their thickness change are very big, and protect
Coating is formed by perfluoropolyether (PFPE), and the general formula of perfluoropolyether (PFPE) is С F3-CF2O-(CF2-CF2O)k- R, wherein k are
The number of the chain link repeated, R are so that single layer is fixed on by the reactive terminal group on processing surface.According to the patent of reference,
The manufacturing method of optical coating includes following operation：The coating of multi-layer anti-reflection coating and protective coating.Here, a variety of methods are used
Manufacture anti-reflection coating, such as gas-gas deposition of gas-gas deposition, plasma enhancing, laser ablation, thermal evaporation,
Gas-vapour phase condensation, ion auxiliary electron beam evaporation, atomic layer deposition.
The formation of protective coating can be realized for example by thermal evaporation, vapor phase deposition or atomic layer deposition.
In outdoor or wet environment, (range of relative humidity (RH) is 40%<RH<100%) in, by described optics
Coating is heat-treated in time interval in 5 to 60 minutes in 60 DEG C to 200 DEG C of temperature, so as to acceleration protection coating molecule
The forming process of key between surface layer.
The shortcomings that coating and method of referenced patents, is as follows：
Protective coating is had a low resistance for external erosion, the reason is that coating is applied directly to the anti-reflection coating to be formed
On, structure is not by being modified；
In order to complete described method, big production area is required, and reason is the application of line style facility,
In, all operations (it is 3 to 21 to complete the quasi- required operation number of technology used) are all completed in individual process chamber, this
Cause the cost of product manufacturing higher；
Line facility is of high cost and design height is complicated because each processing vacuum chamber be required for supplement pipe-line equipment,
Gas supply system, process unit etc..
The purpose of the present invention is research and develop have high end user characteristics (anti-reflection property, hydrophobicity, oleophobic property including
The protective nature of wearability) simple and reliable optical coating and be suitble to low production cost the manufacture that mass produces
Technology.
Due to formed between anti-reflection coating and protective coating 5 to 200nm thickness amorphous substance modification
Adhesive layer has been realized in the specific purpose of the complex optics coating including multi-layer anti-reflection coating and protective coating, wherein more
Layer anti-reflection coating is formed by the alternating layer with high index and low refractive index.
In the most preferred embodiment, protective coating is made of siliceous perfluoropolyether, the nothing in specific composite coating
Amorphous mass is amorphous silicon oxide, in anti-reflection coating made of the material of the layer with high index be silicon nitride, with
And the material of the manufactured layer with low refractive index is silica in anti-reflection coating.
If other organic compounds is selected to manufacture protective layer, it is possible to select other adhesion-layer materials respectively.
Alternating layer, adhesive coatings and the protective coating of anti-reflection coating manufacture in such processes：They are by basal layer
Composition, their thickness are the monolayers of 1 to 6 layer of respective material, and it is inclined that the roughness of modified adhesive layer meets distribution standard
Difference is less than the condition of 2nm.
The thickness of protective coating can be 2 to 20nm.
In another embodiment, protective coating is the monomolecular film formed in liquid-gas interface.
First embodiment of the manufacturing method of claimed complex optics coating is related to using in single vacuum processing
Gas-vapour deposition method for not being vented and coating stable at elevated temperature are by multi-layer anti-reflection coating and protective coating
Coated on substrate, the specific purpose of first embodiment by anti-reflection coating and protective coating coating operation it
Between form the adhesive layer of amorphous substance and realize, is formationed of the adhesive layer has used gas-vapour of high-density plasma enhancing
Phase deposition method, then by being etched in gas discharge plasma and/or being modified by ion polishing.
In the most preferred embodiment, protective coating is made of siliceous perfluoropolyether, and amorphous silicon oxide is used for
The amorphous substance of specific composite coating, and the anti-reflection coating for providing high index is made of silicon nitride, and provide
The anti-reflection coating of low refractive index is made of silica.
The painting method of each layer and adhesive layer in anti-reflection coating can be existed using two plasma generating systems
Two stages are realized：During the first stage, a plasma generating system is used to coat basal layer, and in second stage
Period, another plasma generating system repeat these stages until reaching institute's shape for aoxidizing or nitrogenizing aforementioned base layer
At layer appointed thickness.
In the most preferred embodiment of the manufacturing method of complex optics coating, protective coating is by siliceous perfluoropolyether system
At amorphous silicon oxide is selected as amorphous substance.
By the modification procedure of the adhesive layer being etched in gas discharge flame preferably fluorine-containing or contain chlorine plasma
Implement in body.
During the coating of protective coating, gas-vapour phase of siliceous perfluoropolyether is prepared by solution appropriate by evaporating.
Using the modification for the adhesive layer that ion polishing method carries out, using energy be 500 to 4000eV and dosage be 0.05 to
1C/cm2Ar or O2Ion is implemented.
During the coating of anti-reflection coating, 2 to 6 layers of unimolecule are coated in the rotation each time of drum-type substrate carrier
The basal layer of the suitable substance of layer thickness；During the coating of adhesive layer, applied in the rotation each time of drum-type substrate carrier
Cover the basal layer of the amorphous silicon oxide no more than 2 layers of monolayer thickness；And during the coating of protective coating, in roller
Coating is the basal layer of the siliceous perfluoropolyether of 1 or 2 layer of monolayer thickness in the rotation each time of formula substrate carrier.
Completed in the coating procedure of protective coating and after removing drum-type substrate carrier, sequentially carry out vacuum chamber etc. from
Daughter chemical cleaning operation carries out first in oxygen plasma, then it is fluorine-containing or containing chlorine plasma in carry out.
Second of embodiment of the manufacturing method of claimed complex optics coating is related to multi-layer anti-reflection coating
(using gas-vapor deposition method) and protective coating are coated on substrate and coating stable at elevated temperature, this second
The specific purpose of embodiment between anti-reflection coating and the coating operation of protective coating by forming amorphous substance
Intermediate adhesion layer, then by being etched in gas discharge plasma and/or being modified by ion polishing
And realize, the formation of intermediate adhesion layer uses gas-vapour deposition method that high-density plasma enhances, and, protective coating
It is formed monomolecular film, and is formed into intensive monolayer in liquid-gas interface, which is transferred to adhesive layer
Surface.
The coating procedure of each layer and adhesive layer in anti-reflection coating can be existed using two plasma generating systems
Two stages are realized：During the first stage, a plasma generating system is for coating basal layer, in the second stage phase
Between, another plasma generating system repeats these stages until reaching to be formed for aoxidizing or nitrogenizing aforementioned base layer
Layer appointed thickness.
In the most preferably implementation for applying the second embodiment of layer manufacturing method in complex optics, protective coating is by siliceous
Perfluoropolyether is made and amorphous silicon oxide is selected as amorphous substance.
Protective coating coating is included in the intensive monolayer that deionized water surface forms siliceous perfluoropolyether, unimolecule
Layer is transferred to bonding layer surface, is exposed to IR in film transfer (hereinafter referred to as film deposition) and/or protective coating surface and radiates it
Afterwards immediately by the drying substrates with composite coating, and by the substrate thermal annealing with composite coating.
Coating stable is realized at a temperature of 100 to 120 DEG C.
Preferred protective coating is made of the PFPE with trimethoxy silane alcohol end group.
In the most preferred embodiment of complex optics coating, for being selected as the substance of protective layer, by amorphous
Adhesive layer made of SiClx is prerequisite condition.If selecting other organic compounds for protective coating, adhesive layer
Also will be other.However, amorphous silicon layer can also apply to other optical systems.Most importantly adhesive layer changes
Property, this not only has actively impact to entire coated structure, but also provides adhesion strength between protective coating and optical layer, from
And lead to longer Coating Durability.
Attached drawing illustrates the non-limiting embodiment of embodiment of the present invention.
The schematic diagram of Fig. 1-complex optics coating.
Fig. 2-has the reflectivity of anti-reflection coating and the touch screen surface of adhesive layer relative to lambda1-wavelength.
The layout of device in Fig. 3-vacuum processing chamber.
The water of Fig. 4-protective coating moistens contact angle relative to wear-out period number.
The equipment drawing for the monomolecular film-that Fig. 5-coating protective coating-is formed using designation method in liquid-gas interface.
The water moistening contact angle of protective coating prepared by the second embodiment of the claimed method of Fig. 6-basis is opposite
In the wear-out period number of the coating.
Fig. 1 illustrates the schematic diagram of claimed optical coating.On transparent substrate 1, it is coated with anti-reflection coating,
It is made of the layer being repeated cyclically, wherein layer 2 has high (H) refractive index, and 1.7≤n≤3.0, thickness is 2 to 400 nm, layer
It is layer 3 after 2, layer 3 has low (L) refractive index, and 1.3≤n≤1.7, thickness is 2 to 400nm.Layer number can 2 to
Selection in 200 ranges.
In anti-reflective coating layer surface, adhesive layer 4 is formed, thickness is 5 to 200nm, by fluorine-containing or contain chlorine in gas discharge
It is etched in plasma and/or is modified by ion polishing.
Modified film coating has good adhesiveness due to surface active in this way, and because in anti-reflective
The mechanical stress generated in coating is penetrated to relax in modified unformed layer and there is mechanical resistant impact.Moreover, modified is viscous
Closing layer has the hydrophily and roughness for being suitable for coating next layer, and does not influence the optical property of anti-reflection coating.
If the modification of adhesive layer 4 cannot provide required strength character, the layer can in addition adulterate such as carbon from
Son.
Thickness is that 2 to 20nm protective coating 5 is applied to the surface of modified adhesive layer 4.
Protective coating 5 not only make adhesive layer 4 stablize and also for complex optics coating provide such as hydrophobicity, oleophobic property and compared with
The end user characteristics of high-wearing feature.
Embodiment 1
In the embodiment that the complex optics coating of recommendation designs, the number of the layer of anti-reflection coating is 8.The order of layer,
Their thickness and refractive index is referring to following table.All layers are all increased in a vacuum processing chamber using high-density plasma
The method of strong vapor deposition successively coats.
Table
| Layer number | The index of layer | Material | n | Physical thickness [nm] |
| 1 | H | SiNx | 1.8 | 14.5 |
| 2 | L | SiOx | 1.44 | 32.5 |
| 3 | H | SiNx | 1.8 | 65.1 |
| 4 | L | SiOx | 1.44 | 48.1 |
| 5 | H | SiNx | 1.8 | 38 |
| 6 | L | SiOx | 1.44 | 30.6 |
| 7 | H | SiNx | 1.8 | 85.6 |
| 8 | L | SiOx | 1.44 | 81.1 |
In anti-reflective coating layer surface, the amorphous silicon oxide (SiO that thickness is 20nm is formedx) adhesive layer 4, then carry out
It is modified.As modified as a result, by carrying out plasma chemistry etches and ion throwing in containing fluoro plasma in gas discharge
Light falls the amorphous silicon oxide of 10nm from the surface etching of adhesive layer 4.
Fig. 2 describes the reflectivity of the anti-reflection coating with adhesive layer of generation relative to lambda1-wavelength.
The thickness of protective coating 5 is about 8 to 10nm, by the siliceous perfluoropolyether with trimethoxy silane alcohol end group
(PFPE) it is made, protective coating 5 is coated in amorphous silicon oxide using gas-vapor deposition method in same vacuum processing chamber
Modified layer surface.
Vacuum processing chamber 6 is made into the regular prism that bottom is polygon, is coated in vacuum processing chamber 6 claimed
Composite coating.Drum-type substrate carrier 7 is used for substrate being fixed thereon, and drum-type substrate carrier 7 is mounted on along its vertical axis
The center of process chamber 6.
The flange of process unit is in the side of vacuum chamber.Rib is selected according to the number for realizing device necessary to this method
The number in the face of column.Other than process unit, high-vacuum pump 8 is installed on several faces to provide in vacuum processing chamber
The gas distribution needed.
Vapour deposition process is selected to realize high processing performance.Due to mass transport process high fluidity and high intensity (for
It is intrinsic for gas medium), and due to the selectivity of interaction process between initial product, selected method is suitable
Together in the coating for producing following property：It is uniform and homogeneous in terms of thickness with high density, and there is high-purity.Base
It is selected as auxiliary tool in the supporter of plasma to influence coating coating dynamics and coating performance.Reaction volume is medium
Gas ions excite and plasma parameter control used by various technologies can strengthened coat growth course, make these processes move
To lower temperature range, and make to form the process of specified coating micromorphology and structure, the composition of coating and other coatings spy
The more controllable system of property.
Following process units are used to form claimed complex optics coating：At least one high-density plasma occurs
System 9, ion beam sputtering system 10, also, implement complete composite coating sputtering if interrupted in no vacuum cycle,
It so further include liquid reagent vapo(u)rization system 11.It is all if coating composite coating under the interruption of no vacuum cycle
Process unit is mounted in a vacuum processing chamber 6, and it is compound to ensure under the exhaust of no operational volume to make dispositions in advance
Optical coating is formed.
Described process equipment configuration makes in time interval and formation complex optics coating between loading and unloading
Time interval between the operation of single layer minimizes, and drum-type substrate carrier 7 can rotate, so as to relatively easily
Adjust the uniformity of coating coating.
High-density plasma generating system 9 includes at least two vertical or staggered inductively-coupled plasma sources
(ICP) 12, it is run at industrial frequency 13.56MHz.Inductively-coupled plasma sources 12 arrange in this way so as to
The plasma density distribution of high uniformity is provided in discharge space 13, discharge space 13 is in vacuum processing chamber 6 by protection gold
Belong to the region that screen 14 limits.Due to the exterior static magnetic field with induction 1mT, work gas in plasma generating region can be provided
Volume ionization rate increases.Setting is used to form magnetic in outdoor, positioned at 12 subsequent permanent electric magnet 15 of inductively-coupled plasma sources
.Higher plasma density ensures the good optical and mechanical performance of the coating of deposition.Method for coating these coatings
It is even suitable for coating optical coating on temperature-sensitive sample, because the temperature of sample is never greater than 100 in entire process cycle
℃。
Ion beam sputtering system 10 is made of ion source 16 and averager 17.Ion source 16 is by having 500 to 4000 eV
The ion of energy bombards to provide sample.17 flow of emitted electrons of averager prevents positive charge from assembling in sample surfaces and be based on this
The surface is continuously bombarded in offer.
Liquid reagent vapo(u)rization system 11 is for measuring and conveying vapour phase organic compound to the device of sample surfaces.Reagent
Part is sputtered on being heated to the evaporator locular wall of 250 to 300 DEG C of temperature, wherein reagent rapid evaporation and the steaming with them
Hair-like state is transferred to coating crystallizing field.
Complex optics coating forming procedure is made of following several stages.
It loads
Both-sided adhesive material is used to transparent substrate (screen, camera lens, glass, etc.) being fixed on drum-type substrate carrier 7
On face.Due to the jointing material for fixing sample, coating can be coated in the entire full surface of sample, without any the moon
Shadow zone.Suction vacuum processing chamber 6 is until pressure becomes less than 0.005Pa, and the drum-type substrate carrier 7 for being fixed with sample is opened
Begin to rotate in vacuum processing chamber 6.
Plasma clean and surface active
Before anti-reflective coating layer deposition process, using induction discharge plasma clean substrate, molecule to remove
Grain, the gas of absorption, polymer segments, vapor, and the surface key of atom activation substrate surface is so as to improve the viscous of coat
Attached property.For this purpose, the rotation of activation drum-type substrate carrier 7, speed is 150RPM.Gas distributed system 18 is used for will
Oxygen is supplied in vacuum processing chamber 6, and pressure increases to 0.7 to 3Pa, and activates high-density plasma generating system 9.Processing carries out
At least 1.5 minutes.Then, hydrogen is supplied to vacuum processing chamber 6, and oxygen feeding stop, pressure are maintained at same range.Cleaning is held
It is at least again 1.5 minutes continuous.
Cleaning in oxygen plasma eliminates remaining organic pollution, and the cleaning in hydrogen plasma makes table
Face hydrogenates so as to passivated surface key.
Then, it deactivates plasma source and stops hydrogen supply.
Anti-reflection coating coats
Because anti-reflection coating (is rolled over by several layers 2 (with high H refractive indexes) being repeated cyclically and layer 3 with low L
Penetrate index) composition, so these layers are successively coated using chemical gas-vapor deposition method (PECVD) of plasma enhancing.
In the case of coating single phase, gas distributed system 18 is used for be used for the working gas of anti-reflection coating formation
Supplied in vacuum processing chamber 6.Pressure in room rises to 0.5 to 3Pa, and activates high-density plasma generating system 9.It is heavy
Odd-level 2 with high H refractive indexes in product anti-reflection coating.In order to stop depositing, high frequency (HF) power supply is deactivated (in attached drawing
It is not shown).Then, gas medium composition is modified and activates high-density plasma generating system again.Deposit anti-reflective
Penetrate the even level 3 with low L refractive indexes in coating.
In the case of two benches coat, two high-density plasmas for being mounted on the not ipsilateral of process chamber 6 occur
System 9 is used for being formed the layer of anti-reflection coating.One high-density plasma generating system 9 is used to form substance (for example, silicon)
Layer, in this case SiH4It is formed as working gas and the second high-density plasma generating system 9 for aoxidizing
Layer.Here, oxidation refers to any reaction for causing compound to generate, such as is reacted with oxygen, nitrogen, selenium etc..In the oxidation of silicon
Or in nitridation process, it includes O that the working gas in the stage, which should be selected from,2、O3、N2O、N2、NH3Range.As a result, in antireflection
In coating, the layer 2 with high index is formed by silicon nitride, and the layer 3 with low refractive index is formed by silica.
The coating for making to be formed that separates of deposition process and oxidation process has better uniformity.
The deposition of layer 2 and layer 3 should repeat until forming the anti-reflection coating with specified optical property；Then,
Stop reaction gas supply.
Embodiment 2
For the deposition of the layer 2 with high H refractive indexes, working gas Ar, SiH are used4、N2Mixture；And for tool
The deposition for having the layer 3 of low L refractive indexes, uses working gas Ar, SiH4、O2Mixture.Here, it is sent to gas discharge etc.
The HF power densities of gas ions are about 0.2W/cm3, and the rotary speed of substrate carrier 7 is 150RPM.As a result, in anti-reflective
It penetrates in coating, the layer 2 with high index is formed by silicon nitride, and the layer 3 with low refractive index is formed by silica.
Be fixed with the substrate carrier 7 of sample rotary speed provided in the rotation each time of carrier thickness be approximately 0.15 to
The basal layer of 0.5nm coats, and is 2 to 6 layers of monolayer corresponding to thickness, is fixed with the rotary speed of the substrate carrier 7 of sample
Yet form intensive (non-porous) and the flawless coating with minimal mechanical stress.These process characteristics, which impart, applies floor height
Mechanical strength and good optical property.Due to being sent to the high HF power densities of gas discharge plasma, the technique energy
It is enough to implement at a temperature of less than 100 DEG C；This also makes to lead due to the difference between application temperature and the operating temperature of manufactured goods
The mechanical stress of cause reduces.
Adhesive layer deposits
Adhesive layer 4 is coated on the anti-reflection coating of gained by the gas-vapor deposition method enhanced using high-density plasma
Surface.
In the case of coating single phase, gas distributed system 18 is used for be used for the working gas of anti-reflection coating formation
Supplied in vacuum processing chamber 6.Pressure in room rises to 0.5 to 3Pa, and activates high-density plasma generating system 9.For
Stop deposition, deactivates HF power supplys.
In the case of the coating of the two benches of adhesive layer 4, the not ipsilateral of equipment is mounted with two high-density plasmas
Generating system.One high-density plasma generating system is used to form amorphous substance (for example, silicon) layer, in this case
SiH4As working gas.Second high-density plasma generating system is used for the oxidation of layer.Here, oxidation refers to leading to chemical combination
Any reaction that object generates, such as reacted with oxygen, nitrogen, selenium etc..In the embodiment considered, the production for silica,
It includes O that should be selected from for the working gas of silicon oxidation in second stage2、O3、N2The range of O.
The coating for making to be formed that separates of deposition process and oxidation process has better uniformity.
Embodiment 3
The coating of the adhesive layer 4 of amorphous silicon oxide is immediately begun to after coated with multiple layer anti-reflection coating.Keep substrate
The rotary speed of carrier 7, by working gas SiH4、Ar、O2Supplied in process chamber 6.Operating pressure rises to 1Pa, and activates highly dense
Spend plasma generating system.Here, the HF power densities for being sent to gas discharge plasma are about 0.2W/cm3.Coating
Silicon oxide layer.Setting processing speed is so as at most 1 to 2 layer of the coating when the substrate carrier 7 for being fixed with sample often rotates one time
SiOxMonolayer.As a result, coating " growth " becomes intensive and without mechanical stress, and mechanical stress is loose in fabric
It relaxes.Cooling temperature is less than 100 DEG C.
Adhesive layer is modified
After deposition, adhesive layer 4 is modified.
In modified operate, gas discharge it is fluorine-containing or containing chlorine plasma in adhesive layer 4 is etched.For the mesh
, change the composition of working gas.It is substituted for the reaction gas of deposition, for the gas etched applied to adhesive layer.In room
Pressure rises to 0.5 to 3Pa, and activates high-density plasma generating system 9, and the power density in discharge space is higher than 0.1W/
cm3.The surface etching of adhesive layer 4 is fallen, as a result, removal with film surface loosely in conjunction with and be formed in discharge volume and
It is present in the foreign particle on surface after amorphous substance particle on non-sample surface, and removal deposition.
The second operation that adhesive layer is modified is ion polishing.Deactivate high-density plasma generating system 9.Ion beam sputtering
System 10 is used for Ar and O2Supplied in process chamber.Averager 17 and ion source 16 are activated.Ion source 16 is using energy
500 to 4000eV ion and with 0.05 to 1C/cm2Dosage bombard sample.
Processing is persistently carried out until coating 4 obtains required optical property and configuration of surface.Roughness must satisfy distribution
Standard deviation is less than the condition of 2nm.Working gas supply is deactivated, the pressure in vacuum processing chamber is down to no more than 0.01Pa
Value.
Etching in reaction gas provides the higher abrasion resistance of coating 4, and in addition to higher abrasion resistance, ion polishing carries
For the preferable tactile when coating is used.
Embodiment 4
After deposition adhesive layer 4 made of amorphous silicon oxide (thickness is 81nm), surface is in fluorine-containing plasma
It is etched in body, etch depth is 10nm.For this purpose, change the composition of working gas：It is substituted for the reaction gas of deposition
Body, for the gas etched applied to adhesive layer, i.e. NF3、O2、Ar.Pressure in room rises to 0.5 to 3Pa, and activate high density etc.
Gas ions generating system 9.Here, power density is about 0.2W/cm3.The surface of adhesive layer 4 is etched 8nm.It deactivates highly dense
Spend plasma generating system 9.Deactivate reaction gas supply.
Ion beam sputtering system 10 is for supplying Ar and O2, and the voltage of ion source anode is set as 3800V.It will neutralize
Device 17 and ion source 16 activate.Ion beam is used to the adhesive layer 4 of amorphous silicon oxide etching away 2nm；Meanwhile carrying out sample table
Mirror polish.When reaching ion processing dosage 0.05C/cm2When stop surface be modified.Working gas supply is deactivated, and will be at vacuum
Pressure in reason room 6 is down to the value no more than 0.01Pa.
Protective coating coats
First method (modification 1)
The first method for forming protective coating realizes that no vacuum is followed by solution of organic compound is evaporated in vacuo
Ring interrupts.
After coating anti-reflection coating with adhesive layer 4, sample is stayed in the drum-type substrate carrier in vacuum processing chamber 6
On 7.Liquid reagent vapo(u)rization system 11 is activated, solution of organic compound is fitted into liquid reagent vapo(u)rization system 11 and is used as work
Substance.Thickness is that 10 to 20nm protection organic film 5 is formed in sample surfaces, to assign other end user characteristics to table
Face, such as hydrophobicity, oleophobic property, high-wearing feature.
The coating speed of protective coating is selected to be coated by one in each rotation for the substrate carrier 7 for being fixed with sample
The film of layer or two layers of monolayer composition.
When reaching the appointed thickness of protective layer 5, the substance that is stopped supply.Stop substrate carrier 7, empties vacuum chamber
6, and remove the sample with composite coating thereon.
Then, temperature stabilization processing is carried out to sample.
Embodiment 5
In being used to coat the method for protective coating 5 what is be claimed, organosilicon fluorochemical (Dow Corning
2634 (being manufactured by Dow Corning companies of the U.S.)) 1% to 2% solution in fluoride solvent (3M Nevec 7200) uses
Make operation material.The rotary speed of substrate carrier 7 is 2RPM.It needs to spend the coating 5 for forming that thickness is 20nm for 1 minute.As a result
It is that manufactured protective coating 5 is transparent protective film on the surface of adhesive layer 4.
The temperature stabilization of coating carries out one hour at 120 DEG C of temperature and 50% relative air humidity.Temperature is steady
Fixedization provides fluorine-containing protective coating and bonds the covalent bonding between layer surface.
By in every 1cm2Metallized fabrics wear surface is used in surface to be measured under conditions of loading 1kg, carries out protective coating
The abrasion test on surface.
The moistening contact angle of several samples is relative to wear-out period number referring to Fig. 4.Curve shows only to wear week at 5000
Contact angle is moistened after phase is just reduced to 110 ° or less.
The cleaning of the after-processing chamber of complex optics coating application procedures
After removing manufactured goods, plasma chemistry cleaning is carried out to process chamber 6, is formed to remove in protective coating
Remaining organic component and inorganic C compounds are etched away from indoor fitting part later.
Plasma chemistry is cleaned longer interval between making device service maintenance program.In order to remove organic component, make
With the processing using oxygen plasma；It is fluorine-containing or containing chlorine plasma in be removed the etching of inorganic compound.
In order to clean, working gas is supplied in vacuum processing chamber 6 using gas distributed system, working gas is selected from packet
Include NF3、CF4、C4F8、CHF3、O2、Cl2Range.Pressure in room 6 rises to 0.5 to 3Pa, and high-density plasma is activated to send out
Raw system 9.In order to stop cleaning, HF power supplys are deactivated.
Embodiment 6
After removing drum-type substrate carrier 7, cleaned.By working gas (O2) be supplied in process chamber 6.Work pressure
Power rises to 1Pa, and activates high-density plasma generating system 9.Here, HF power densities are about 0.2W/cm3.Indoor table
The time of surface treatment is 3 minutes.Then, O is deactivated2Supply, be changed to supply NF3, use identical operating pressure and high density etc.
Gas ions generating system power supply.Scavenging period is 10 minutes.Then, high-density plasma generating system is deactivated, and is deactivated anti-
Gas is answered to supply.
Now, equipment is ready for next cycle of described method.
Protective coating coats
Second method (modification 2)
The second method for forming protective coating 5 is interrupted using vacuum cycle and is realized, single point is formed using in liquid-gas interface
The method of sub- film.
This method includes：
Single layer, i.e., intensive monolayer are formed on deionized water surface；
Single layer is transferred to substrate (deposition)；
Drying immediately has the substrate of composite coating after film deposition；
Thermal annealing.
Sample, which removes from vacuum chamber 6 and is transferred to conveying equipment, is used to form monomolecular film and multimolecular film.Equipment is used for
The unimolecule protective film with controllable thickness (2 to 10nm) is formed on optical texture surface.
Interrupt cycle the advantages of be make in the range of nonfunctional protective layer's coating procedure anti-reflection coating optical texture into
One step stabilizes.
The schematic diagram of the conveying equipment of unimolecule protective layer is used to form referring to Fig. 5.Substrate 19, as anti-with formation
The substrate of reflectance coating and adhesive layer is dipped into the water-bath 20 with deionized water 21, until transportation system 22.Deionized water
Water level, pH and composition remain unchanged.Meanwhile removable obstacle 23 and cylindrical obstacle 24 are used to form single layer 25, single layer 25 is
The monomolecular film of surfactant with specified packing of molecules density and direction.Surface Tension Sensor 26 is divided for controlling
Sub- bulk density.By in single layer pressure set molecular orientation, the reason is that in monolayer deposition region operation material molecular concentration
The obstacle 23 and 24 of water meter area is limited by setting to provide.Substrate 19 is set to pass through unimolecule of the single layer 25 to generate
Film transfer to composite coating adhesive layer 4.Substrate transmission speed is set in the range of 0.1 to 10mm/s.
During wear-resistant coating is formed, the substrate 19 with complex optics coating is further dried, for example, by using
Following methods：By removing excess liquid on specially designed pallet and/or by making protective coating surface further expose
It is radiated in IR.
Similar to the first embodiment for the complex optics coating manufacture that no vacuum cycle is interrupted, the coating of formation must
It must be stabilized by annealing under specified humidity.
Embodiment 7
Solution (0.5%) of the PFPE in 7200 solvents of 3M Nevec is used as forming the work of single layer on deionized water surface
Make substance.
In surface pressing 30mN/m and transportation system 22 under the movement speed 1mm/s of substrate 19, perfluoropolyether is coated
Film.As a result, the protective layer 5 prepared on the surface of adhesive layer 4 is the sightless hyaline membrane of naked eyes.
Temperature stabilization carries out one hour at 120 DEG C of temperature and 50% relative air humidity.
By in every 1cm2Metallized fabrics wear surface is used in surface to be measured under conditions of loading 1kg, carries out protective coating
The abrasion test on surface.
The moistening contact angle of the coating prepared according to claimed the second embodiment of method relative to wear-out period number,
Referring to Fig. 6.Curve shows that the protective coating ratio prepared according to the method for description does not have vacuum cycle to interrupt completely in a vacuum chamber
The coating of preparation is more wear-resisting.Even if after 15000 wear-out periods water moisten contact angle if be not lowered to 105 ° with
Under.
The embodiment of complex optics coating shaping method proposed by the present invention provides higher processing performance, and energy
It is enough to form the coating that there are more preferable performance characteristics than similar commercial goods.Due to apply high-density plasma enhancing it is equal from
Daughter chemical deposition can form high quality optical layer without additionally heating sample, to keep the mechanical stress in structure minimum
Change.Additional ion beam or plasma chemical treatment makes the size of polycrystal in film minimize, and keeps film amorphous and reduces hole
Porosity, to significantly improve film to the resistance of mechanism and make its stable optical performance.Since material coats stage and its
Oxidation or nitridation stage spatially separate, therefore the film pre-oxidation thickness coated becomes controllable, this can control film in turn
The size of middle polycrystal and the performance of film.
Bibliography
1. U.S. Patent No. 8817376 disclosed on 08 26th, 2014
2. U.S. Patent No. 2014113083 disclosed on 04 24th, 2014
Claims (23)
1. a kind of complex optics coating comprising the multilayer formed by the layer alternately with high index and low refractive index
Anti-reflection coating and protective coating, which is characterized in that form thickness between the anti-reflection coating and the protective coating
It is the adhesive layer of the modification of 5 to 200nm amorphous substance.
2. complex optics coating according to claim 1, wherein the protective coating is made of siliceous perfluoropolyether, with
And the amorphous substance is amorphous silicon oxide.
3. complex optics coating according to claim 2, wherein the protective coating is by with trimethoxy silane alcohol end
The PFPE of base is made.
4. complex optics coating according to claim 1, wherein the layer with high index in the anti-reflection coating
Material be that the material of layer with low refractive index is silica in silicon nitride and the anti-reflection coating.
5. complex optics coating according to claim 1, wherein the alternating layer of the anti-reflection coating, the adhesive layer
It is made in such a way that the basal layer by the monolayer thickness of 1 to 6 layer of suitable material forms with the protective coating.
6. complex optics coating according to claim 1, wherein the roughness of the adhesive layer of the modification meets distribution mark
Quasi- deviation is less than the condition of 2nm.
7. complex optics coating according to claim 1, wherein the thickness of the protective coating is 2 to 20nm.
8. complex optics coating according to claim 1, wherein the protective coating is the list formed in liquid-gas interface
Molecular film.
9. a kind of manufacturing method of complex optics coating, including there is no gas-gas deposition of exhaust in using single vacuum to handle
Multi-layer anti-reflection coating and protective coating are coated on substrate by method and coating stable at elevated temperature, feature
It is, the gas-vapour deposition method enhanced using high-density plasma is in the anti-reflection coating and the protective coating
The adhesive layer of amorphous substance is formed between coating operation, then by being etched in gas discharge plasma and/or
It is modified by ion polishing.
10. the manufacturing method of complex optics coating according to claim 9, wherein each in the anti-reflection coating
The coating procedure of layer and the adhesive layer is realized using two plasma generating systems two stages：Phase in the first stage
Between, a plasma generating system is used to coat basal layer, and during second stage, another plasma system
System repeats described two stages until reaching the appointed thickness for being formed by layer for aoxidizing the basal layer.
11. the manufacturing method of complex optics coating according to claim 9, wherein the protective layer is gathered by siliceous perfluor
Ether is made and amorphous silicon oxide is selected as the amorphous substance.
12. the manufacturing method of complex optics coating according to claim 9, wherein by gas discharge plasma
The modification of the adhesive layer of middle etching it is fluorine-containing or containing chlorine plasma in implement.
13. the manufacturing method of complex optics coating according to claim 9, wherein during coating the protective coating,
Gas-vapour phase of siliceous perfluoropolyether is prepared by solution appropriate by evaporating.
14. the manufacturing method of complex optics coating according to claim 9, wherein carried out using ion polishing method viscous
Close layer modification using energy be 500 to 4000eV and dosage be 0.05 to 1C/cm2Ar or O2Ion is implemented.
15. the manufacturing method of complex optics coating according to claim 9, wherein in the coating of the anti-reflection coating
Period, the basal layer of the suitable substance of 2 to 6 layers of monolayer thickness of coating in the rotation each time of drum-type substrate carrier.
16. the manufacturing method of complex optics coating according to claim 9, wherein during the coating of the adhesive layer,
Basis of the coating no more than the amorphous silicon oxide of 2 layers of monolayer thickness in the rotation each time of drum-type substrate carrier
Layer.
17. the manufacturing method of complex optics coating according to claim 9, wherein in the coating phase of the protective coating
Between, the basis of the siliceous perfluoropolyether of 1 or 2 layer of monolayer thickness of coating in the rotation each time of drum-type substrate carrier
Layer.
18. the manufacturing method of complex optics coating according to claim 9, wherein in the coated of the protective coating
After journey is completed and removes drum-type substrate carrier, vacuum chamber plasma chemistry cleaning operation is sequentially carried out, first in oxygen
Carried out in plasma, then it is fluorine-containing or containing chlorine plasma in carry out.
19. a kind of manufacturing method of complex optics coating, including gas-vapor deposition method is used to be coated on multi-layer anti-reflection coating
It is coated on coating stable on substrate and at elevated temperature on substrate, by protective coating, which is characterized in that using highly dense
Gas-vapour deposition method of degree plasma enhancing shape between the anti-reflection coating and the coating operation of the protective coating
At the intermediate adhesion layer of amorphous substance, then by being etched in gas discharge plasma and/or being thrown by ion
Light is modified, and, the protective coating is formed monomolecular film, and intensive list is formed into liquid-gas interface
Molecular layer, the monolayer are transferred to the surface of the adhesive layer.
20. the manufacturing method of complex optics coating according to claim 19, wherein each layer in the anti-reflection coating
It is realized two stages using two plasma generating systems with the coating procedure of the adhesive layer：During the first stage,
One plasma generating system is used to coat basal layer, and during second stage, another plasma generating system
For aoxidizing the basal layer, described two stages are repeated until reaching the appointed thickness for being formed by layer.
21. the manufacturing method of complex optics coating according to claim 19, wherein the protective layer is gathered by siliceous perfluor
Ether is made and amorphous silicon oxide is selected as the amorphous substance.
22. the manufacturing method of complex optics coating according to claim 19, wherein the coating packet of the protective coating
It includes：The intensive monolayer is formed on deionized water surface, the monolayer is transferred to the surface of the adhesive layer；
The surface of the single layer transfer and/or the protective coating is exposed to after IR radiation immediately by the base with the composite coating
Plate is dried；And by the substrate thermal annealing with the composite coating.
23. the manufacturing method of complex optics coating according to claim 19, wherein at a temperature of 100 to 120 DEG C into
The row coating stable.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/BY2015/000005 WO2017070769A1 (en) | 2015-10-29 | 2015-10-29 | Composite optical coating and method for producing thereof (variants) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108349792A true CN108349792A (en) | 2018-07-31 |
Family
ID=58629751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580082993.4A Pending CN108349792A (en) | 2015-10-29 | 2015-10-29 | Complex optics coating and its manufacturing method（Modification） |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR102398357B1 (en) |
| CN (1) | CN108349792A (en) |
| EA (1) | EA034006B1 (en) |
| WO (1) | WO2017070769A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110218988A (en) * | 2019-06-10 | 2019-09-10 | 浙江水晶光电科技股份有限公司 | AR membrane preparation device, AR membrane preparation method and AR film |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI780166B (en) * | 2017-06-23 | 2022-10-11 | 美商康寧公司 | Coated articles that include easy-to-clean coatings |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4898790A (en) * | 1986-12-29 | 1990-02-06 | Ppg Industries, Inc. | Low emissivity film for high temperature processing |
| JP2003094548A (en) * | 2001-09-26 | 2003-04-03 | Sony Corp | Reflection-proof film |
| CN1946646A (en) * | 2004-02-24 | 2007-04-11 | 法国圣戈班玻璃厂 | Substrate, notably of glass, with a hydrophobic surface having an improved durability of the hydrophobic properties |
| CN102272066A (en) * | 2009-01-09 | 2011-12-07 | 法国圣戈班玻璃厂 | Hydrophobic substrate including a plasma-activated silicon oxycarbide primer |
| CN103382549A (en) * | 2013-07-27 | 2013-11-06 | 中国乐凯集团有限公司 | Production method for multilayered structural high barrier film |
| CN103582617A (en) * | 2011-05-31 | 2014-02-12 | 肖特公开股份有限公司 | Substrate element for coating with an easy-to-clean coating |
| CN104080754A (en) * | 2011-05-31 | 2014-10-01 | 肖特公开股份有限公司 | Substrate element for coating with an easy-to-clean coating |
| CN104321290A (en) * | 2011-11-30 | 2015-01-28 | 康宁股份有限公司 | Process for making of glass articles with optical and easy-to-clean coatings |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4823569B2 (en) * | 2005-05-23 | 2011-11-24 | 株式会社オートネットワーク技術研究所 | Optical glass component and manufacturing method thereof |
| JP6093362B2 (en) * | 2011-09-28 | 2017-03-08 | ビューラー アルツェナウ ゲゼルシャフト ミット ベシュレンクテル ハフツングＢｕｅｈｌｅｒ Ａｌｚｅｎａｕ ＧｍｂＨ | Method and apparatus for generating a reflection reducing layer on a substrate |
| US10185234B2 (en) * | 2012-10-04 | 2019-01-22 | Asml Netherlands B.V. | Harsh environment optical element protection |
-
2015
- 2015-10-29 CN CN201580082993.4A patent/CN108349792A/en active Pending
- 2015-10-29 WO PCT/BY2015/000005 patent/WO2017070769A1/en active Application Filing
- 2015-10-29 EA EA201800042A patent/EA034006B1/en not_active IP Right Cessation
- 2015-10-29 KR KR1020187002205A patent/KR102398357B1/en active IP Right Grant
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4898790A (en) * | 1986-12-29 | 1990-02-06 | Ppg Industries, Inc. | Low emissivity film for high temperature processing |
| JP2003094548A (en) * | 2001-09-26 | 2003-04-03 | Sony Corp | Reflection-proof film |
| CN1946646A (en) * | 2004-02-24 | 2007-04-11 | 法国圣戈班玻璃厂 | Substrate, notably of glass, with a hydrophobic surface having an improved durability of the hydrophobic properties |
| CN102272066A (en) * | 2009-01-09 | 2011-12-07 | 法国圣戈班玻璃厂 | Hydrophobic substrate including a plasma-activated silicon oxycarbide primer |
| CN103582617A (en) * | 2011-05-31 | 2014-02-12 | 肖特公开股份有限公司 | Substrate element for coating with an easy-to-clean coating |
| CN104080754A (en) * | 2011-05-31 | 2014-10-01 | 肖特公开股份有限公司 | Substrate element for coating with an easy-to-clean coating |
| CN104321290A (en) * | 2011-11-30 | 2015-01-28 | 康宁股份有限公司 | Process for making of glass articles with optical and easy-to-clean coatings |
| CN103382549A (en) * | 2013-07-27 | 2013-11-06 | 中国乐凯集团有限公司 | Production method for multilayered structural high barrier film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110218988A (en) * | 2019-06-10 | 2019-09-10 | 浙江水晶光电科技股份有限公司 | AR membrane preparation device, AR membrane preparation method and AR film |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102398357B1 (en) | 2022-05-13 |
| WO2017070769A1 (en) | 2017-05-04 |
| EA201800042A1 (en) | 2018-05-31 |
| KR20180093866A (en) | 2018-08-22 |
| EA034006B1 (en) | 2019-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100465116C (en) | Method for manufacturing layers and layer systems, and coating substrates | |
| Takikawa et al. | Properties of titanium oxide film prepared by reactive cathodic vacuum arc deposition | |
| JP6381649B2 (en) | Inclined thin film | |
| US20070059942A1 (en) | Plasma cvd process for manufacturing multilayer anti-reflection coatings | |
| KR20120139919A (en) | Coating method and appratus for anti-fingerprint and anti-reflection | |
| US10329192B2 (en) | Composition of fingerprint-resistant layer consisting of a plurality of thin films and preparation method therefor | |
| CN102084025A (en) | Film-forming method and oil repellent base | |
| WO2010125926A1 (en) | Antifouling laminate | |
| WO2017029890A1 (en) | Laminate | |
| CN108349792A (en) | Complex optics coating and its manufacturing method（Modification） | |
| JP2014043600A (en) | Film deposition method | |
| Jacobson et al. | Development of silver coating options for the Gemini 8-m telescopes project | |
| JP2007533856A5 (en) | ||
| KR20150114891A (en) | Thin film type transparent glass having high hardness, method for manufacturing the same, thin film type transparent glass having high hardness and conductivity, and touch panel including the same | |
| US6610179B2 (en) | System and method for controlling deposition thickness using a mask with a shadow that varies with respect to a target | |
| CN111908803A (en) | Super-hydrophilic and high-wear-resistance film layer and preparation method thereof | |
| CN105209568A (en) | Composition of fingerprint-resistant layer consisting of a plurality of thin films and preparation method therefor | |
| KR20120130468A (en) | Deposition method of anti-finger layer | |
| CN110465203A (en) | The method for improving the adhesive force of anti-pollution film | |
| JPH11256339A (en) | Water-repellent coating film, contamination preventing product and production of water-repellent coating film | |
| US8900423B2 (en) | Low refractive index material by sputtering deposition method | |
| CN100473754C (en) | Method for obtaining a thin, stabilized fluorine-doped silica layer, resulting thin layer and use thereof in ophthalmic optics | |
| KR20140050057A (en) | Antireflection glazing unit equipped with a porous coating | |
| JP2008062561A (en) | Method of manufacturing article equipped with hydrophilic laminated film, and article equipped with hydrophilic laminated film | |
| WO2007117603A2 (en) | Nanofilm compositions and methods of manufacture and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180731 |