CN106277811A - A kind of glass substrate and the film plating process of glass surface - Google Patents
A kind of glass substrate and the film plating process of glass surface Download PDFInfo
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- CN106277811A CN106277811A CN201610662629.1A CN201610662629A CN106277811A CN 106277811 A CN106277811 A CN 106277811A CN 201610662629 A CN201610662629 A CN 201610662629A CN 106277811 A CN106277811 A CN 106277811A
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- Prior art keywords
- glass
- microsphere
- film
- glass substrate
- reverse micelle
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- 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
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- 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
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
- C03C17/2453—Coating containing SnO2
-
- 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
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
- C03C17/2456—Coating containing TiO2
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
Abstract
The invention provides a kind of glass substrate, by glass, through reverse micelle microsphere microemulsion surface, process obtains for it；Described reverse micelle microsphere microemulsion includes non-polar solven and the chemical corrosion liquid of surfactant parcel；Described glass substrate has micrometer grade hole hole.The invention provides the film plating process of a kind of glass surface, use reverse micelle microsphere microemulsion that glass is carried out surface process, obtain the glass substrate with micrometer grade hole hole；Plated film on described glass baseplate surface, obtains the glass material after plated film.Present invention application reverse micelle microsphere etching glass surface, forms the structure in micrometer grade hole hole；Gained glass substrate is that micrometer grade hole cheats glass, and it presents loose structure, and surface area is big.The present invention carries out plated film at described micrometer grade hole hole glass surface, and film can be embedded in glass orifice, can obtain the three-dimensional membrane structure of tangent plane undulate.The film plating process utilizing the glass substrate that the present invention provides improves between thin film and substrate and adhesion between film layer.
Description
Technical field
The present invention relates to coating technique field, particularly relate to the film plating process of a kind of glass substrate and glass surface.
Background technology
Glass material has good optics, electricity, mechanically and chemically stability, and therefore glass substrate is at optics device
Part, microwave device, building aspect and automobile aspect etc. have a wide range of applications.At glass surface plating, alloy or metal
Oxidation film, can give the function that glass is new, generally be widely used in the fields such as building, photovoltaic, electronics.
Existing coating film on glass technology mainly includes magnetron sputtering method, sol-gel technique, chemical vapour deposition technique, true
Empty evaporation coating techniques etc., wherein, the adhesiveness between film and glass has been largely fixed thin film in actual applications
Reliability and stability.It is the most chemical that the Chinese patent literature of Publication No. CN 103613289 A discloses one
Copper coating, the method includes: one layer of organic film of coating on the glass substrate, uses traditional chemical copper facing work after drying again
Process copper layer；Wherein organic film preparation method comprises the following steps: (1) by organic film material with 0.1%～
The percent by volume of 20% is dissolved in volatile organic solvent；(2) by described organic solvent with spin coating, spray, soak or be coated with
Brush method is coated on glass substrate；(3) glass substrate of described organic solvent to be coated is dried or dries；(4) by glass
Substrate uses the characteristic of organic film material to carry out imidization or hot setting.
Said method is mainly by coating one layer of organic film at glass baseplate surface, then uses tradition copper coating to enter
Row plated film, this can improve the adhesion between thin film and glass substrate to a certain extent.But due to glass body and membrane material
Heterogeneity, and interface mainly combines by physical action, chemical action, therefore, it is also desirable to there is more feasible method
Further enhance the adhesion of film and glass, thus improve stability and the reliability of film function.
Summary of the invention
In view of this, the application provides the film plating process of a kind of glass substrate and glass surface, uses the present invention to provide
Glass substrate carries out plated film, can improve the adhesion between thin film and matrix and film layer.
The present invention provides a kind of glass substrate, and by glass, through reverse micelle microsphere microemulsion surface, process obtains for it；Described instead
Micelle microsphere microemulsion includes non-polar solven and the chemical corrosion liquid of surfactant parcel；
Described glass substrate has micrometer grade hole hole.
Preferably, during described non-polar solven is selected from linear paraffin, substituted straight chain alkane, branched paraffin and aromatic hydrocarbon
Plant or several.
Preferably, described surfactant is selected from sodium alkyl benzene sulfonate, sodium alkyl sulfonate, sodium alkyl sulfate, fatty alcohol
Polyethenoxy ether sodium sulfate, sodium alkyl sulfonate etc., Dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, 16
Alkyl front three ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, cetyl trimethyl ammonium heteropoly acids, dodecyl Radix Betae
Alkali, N-amido propyl dimethyl carboxymethyl ammonium glycine betaine, polyol-based non-ionic surfactant, polyoxyethylene-type nonionic table
One or more in face activating agent and PULLRONIC F68 type nonionic surfactant.
Preferably, described chemical corrosion liquid is selected from acids corrosive liquid or bases corrosive liquid.
Preferably, described reverse micelle microsphere microemulsion also includes alcohol.
The present invention provides the film plating process of a kind of glass surface, comprises the following steps:
A) use reverse micelle microsphere microemulsion that glass is carried out surface process, obtain the glass base with micrometer grade hole hole
Plate；Described reverse micelle microsphere microemulsion includes non-polar solven and the chemical corrosion liquid of surfactant parcel；
B) plated film on described glass baseplate surface, obtains the glass material after plated film.
Preferably, described step A) in, described non-polar solven from linear paraffin, substituted straight chain alkane, branched paraffin and
One or more in aromatic hydrocarbon；Described chemical corrosion liquid is selected from acids corrosive liquid or bases corrosive liquid.
Preferably, described step A) in, the time that described surface processes is 0.5h～10h, the temperature that described surface processes
It it is 10 DEG C～120 DEG C.
Preferably, described step B) in, the mode of described plated film is magnetron sputtering method or chemical vapour deposition technique.
Preferably, described step A) also include before: use cleanout fluid that glass is washed, the glass after being washed
Glass；Described cleanout fluid includes aqueous solution or anhydrous solvent；
Described step A) be: use reverse micelle microsphere microemulsion that the glass after washing is carried out surface process, cleaned,
To the glass substrate with micrometer grade hole hole.
Compared with prior art, present invention application reverse micelle microsphere etching glass surface, form the structure in micrometer grade hole hole；
Gained glass substrate is that micrometer grade hole cheats glass, and it presents loose structure, and surface area is big, and Stability Analysis of Structures is wear-resisting.Further, this
Bright described micrometer grade hole hole glass surface carry out plated film, film can be embedded in glass orifice, can obtain tangent plane undulate
Three-dimensional membrane structure.Therefore, the film plating process utilizing the glass substrate that the present invention provides not only increases between thin film and substrate
Adhesion, and improve the adhesion between film layer, thus improve stability and the reliability of film function, it is beneficial to application.
Accompanying drawing explanation
Fig. 1 is the surface SEM figure of the micrometer grade hole hole glass that embodiment 1 prepares；
Fig. 2 is the section SEM figure of the micrometer grade hole hole glass that embodiment 1 prepares；
Fig. 3 is the surface atom force microscope 3D figure of the micrometer grade hole hole glass that embodiment 1 prepares；
Fig. 4 is the surface laser microscope 3D figure of the micrometer grade hole hole glass that embodiment 1 prepares；
Fig. 5 is embodiment 1 surface SEM figure of plated film on glass micrometer grade hole hole；
Fig. 6 is embodiment 1 section SEM figure of plated film on glass micrometer grade hole hole；
Fig. 7 is the scratch test figure of AZO thin film on former sheet glass surface；
Fig. 8 is the scratch test figure of AZO thin film on cellular glass surface of the present invention.
Detailed description of the invention
Below the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment
It is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained under not making creative work premise, broadly falls into the model of present invention protection
Enclose.
The invention provides a kind of glass substrate, by glass, through reverse micelle microsphere microemulsion surface, process obtains for it；Described
Reverse micelle microsphere microemulsion includes non-polar solven and the chemical corrosion liquid of surfactant parcel；
Described glass substrate has micrometer grade hole hole.
The glass substrate that the present invention provides is that micrometer grade hole cheats glass, and it presents loose structure, and surface area is big, and structure is steady
Fixed, wear-resisting, beneficially plated film.
The glass baseplate surface that the embodiment of the present invention provides has hole, hole pattern, and wherein, hole can be 100nm～600nm deeply,
Near coal-mine wide be 1 μm～3 μm, i.e. have micrometer grade hole hole.Described glass substrate by glass through reverse micelle microsphere microemulsion
Surface processes and obtains, and wherein, described glass is substrate commonly used in the art or substrate material, and the present invention is not particularly limited.?
In the embodiment of the present invention, glass-cutting can become required size carry out subsequent treatment.Present invention preferably employs the glass after washing
Carry out surface process；Glass after described washing can use cleanout fluid washing to obtain.
In an embodiment of the present invention, described cleanout fluid includes aqueous solution or anhydrous solvent, can be the impurity of glass surface
Clean up, but do not make its surface texture produce change.Wherein, described aqueous solution such as water, acid solution, aqueous slkali or detergent
Aqueous solution etc.；Described anhydrous solvent such as ethanol, acetone or emulsion etc..Described cleanout fluid is preferably distilled water, dilute hydrochloric acid, dilute sulfur
Two or more in acid, ammonia, dehydrated alcohol, distilled water and acetone.Herein, it is two or more when cleanout fluid
During material, both or two or more material is i.e. used to be respectively washed glass.Described cleanout fluid is more preferably dilute hydrochloric acid, dilute sulfur
Acid, ammonia, dehydrated alcohol, distilled water and acetone；Wherein, the mass concentration of dilute hydrochloric acid and dilute sulfuric acid can be 5%～20%, as
7%.In an embodiment of the present invention, when using cleanout fluid cleaning glass, dilute hydrochloric acid, dilute sulfuric acid, ammonia, dehydrated alcohol, distillation
The volume ratio of water and acetone is preferably (1～2): (1～2): (1～2): (10～20): (10～20): (10～20), more preferably
For (1～1.8): (1～1.8): (1～1.8): (12～18): (12～18): (12～18).Herein, described volume ratio represents phase
Volume ratio relation between Hu, does not limit use order and kind.
Glass can be washed by the present invention by cleanout fluid the most successively；In some embodiments of the invention, described
Cleanout fluid is followed successively by dilute hydrochloric acid, acetone, distilled water.In some embodiments of the invention, described cleanout fluid is followed successively by acetone, second
Alcohol, distilled water.In other embodiments of the present invention, described cleanout fluid is followed successively by dilute hydrochloric acid, distilled water.Another in the present invention
In some embodiments, described cleanout fluid is followed successively by ammonia, acetone, distilled water.In other embodiments of the present invention, described clearly
Washing liquid is followed successively by dilute sulfuric acid, dehydrated alcohol, distilled water.In these embodiments, the ratio of material used is satisfied by above-mentioned volume
Ratio.
Present invention application reverse micelle microsphere microemulsion etching glass surface, forms the structure in micrometer grade hole hole and improves table
Area.Described reverse micelle microsphere microemulsion is also referred to as reverse micelle microsphere liquid, reverse micelle microsphere emulsion etc., and it includes non-polar solven.
Described non-polar solven preferably is selected from one or more in linear paraffin, substituted straight chain alkane, branched paraffin and aromatic hydrocarbon, as just
The linear paraffins such as hexane, normal heptane, normal octane, n-nonane, n-decane, isopentane, neopentane, 3-methyl-5 ethyl octane, 2,
The branched paraffins such as 3-dimethylbutane, 5-propyl group-4-isopropyl nonane, the aromatic hydrocarbon such as benzene or alkylbenzene, and carbon tetrachloride, two
The substituted straight chain alkane such as chlorination carbon.Described non-polar solven more preferably one or more in linear paraffin and branched paraffin；
In some embodiments of the invention, described non-polar solven is normal hexane and 3-methyl-5-ethyl octane.In the present invention one
In a little embodiments, described non-polar solven is pentane.In other embodiments of the present invention, described non-polar solven is just
Heptane and isopentane.In other embodiments of the present invention, described non-polar solven is n-decane and 5-propyl group-4-isopropyl
Nonane.In other embodiments of the present invention, described positive polarity solvent is isopentane and 3-methyl-5-ethyl octane.Work as institute
Stating non-polar solven when being two kinds of materials, both volume ratios can be 1:1.
In the present invention, described reverse micelle microsphere microemulsion includes the chemical corrosion liquid that surfactant wraps up.Wherein, institute
State surfactant and include that cationic surfactant, anion surfactant, amphoteric surfactant, non-ionic surface are lived
Property agent etc., preferably cationic surfactant or anion surfactant.Described surfactant is more preferably from alkylbenzene
The anionic surfaces such as sodium sulfonate, sodium alkyl sulfonate, sodium alkyl sulfate, polyoxyethylenated alcohol sodium sulfate, sodium alkyl sulfonate
Activating agent, Dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, cetyl front three ammonium chloride, dodecyl
The cationic surfactants such as dimethyl benzyl ammonium chloride, cetyl trimethyl ammonium heteropoly acids, empgen BB, N-
The amphoteric surfactantes such as amido propyl dimethyl carboxymethyl ammonium glycine betaine, polyol type, polyoxyethylene-type and polyoxyethylene-poly-
The nonionic surfactants such as oxypropylene type；Selected surfactant be preferably therein one or more.
In the present invention, the chemical corrosion liquid of described surfactant parcel aqueous.Described chemical corrosion liquid preferably is selected from acid
Class corrosive liquid or bases corrosive liquid, such as HCl, H2SO4、HNO3、HF、HPO3、H2CO3、CH3The acids corrosive liquids such as COOH solution,
NaOH、KOH、NaHCO3、Na2HPO4、NH4The bases corrosive liquids such as OH solution, selected chemical corrosion liquid is one therein or several
Kind.Described chemical corrosion liquid is more preferably from HCl, H2SO4、HNO3、HF、H2CO3、CH3COOH、NaOH、KOH、NaHCO3、Na2HPO4
And NH4Two or more solution in OH；Wherein, H2SO4Mass concentration can be 98%, the mass concentration of HF can be
The mass concentration of 40%, HCl can be 37%, and the concentration of bases corrosive liquid is preferably 0.1M～1M.Some enforcements in the present invention
In example, described chemical corrosion liquid includes H2SO4And HF.In some embodiments of the invention, described chemical corrosion liquid includes
H2SO4, HF and HCl.In other embodiments of the present invention, described chemical corrosion liquid includes KOH and NaHCO3.In the present invention
Other embodiments in, described chemical corrosion liquid includes.NaOH and Na2HPO4.In other embodiments of the present invention, institute
Stating chemical corrosion liquid is HF.
Wherein, HCl, H2SO4、HNO3、HF、H2CO3、CH3COOH、NaOH、KOH、NaHCO3、Na2HPO4、NH4OH mole
Than being preferably (2～5): (0.2～5): (0.2～5): (2～20): (2～5): (0.2～5): (0.2～5): (2～20): (2
～5): (0.2～5): (0.2～5): (2～20), more preferably (2～5): (0.3～5): (0.3～5): (2～18): (2～
5): (0.3～5): (0.3～5): (2～18): (2～5): (0.3～5): (0.3～5): (2～18).Herein, described mol ratio
The proportionate relationship of the amount of expression material each other, does not limit kind.When the chemical corrosion liquid of above-mentioned aqueous chooses two
When kind or three kinds of solution, it is satisfied by above-mentioned molar ratio.
In the present invention, described reverse micelle microsphere microemulsion the most also includes alcohol, more preferably includes the alcohol of C2～C12.Institute
State alcohol include but not limited to normal propyl alcohol, glycerol, n-butyl alcohol, 1,4-butanediol, n-amyl alcohol, hexanol, n-heptanol, n-octyl alcohol,
Isopropanol, isoamyl alcohol, preferably glycerol, n-butyl alcohol, BDO or isoamyl alcohol.
In the present invention, described reverse micelle microsphere microemulsion may be simply referred to as emulsion, microemulsion, reactant liquor.In the present invention one
In a little embodiments, described reactant liquor preferably include normal hexane, normal heptane, normal octane, n-nonane, n-decane, isopentane, new penta
Alkane, 3-methyl-5-ethyl octane, 2,3-dimethylbutane, 5-propyl group-4-isopropyl nonane, benzene or alkylbenzene, carbon tetrachloride,
One or more non-polar solvens in carbon dichloride and the combination of alcohol, more preferably normal hexane, normal heptane, normal octane, positive nonyl
Alkane, n-decane, isopentane, neopentane, 3-methyl-5 ethyl octane, 2,3-dimethylbutane, 5-propyl group-4-isopropyl nonane,
The combination of a kind of and alcohol in benzene or alkylbenzene, carbon tetrachloride, carbon dichloride.Now, described normal hexane, normal heptane, normal octane,
N-nonane, n-decane, isopentane, neopentane, 3-methyl-5 ethyl octane, 2,3-dimethylbutane, 5-propyl group-4-isopropyl nonyl
The mol ratio of a kind of and alcohol in alkane, benzene or alkylbenzene, carbon tetrachloride, carbon dichloride is preferably (1～3): (0.1～1).
The source of described reverse micelle microsphere microemulsion is not particularly limited by the present invention, prepares the most in accordance with the following methods
Arrive: non-polar solven and alcohol are mixed in water, add surfactant, obtain oil phase；Chemical corrosion liquid is added described oil
Phase, mixing, obtain reverse micelle microsphere microemulsion.Wherein, the temperature of two step mixing is both preferably room temperature, more preferably 20 DEG C～50
℃.The time of two step mixing is both preferably 2h～20h, more preferably 5～20h.The present invention is to described reverse micelle microsphere microemulsion
Consumption be also not particularly limited, can submergence or cover glass surface.
Present invention also offers the film plating process of a kind of glass surface, comprise the following steps:
A) use reverse micelle microsphere microemulsion that glass is carried out surface process, obtain the glass base with micrometer grade hole hole
Plate；Described reverse micelle microsphere microemulsion includes non-polar solven and the chemical corrosion liquid of surfactant parcel；
B) plated film on described glass baseplate surface, obtains the glass material after plated film.
The glass surface film plating process that the present invention provides is a kind of three-dimensional coating technique, can improve thin film and glass substrate,
And the adhesion between film layer.
Glass-cutting can be become required size by the embodiment of the present invention, carries out subsequent treatment.Described glass is commonly used in the art
Substrate or substrate material, the present invention is not particularly limited.The present invention the most also includes: use cleanout fluid to wash glass
Wash, the glass after being washed.
Glass, before surface processes, is put in cleanout fluid and is washed or clean, glass surface by the embodiment of the present invention
Impurity clean up, and the structure of glass surface does not produce change, beneficially subsequent treatment.Described cleanout fluid preferably includes water
Solution or anhydrous solvent, its content is consistent with previously described corresponding contents, and this is no longer going to repeat them.Enforcement in the present invention
In example, the preferred ultrasonic cleaning of mode of described washing；Can ultrasonic cleaning 1min～120min, preferably 10min～100min.
Obtain cleanout fluid process after glass after, the embodiment of the present invention by it in reverse micelle microsphere microemulsion, necessarily
Temperature range carries out surface process, after processing a period of time, obtains micrometer grade hole hole glass, namely has micrometer grade hole hole
Glass substrate.
In the present invention, described reverse micelle microsphere microemulsion includes that the chemistry of non-polar solven and surfactant parcel is rotten
Erosion liquid.The present invention uses reverse micelle microsphere microemulsion that glass is carried out surface process, in processing procedure, and this emulsion and glass table
Face is reacted, and makes micrometer grade hole hole structure at glass surface.This reaction is hydro-thermal reaction, can etching glass surface.Through institute
State reaction treatment, surface can be obtained there is the glass in micrometer grade hole hole, be glass substrate described above.
Wherein, the content of described reverse micelle microsphere microemulsion is as it was noted above, this is no longer going to repeat them.As preferably,
When reverse micelle microsphere microemulsion is clarified, then glass is put into wherein carry out surface process.The time that described surface processes is preferred
For 0.5h～10h, more preferably 1h～10h, most preferably 1h～9h.The temperature that described surface processes is preferably 10 DEG C～120
DEG C, more preferably 20 DEG C～120 DEG C, most preferably 30 DEG C～100 DEG C.
After obtaining the glass after reaction treatment, the present invention the most also includes being carried out, and obtains having micrometer grade hole
The glass substrate in hole.
In the present invention, the most also include after described hydro-thermal reaction putting into glass in cleanout fluid clean 5min～
100min, more preferably cleans 10min～90min, most preferably cleans 15min～60min.Described cleanout fluid preferably is selected from dilute salt
One or more in acid, dilute sulfuric acid, dehydrated alcohol, distilled water and acetone, more preferably dilute hydrochloric acid, dilute sulfuric acid, dehydrated alcohol,
Two or more in distilled water and acetone.Herein, when cleanout fluid is two or more material, i.e. use this two
Plant or two or more material is respectively washed glass.Described cleanout fluid is most preferably dilute hydrochloric acid, dilute sulfuric acid, dehydrated alcohol, distilled water
And acetone；The embodiment of the present invention use cleanout fluid clean glass time, dilute hydrochloric acid, dilute sulfuric acid, ammonia, dehydrated alcohol, distilled water and
The volume ratio of acetone is preferably (1～2): (1～2): (1～2): (10～20): (10～20): (10～20), and more preferably (1
～1.8): (1～1.8): (1～1.8): (12～18): (12～18): (12～18).Herein, described volume ratio represent mutual it
Between volume ratio relation, use order and kind are not limited.
Glass can be carried out by the present invention by cleanout fluid the most successively；In some embodiments of the invention, described
Cleanout fluid is preferably distilled water.For ease of distinguishing, before can being processed on surface, cleanout fluid used is referred to as the first cleanout fluid, surface
Cleanout fluid used after reason is referred to as the second cleanout fluid.In the present invention, the mode of above-mentioned cleaning is preferably ultrasonic cleaning.Above-mentioned super
Sound is preferably after cleaning and air-dries, and described air-dried mode is not defined by the present invention, uses those skilled in the art to know
The mode air-dried, can be that nitrogen dries up or hot blast drying etc..
The glass of the present invention is after above-mentioned process, and surface presents " cratered " shape pattern of more rule, and it is the most micro-
Meter level.The present invention carries out plated film on the surface of such glass substrate, obtains the glass material after plated film, and its surface has cuts
Face is wavy three-dimensional membrane structure.
In an embodiment of the present invention, the mode of described plated film can be magnetron sputtering method or chemical vapour deposition technique (CVD).
Magnetron sputtering method plated film is not particularly limited by the present invention, can plate a tunic or multilayer film；Al-Doped ZnO film can be plated
(AZO film), indium tin oxide films (ito thin film), titanium deoxid film, diamond like carbon film (DLC film), SiCO siloxicon film
In one or more.The present invention is coated with thin film to chemical vapour deposition technique and is also not particularly limited, it is preferred to use atmospheric pressure cvd method
Plated film；SnO can be coated with2: F (FTO) thin film, SnO2:F/SnO2: Sb (SUN-E) thin film etc..
In sum, the present invention not only increases the bonded area between thin film and substrate and film layer, and film embeds simultaneously
In glass orifice, all improve the adhesion between thin film and substrate and film layer, thus improve film function stability and can
By property, it is beneficial to application.
In order to be further appreciated by the application, the glass substrate that the application provided below in conjunction with embodiment and glass surface
Film plating process is specifically described.
In following example, involved solution concentration is mass concentration.Glass used is purchased from the prosperous public affairs of Hainan Air China three
Department, it is common float glass process soda-lime-silica glass, and thickness is 3mm, and composition sees table 1, and table 1 is the one-tenth of glass used by the embodiment of the present invention
Point.
The composition of glass used by table 1 embodiment of the present invention
Embodiment 1
Glass-cutting is become required size.
Glass is put into ultrasonic cleaning 10min in cleanout fluid: in the ratio of 1:10:10 measure dilute hydrochloric acid (7%), acetone,
Distilled water, i.e. measures 10mL dilute hydrochloric acid, 100mL acetone, 100mL distilled water, is carried out glass clearly by cleanout fluid the most successively
Wash.
Glass after being processed by cleanout fluid is put in reverse micelle microsphere liquid, carries out reaction treatment.The tool of reverse micelle microsphere liquid
Body compound method includes: in the ratio of 10:10:1, measures normal hexane (30mL), 3-methyl-5-ethyl octane (30mL) and the third three
Alcohol (3mL), in the teflon seal container filling distilled water, adds surfactant sodium dodecyl base trimethylammonium bromide
3g, measures 1mL H2SO4And 1mL HF (40%) is in the above-mentioned teflon seal container filling oil phase, by upper (98%)
State reagent mixing, after stirring, be configured to reverse micelle microsphere liquid.Stirring, after reverse micelle microsphere liquid is clarified, by above-mentioned washing
After glass substrate put in this emulsion, under conditions of temperature is 60 DEG C surface process 5h.
Glass after reaction treatment is put into ultrasonic cleaning 10min in distilled water, surface must be arrived there is micrometer grade hole hole
Glass, i.e. micrometer grade hole hole glass.
Gained micrometer grade hole hole glass is carried out morphology observation, analysis, and Fig. 1 is the micrometer grade hole that embodiment 1 prepares
The surface SEM figure of hole glass, Fig. 2 is the cross section SEM figure of the micrometer grade hole hole glass that embodiment 1 prepares, and Fig. 3 is embodiment
The atomic force microscope 3D figure of the micrometer grade hole hole glass that 1 prepares, Fig. 4 is the micrometer grade hole hole that embodiment 1 prepares
The surface laser microscope 3D figure of glass.From Fig. 1 and Fig. 2 it is clear that the glass surface after surface processes has hole, hole
Pattern, hole is 100nm～600nm deeply, near coal-mine a width of 1 μm～3 μm.Further, Fig. 3 scope of testing is 25*25 micron, sweep speed
For 1Hz；Fig. 4 laser microscope test scope is 95*70 micron.Glass table after the further visible surface of Fig. 3 and Fig. 4 processes
Mask has micrometer grade hole to cheat.
Embodiment 2
Glass-cutting is become required size.
Glass is put into ultrasonic cleaning 10min in cleanout fluid: measure acetone, ethanol, distilled water in the ratio of 3:3:2, i.e.
Measure 60mL acetone, 60mL ethanol, 40mL distilled water, the most successively glass is carried out by cleanout fluid.
Glass after being processed by cleanout fluid is put in reverse micelle microsphere liquid, carries out reaction treatment.The tool of reverse micelle microsphere liquid
Body compound method includes: in the ratio of 10:1, measures pentane (60mL) and n-butyl alcohol (6mL) in the polytetrafluoro filling distilled water
Ethylene seals in container, adds surfactant sodium alkyl benzene sulfonate and Dodecyl trimethyl ammonium chloride 3g, measures 1mL
H2SO4(98%), 0.5mL HF (40%) and 0.5mLHCl (37%) is in the above-mentioned teflon seal container filling oil phase
In, after mix homogeneously, it is configured to reverse micelle microsphere liquid.Stirring, after reverse micelle microsphere liquid is clarified, by the glass after above-mentioned washing
Substrate is put in this emulsion, and under conditions of temperature is 90 DEG C, surface processes 1h.
Glass after reaction treatment is put into ultrasonic cleaning 10min in distilled water, surface must be arrived there is micrometer grade hole hole
Glass.
Embodiment 3
Glass-cutting is become required size.
Glass is put into ultrasonic cleaning 10min in cleanout fluid: measure dilute hydrochloric acid (7%), distilled water in the ratio of 1:15, i.e.
Measure 10mL dilute hydrochloric acid, 150mL distilled water, the most successively glass is carried out by cleanout fluid.
Glass after being processed by cleanout fluid is put in reverse micelle microsphere liquid, carries out reaction treatment.The tool of reverse micelle microsphere liquid
Body compound method includes: in the ratio of 10:10:1, measures normal heptane (30mL), isopentane (30mL) and glycerol (3mL) in Sheng
Have in the teflon seal container of distilled water, add surfactant sodium dodecyl base trimethylammonium bromide 3g, measure 1mL
KOH solution, 1mL NaHCO3Solution in the above-mentioned teflon seal container filling oil phase, KOH and NaHCO3Concentration is respectively
For 0.7M, 0.3M.After mix homogeneously, it is configured to reverse micelle microsphere liquid.Stirring, after reverse micelle microsphere liquid is clarified, washes above-mentioned
Glass substrate after washing is put in this emulsion, and under conditions of temperature is 70 DEG C, surface processes 3h.
Glass after reaction treatment is put into ultrasonic cleaning 30min in distilled water, surface must be arrived there is micrometer grade hole hole
Glass.
Embodiment 4
Glass-cutting is become required size.
Glass is put into ultrasonic cleaning 10min in cleanout fluid: measure ammonia, acetone, distilled water in the ratio of 1:15:15,
I.e. measure 10mL ammonia, 150mL acetone, 150mL distilled water, the most successively glass is carried out by cleanout fluid.
Glass after being processed by cleanout fluid is put in reverse micelle microsphere liquid, carries out reaction treatment.The tool of reverse micelle microsphere liquid
Body compound method includes: in the ratio of 10:10:1, measures n-decane (30mL), 5-propyl group-4-isopropyl nonane (30mL) and 1,
4-butanediol (3mL), in the teflon seal container filling distilled water, adds surfactant sodium alkyl benzene sulfonate 3g,
Measure 1mL NaOH solution and 1mLNa2HPO4Solution in the above-mentioned teflon seal container filling oil phase, NaOH solution
And Na2HPO4The concentration of solution is respectively 0.8M, 0.2M, after mix homogeneously, is configured to reverse micelle microsphere liquid.Stirring, treats reverse micelle
After the clarification of microsphere liquid, putting in this emulsion by the glass substrate after above-mentioned washing, under conditions of temperature is 40 DEG C, surface processes
6h。
Glass after reaction treatment is put into ultrasonic cleaning 20min in distilled water, surface must be arrived there is micrometer grade hole hole
Glass.
Embodiment 5
Glass-cutting is become required size.
Glass is put into ultrasonic cleaning 10min in cleanout fluid: measure dilute sulfuric acid (7%), anhydrous second in the ratio of 1:10:10
Alcohol, distilled water, i.e. measure 10mL dilute sulfuric acid (7%), 100mL dehydrated alcohol, and 100mL distilled water, the most successively by cleanout fluid
Glass substrate is carried out.
Glass after being processed by cleanout fluid is put in reverse micelle microsphere liquid, carries out reaction treatment.The tool of reverse micelle microsphere liquid
Body compound method includes: in the ratio of 15:15:2, measures isopentane (30mL), 3-methyl-5 ethyl octane (30mL) and isoamyl
Alcohol (4mL), in the teflon seal container filling distilled water, adds surfactant sodium dodecyl base trimethylammonium bromide
1.5g and cetyl front three ammonium chloride 1.5g, measures 2ml HF (40%) and holds in the above-mentioned teflon seal filling oil phase
In device, after mix homogeneously, it is configured to reverse micelle microsphere liquid.Stirring, after reverse micelle microsphere liquid is clarified, by the glass after above-mentioned washing
Glass substrate is put in this emulsion, and surface processes 9h at normal temperatures.
Glass after reaction treatment is put into ultrasonic cleaning 30min in distilled water, surface must be arrived there is micrometer grade hole hole
Glass.
Embodiment 6
Magnetron sputtering AZO film
In magnetron sputtering process, carry out the setting of parameter.Selecting zinc oxide and quality of alumina ratio is the AZO of 98:2
Target, fixing target-substrate distance is 50mm, operating air pressure is 0.5Pa, sputtering power is 300W, and argon gas flow is 60sccm, sputtering
Time is 40min, chooses that simple glass (former sheet glass) and embodiment 1 gained micrometer grade hole hole glass is each a piece of to be spattered simultaneously
Penetrate, respectively obtain the glass material after plated film.Simple glass is purchased from Hainan Air China San Xin Corporation, and it is common float glass process sodium calcium silicon glass
Glass, thickness is 3mm, and composition sees table 1.
The impact that at two kinds of glass surfaces, magnetron sputtering is plated monolayer AZO thin film is studied, in the embodiment of the present invention 6,
On cellular glass surface, the scanning electron microscope (SEM) photograph of AZO film is as shown in Figure 5 and Figure 6, and Fig. 5 is that embodiment 1 is on glass micrometer grade hole is cheated
The surface SEM figure of plated film, Fig. 6 is embodiment 1 section SEM figure of plated film on glass micrometer grade hole hole.By nanometer mechanics system
System instrument tests cut according to known method, and in the embodiment of the present invention 6, on two kinds of glass surfaces, the scratch test of AZO thin film is surveyed
As shown in Figure 7 and Figure 8, Fig. 7 is the scratch test figure of AZO thin film on former sheet glass surface, and Fig. 8 is cellular glass table of the present invention in examination
The scratch test figure of AZO thin film on face, data are shown in Table 2, and table 2 is AZO thin film on cellular glass of the present invention and former sheet glass surface
Scratch test comparing result.As shown in Table 2, compared with at the glass substrate that surface is plane, thin on cellular glass surface
Between film and substrate, and the adhesion between film layer compare increasing more than ten times larger.
The scratch test comparing result of AZO thin film on table 2 cellular glass of the present invention and former sheet glass surface
| Marginal value | |
| Former sheet glass | 4.85mN |
| Micrometer grade hole hole glass (cellular glass) | 50.04mN |
Embodiment 7
Magnetron sputtering ito thin film
In magnetron sputtering process, carry out the setting of parameter.Choosing ITO is sputtering target material, opens desired gas, fixing target
Cardinal distance is 50mm, operating air pressure is 1.0Pa, sputtering power is 200W, and argon gas flow is 50sccm, and sputtering time is
20min, chooses that simple glass and micrometer grade hole hole glass is each a piece of to be sputtered simultaneously, respectively obtains the glass material after plated film
Material.
The impact that at two kinds of glass surfaces, magnetron sputtering is plated monolayer ito thin films is studied: in by embodiment 7 two
The ito thin film planted on glass surface carries out scratch test test, compared with at the glass substrate that surface is plane, at cellular glass
On surface between thin film and substrate, and the adhesion between film layer compares increase more than 15 times.
Embodiment 8
Magnetron sputtering titanium deoxid film
In magnetron sputtering process, carry out the setting of parameter.Choosing titanium dioxide is target, opens desired gas, fixing
Target-substrate distance is 50mm, operating air pressure is 0.5Pa, sputtering power is 200W, and argon gas flow is 60sccm, and sputtering time is
40min, chooses that simple glass and micrometer grade hole hole glass is each a piece of to be sputtered simultaneously, respectively obtains the glass material after plated film
Material.
The impact that at two kinds of glass surfaces, magnetron sputtering is plated monolayer titanium deoxid film is studied, by embodiment
In 8, the titanium deoxid film on two kinds of glass surfaces carries out scratch test test, compared with at the glass substrate that surface is plane,
On cellular glass surface between thin film and substrate, and the adhesion between film layer compares increase more than 13 times.
Embodiment 9
Magnetron sputtering two thin walls: SiCO and DLC film
In magnetron sputtering process, carry out the setting of parameter.Select SiCO target and DLC target, open desired gas, fixing target
Cardinal distance is 50mm, operating air pressure be 0.5Pa, DLC target as sputter power be 200W, SiCO target as sputter power be 150W, argon
Gas flow is 80sccm, and temperature is set as 200 DEG C, and sputtering time is respectively 20min, chooses simple glass and cheats glass with micrometer grade hole
Glass is each a piece of to be sputtered simultaneously, respectively obtains the glass material after plated film.
Magnetron sputtering is studied in the impact of two kinds of double-deck SiCO of glass surface plating and DLC film: by enforcement
In example 9, the double-deck SiCO on two kinds of glass surfaces and DLC film carry out scratch test test, data and the glass on surface being plane
Glass substrate is compared, on cellular glass surface between thin film and substrate, and the adhesion between film layer compare increase nine times with
On.
Embodiment 10
Atmospheric pressure cvd method is coated with SnO2: F (FTO) thin film
In atmospheric pressure cvd coating process, major parameter is provided that chooses monobutyl-tin-trichloride and trifluoroacetic acid and water is
Raw material, this experiment carrier gas used is mainly dry air (can be directly as carrier gas and oxidant), and carrier gas flux is 20L/min,
Plated film device nozzle distance substrate is 6mm, and substrate temperature is set to 400 DEG C～600 DEG C, and pedestal rate travel is 6mm/s, during plated film
Between be 105s, each component sprays to glass baseplate surface along with carrier gas from the outlet of plated film device after the vaporizer of 150 DEG C gasifies, all
Operating environment is carried out the most at ambient pressure, chooses simple glass and cheats each a piece of thin-film-coating that carries out of glass with micrometer grade hole, obtains respectively
Glass material after plated film.
The impact that at two kinds of glass surfaces, aumospheric pressure cvd is plated monolayer SnO2:F thin film is studied: by right
SnO on two kinds of glass surfaces in embodiment 102: F thin film carries out scratch test test, with the glass substrate on surface being plane
Comparing, on cellular glass surface between thin film and substrate, and the adhesion between film layer compares more than increase twelvefold.
Embodiment 11
Atmospheric pressure cvd method is coated with SnO2:F/SnO2: Sb (SUN-E) thin film
In atmospheric pressure cvd coating process, major parameter is provided that selection monobutyl-tin-trichloride and trifluoroacetic acid and water are
Teleblem, monobutyl-tin-trichloride and Butter of antimony. and water are counterdie.This experiment carrier gas used is mainly dry air and (can directly make
For carrier gas and oxidant), counterdie and teleblem carrier gas flux are 25L/min, and plated film device nozzle distance substrate is 6mm, substrate temperature
Being set to 300 DEG C～500 DEG C, pedestal rate travel is 5mm/s, and the spacing of two plated film nozzles is 100mm, and the plated film time is
225s, counterdie and teleblem respectively enter corresponding pipeline, and evaporation tube temperature is 150 DEG C, and all operations environment is the most at ambient pressure
Carry out, choose that simple glass and micrometer grade hole hole glass is each a piece of carries out thin-film-coating, respectively obtain the glass material after plated film.
To aumospheric pressure cvd at two kinds of double-deck SnO of glass surface plating2:F/SnO2: the impact of Sb thin film is ground
Study carefully: by the double-deck SnO on two kinds of glass surfaces in embodiment 112:F/SnO2: Sb thin film carries out scratch test test, with
Surface is that the glass substrate of plane is compared, on cellular glass surface between thin film and substrate, and the adhesion between film layer
Relatively increase more than ten octuple.
As seen from the above embodiment, present invention application reverse micelle microsphere etching glass surface, form the knot in micrometer grade hole hole
Structure；Gained glass substrate is that micrometer grade hole cheats glass, and it presents loose structure, and surface area is big, and Stability Analysis of Structures is wear-resisting.Further, originally
Inventing and carry out plated film at described micrometer grade hole hole glass surface, film can be embedded in glass orifice, can obtain tangent plane undulate
Three-dimensional membrane structure.Therefore, the film plating process utilizing the glass substrate that the present invention provides not only increases between thin film and substrate
Adhesion, and improve the adhesion between film layer, thus improve stability and the reliability of film function, be beneficial to application.
The above is only the preferred embodiment of the present invention, it is noted that for making the professional technique of the art
Personnel, on the premise of without departing from the technology of the present invention principle, are that by the multiple amendment to these embodiments, and these
Amendment also should be regarded as the scope that the present invention should protect.
Claims (10)
1. a glass substrate, it is characterised in that process obtains through reverse micelle microsphere microemulsion surface by glass；Described reverse micelle
Microsphere microemulsion includes non-polar solven and the chemical corrosion liquid of surfactant parcel；
Described glass substrate has micrometer grade hole hole.
Glass substrate the most according to claim 1, it is characterised in that described non-polar solven is selected from linear paraffin, replacement
One or more in linear paraffin, branched paraffin and aromatic hydrocarbon.
Glass substrate the most according to claim 1, it is characterised in that described surfactant selected from sodium alkyl benzene sulfonate,
Sodium alkyl sulfonate, sodium alkyl sulfate, polyoxyethylenated alcohol sodium sulfate, sodium alkyl sulfonate etc., trimethyl bromine
Change ammonium, cetyl trimethylammonium bromide, cetyl front three ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, hexadecane
Base trimethyl ammonium heteropoly acids, empgen BB, N-amido propyl dimethyl carboxymethyl ammonium glycine betaine, polyol type non-from
Sub-surface activating agent, Determination of Polyoxyethylene Non-ionic Surfactants and PULLRONIC F68 type nonionic surfactant
In one or more.
Glass substrate the most according to claim 1, it is characterised in that described chemical corrosion liquid is selected from acids corrosive liquid or alkali
Class corrosive liquid.
5. according to the glass substrate according to any one of Claims 1 to 4, it is characterised in that described reverse micelle microsphere microemulsion
Also include alcohol.
6. a film plating process for glass surface, comprises the following steps:
A) use reverse micelle microsphere microemulsion that glass is carried out surface process, obtain the glass substrate with micrometer grade hole hole；Institute
State reverse micelle microsphere microemulsion and include non-polar solven and the chemical corrosion liquid of surfactant parcel；
B) plated film on described glass baseplate surface, obtains the glass material after plated film.
Film plating process the most according to claim 6, it is characterised in that described step A) in, described non-polar solven is from straight
One or more in alkane, substituted straight chain alkane, branched paraffin and aromatic hydrocarbon；Described chemical corrosion liquid corrodes selected from acids
Liquid or bases corrosive liquid.
Film plating process the most according to claim 6, it is characterised in that described step A) in, the time that described surface processes
For 0.5h～10h, the temperature that described surface processes is 10 DEG C～120 DEG C.
Film plating process the most according to claim 6, it is characterised in that described step B) in, the mode of described plated film is magnetic
Control sputtering method or chemical vapour deposition technique.
10. according to the film plating process according to any one of claim 6～9, it is characterised in that described step A) also wrap before
Include: use cleanout fluid that glass is washed, the glass after being washed；Described cleanout fluid includes aqueous solution or anhydrous solvent；
Described step A) be: use reverse micelle microsphere microemulsion that the glass after washing is carried out surface process, cleaned, had
There is the glass substrate that micrometer grade hole is cheated.
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