CN113372014A - Composite coated glass and preparation method thereof - Google Patents
Composite coated glass and preparation method thereof Download PDFInfo
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- CN113372014A CN113372014A CN202110713866.7A CN202110713866A CN113372014A CN 113372014 A CN113372014 A CN 113372014A CN 202110713866 A CN202110713866 A CN 202110713866A CN 113372014 A CN113372014 A CN 113372014A
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- 239000011521 glass Substances 0.000 title claims abstract description 161
- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 135
- 239000011248 coating agent Substances 0.000 claims abstract description 132
- 238000005240 physical vapour deposition Methods 0.000 claims abstract description 84
- 239000000758 substrate Substances 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 41
- 238000002834 transmittance Methods 0.000 claims abstract description 24
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 20
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 14
- 229910052681 coesite Inorganic materials 0.000 claims description 25
- 229910052906 cristobalite Inorganic materials 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 229910052682 stishovite Inorganic materials 0.000 claims description 25
- 229910052905 tridymite Inorganic materials 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 23
- 238000000151 deposition Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000012495 reaction gas Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 7
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 6
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 2
- 230000004075 alteration Effects 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- 230000003712 anti-aging effect Effects 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000000429 assembly Methods 0.000 abstract 1
- 230000000712 assembly Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 23
- 239000007788 liquid Substances 0.000 description 16
- 239000010410 layer Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000011247 coating layer Substances 0.000 description 10
- 238000005253 cladding Methods 0.000 description 9
- 238000005496 tempering Methods 0.000 description 8
- 238000010030 laminating Methods 0.000 description 7
- 239000013077 target material Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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Classifications
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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
- 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
-
- 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
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide 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
- 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
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3447—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a halide
- C03C17/3452—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a halide comprising a fluoride
-
- 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
- C03C2218/152—Deposition methods from the vapour phase by cvd
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The application belongs to the technical field of glass, and particularly relates to composite coated glass and a preparation method thereof. The preparation method of the composite coated glass comprises the following steps: obtaining a glass substrate, and preparing a PVD coating on at least one side surface of the glass substrate by adopting a vacuum magnetron sputtering method; and preparing a CVD coating on the surface of the PVD coating, which is far away from the glass substrate, by adopting a chemical vapor deposition method to obtain the composite coated glass. The preparation method of the composite coated glass provided by the embodiment of the application is simple in process and suitable for industrial large-scale production and application, the prepared composite coated glass improves the transmittance and the environmental durability of the composite coated glass simultaneously through the synergistic effect of the PVD coating and the CVD coating, the chromatic aberration of the film surface is small, the power of the assembly is high, the anti-aging capability is strong, and the application requirements of high-end photovoltaic assemblies can be met.
Description
Technical Field
The application belongs to the technical field of glass, and particularly relates to composite coated glass and a preparation method thereof.
Background
The global solar photovoltaic market is rapidly developed. With the accumulation and progress of technology, the pursuit of high-power solar crystalline silicon cells has never been stopped. Meanwhile, different types of solar components are subdivided aiming at different use environments so as to face different customer requirements. Higher requirements are also put on photovoltaic glass enterprises. In particular, solar module enterprises put forward the requirements of high-efficiency and high-environmental-durability AR (anti-reflection glass or anti-reflection glass) coated front-plate photovoltaic glass for photovoltaic glass enterprises.
The common AR coated glass is generally a single-layer film and is generally prepared by adopting a roller coating process or a CVD coating process, and the prepared AR coated glass passes through porous SiO2The sol is used for film forming, a film layer shows deep blue and purple, the light transmittance attenuation is large, an ideal anti-reflection effect is difficult to achieve, the color difference of the film surface is large, the power attenuation of a component is easy to exceed the standard, the power of the component is low, the environmental durability is poor, and the requirement of a high-end component is difficult to meet.
Disclosure of Invention
The application aims to provide composite coated glass and a preparation method thereof, and aims to solve the problems of poor anti-reflection effect, large film surface chromatic aberration, low module power and poor environment durability of the conventional AR coated glass to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a composite coated glass, comprising the steps of:
obtaining a glass substrate, and preparing a PVD coating on at least one side surface of the glass substrate by adopting a vacuum magnetron sputtering method;
and preparing a CVD coating on the surface of the PVD coating, which is far away from the glass substrate, by adopting a chemical vapor deposition method to obtain the composite coated glass.
Furthermore, the refractive index of the PVD coating is 1.45-2.30.
Further, the material of the PVD coating comprises SiO2Titanium oxide, niobium oxide.
Furthermore, the thickness of the PVD coating is 50-100 nm.
Furthermore, the refractive index of the CVD coating is 1.26-1.33.
Further, the material of the CVD coating layer includes SiO2And magnesium fluoride.
Further, the thickness of the CVD coating is 80-130 nm.
Further, the conditions of the vacuum magnetron sputtering method include: and carrying out magnetron sputtering deposition on the surface of the glass substrate under the conditions that the vacuum degree is not higher than 10 < -3 > Pa, working gas is inert gas, reaction gas is oxygen, the purity of the target is not lower than 5N, the power is 10-30 KW and the voltage is 200-400V.
Further, the conditions of the chemical vapor deposition method include: and depositing coating sol on the surface of the PVD coating under the conditions that the temperature is 20-40 ℃ and the humidity is 40-70%, and curing to form the CVD coating.
Further, the curing process includes: and after the plating sol is deposited on the surface of the PVD coating, drying at the temperature of 150-200 ℃ to remove the solvent in the sol, and then sintering at the temperature of 680-720 ℃ at high temperature to form the CVD coating, thereby obtaining the composite coated glass.
In a second aspect, the application provides a composite coated glass, composite coated glass includes the glass substrate, and the setting of laminating at least is in the PVD cladding material of glass ground basic unit side surface, and the laminating setting is in the PVD cladding material deviates from the CVD cladding material on glass substrate surface.
Furthermore, the refractive index of the PVD coating is 1.45-2.30.
Further, the material of the PVD coating comprises SiO2Titanium oxide, niobium oxide.
Furthermore, the thickness of the PVD coating is 50-100 nm.
Furthermore, the refractive index of the CVD coating is 1.26-1.33.
Further, the material of the CVD coating layer includes SiO2At least one of magnesium fluoride;
further, the thickness of the CVD coating is 80-130 nm.
Furthermore, the b value of the composite coated glass is-1 to-4, the transmittance is 93.8 to 94.3 percent, and the pencil hardness is not lower than 3H.
According to the preparation method of the composite coated glass provided by the first aspect of the application, the PVD coating is prepared on the surface of the glass substrate by adopting a vacuum magnetron sputtering method, the adhesion between the film layer and the surface of the glass substrate is high, the density of the PVD coating prepared by the vacuum magnetron sputtering method is high, external water vapor micromolecules can be effectively prevented from attacking the glass substrate, the surface of the glass substrate is prevented from being hydrolyzed and generating irreversible corrosion, and the risks of color difference and power reduction of a photovoltaic assembly are reduced. Then, a CVD coating is prepared on the surface of the PVD coating by adopting a chemical vapor deposition method and serves as a top layer, the CVD coating is a closed porous film, the transmittance of the composite coated glass can be effectively improved, and the anti-reflection effect is good. The preparation method of the composite coated glass is simple in process and suitable for industrial large-scale production and application, the prepared composite coated glass improves the transmittance and the environmental durability of the composite coated glass simultaneously through the synergistic effect of the PVD coating and the CVD coating, the film surface chromatic aberration is small, the optical power is high, the anti-aging capability is strong, and the application requirements of high-end photovoltaic modules can be met.
The composite coated glass that this application second aspect provided is in including laminating the glass substrate that sets up in proper order and laminating the setting at least the PVD cladding material of glass substrate side surface to and the laminating setting is in the PVD cladding material deviates from the CVD cladding material on glass substrate surface. The PVD coating has high adhesion with the surface of the glass substrate, and the coating has high density, can effectively defend external water vapor micromolecules from attacking the glass substrate, prevents the surface of the glass substrate from being corroded, and reduces the risks of color difference and power reduction of a photovoltaic module. The CVD coating is a closed porous film, so that the transmittance of the composite coated glass can be effectively improved, and the anti-reflection effect is good. The composite coated glass has the advantages that the transmittance and the environmental durability of the composite coated glass are improved simultaneously through the synergistic effect of the PVD coating and the CVD coating, the film surface chromatic aberration is small, the optical power is high, the anti-aging capacity is strong, and the application requirements of high-end photovoltaic modules can be met.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a composite coated glass provided in an embodiment of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The term "PVD" is an abbreviation for "Physical Vapor Deposition" and refers to Physical Vapor Deposition; the term "CVD" is an abbreviation for "Chemical Vapor Deposition" and denotes Chemical Vapor Deposition.
The first aspect of the embodiments of the present application provides a method for preparing composite coated glass, comprising the following steps:
s10, obtaining a glass substrate, and preparing a PVD coating on at least one side surface of the glass substrate by adopting a vacuum magnetron sputtering method;
s20, preparing a CVD coating on the surface of the PVD coating, which is far away from the glass substrate, by adopting a chemical vapor deposition method to obtain the composite coated glass.
According to the preparation method of the composite coated glass provided by the first aspect of the embodiment of the application, firstly, the PVD coating is prepared on the surface of the glass substrate by adopting a vacuum magnetron sputtering method, the adhesion between the film layer and the surface of the glass substrate is high, the density of the PVD coating prepared by the vacuum magnetron sputtering method is high, external water vapor micromolecules can be effectively prevented from attacking the glass substrate, the surface of the glass substrate is prevented from being hydrolyzed and generating irreversible corrosion, and the risks of color difference and power reduction of a photovoltaic module are reduced. Then, a CVD coating is prepared on the surface of the PVD coating by adopting a chemical vapor deposition method and serves as a top layer, the CVD coating is a closed porous film, the transmittance of the composite coated glass can be effectively improved, and the anti-reflection effect is good. The preparation method of the composite coated glass provided by the embodiment of the application is simple in process and suitable for industrial large-scale production and application, the prepared composite coated glass improves the transmittance and the environmental durability of the composite coated glass simultaneously through the synergistic effect of the PVD coating and the CVD coating, the film surface chromatic aberration is small, the optical power is high, the anti-aging capability is strong, and the application requirements of high-end photovoltaic modules can be met.
In some embodiments, in step S10, the glass substrate includes, but is not limited to, a super white embossed glass substrate.
In some embodiments, in the step S10, the conditions of the vacuum magnetron sputtering method include: under the vacuum degree of not more than 10-3Pa, working gas is inert gas, reaction gas is oxygen, the purity of the target is not lower than 5N, the power is 10-30 KW, and the voltage is 200-400V. In some casesIn the specific embodiment, after the surface of the ultra-white embossed glass substrate is cleaned, the surface faces upwards and enters the vacuum degree of not more than 10-3In a stainless steel sealed cavity of Pa, a magnetron sputtering double-rotation cathode is utilized, under the conditions that the purity of a target material is not lower than 5N, working gas is Ar, nitrogen and other gases, reaction gas is oxygen, the power is 10-30 KW, and the voltage is 200-400V, a PVD coating is formed on the surface of the ultra-white embossed glass substrate through magnetron sputtering deposition, the coating is good in compactness, high in surface flatness and high in refractive index, and a better protection effect is achieved on the ultra-white embossed glass substrate.
In some embodiments, the refractive index of the PVD coating is 1.45-2.30, the PVD coating is a high-refractive-index film layer, the high-refractive-index coating can improve the optical performance of the composite coated glass, and if the refractive index is too low, defects are generated in the PVD coating, and the density of the film layer is reduced, so that the protection effect of the PVD coating on the glass substrate is reduced. In some embodiments, the refractive index of the PVD coating layer can be 1.45-1.60, 1.6-1.80, 1.8-2.00, 2-2.30, etc.
In some embodiments, the material of the PVD coating comprises SiO2At least one of titanium oxide and niobium oxide, which have high refractive index, and silicon, titanium or niobium is used as a target material to form SiO-containing materials by a vacuum magnetron sputtering method in an oxygen-containing atmosphere2Titanium oxide and niobium oxide.
In some embodiments, the thickness of the PVD coating is 50-100 nm, the PVD coating with the thickness can effectively protect the glass substrate, prevent the glass substrate from being attacked by outer water vapor and other small molecules to cause irreversible damage to the surface of the glass due to hydrolysis, corrosion and the like, improve the stability and environmental tolerance of the composite coated glass, and improve the application effect of the composite coated glass. In some embodiments, the thickness of the PVD coating may be 50-60 nm, 60-70 nm, 70-80 nm, 80-90 nm, 90-100 nm, etc.
In some embodiments, in the step S20, the conditions of the chemical vapor deposition method include: and depositing coating sol on the surface of the PVD coating under the conditions that the temperature is 20-40 ℃ and the humidity is 40-70%, and curing to form the CVD coating.In some embodiments, diluted SiO is sucked in by an electro-optical roller and a rubber roller under the conditions of normal temperature and normal pressure2When the coating sol is mixed, the rotating speed of a roller is matched with the linear speed of a belt, generally 9-14 m/min, the belt bears an ultra-white embossed glass substrate, the surface of the substrate is coated with a PVD coating, and then a layer of SiO is uniformly coated on the surface of the PVD coating through a rubber roller2And (5) waiting for coating sol, and forming a CVD coating after curing treatment.
In some embodiments, the step of curing comprises: after coating sol is deposited on the surface of the PVD coating, drying at the temperature of 150-200 ℃ to remove the solvent in the sol, then sintering at the temperature of 680-720 ℃ at high temperature to form a CVD coating, and sintering the CVD coating, the PVD coating and the glass substrate to form the finished composite coated glass.
In some embodiments, the CVD coating has a refractive index of 1.26 to 1.33. The CVD coating is prepared by a chemical vapor deposition method, so that the film layer contains a porous structure, the porous CVD coating with the refractive index can improve the light transmittance of the composite coated glass, and the light transmittance of the glass can be reduced if the refractive index is too high. In some embodiments, the refractive index of the CVD coating may be 1.26-1.30, 1.30-1.33, etc.
In some embodiments, the material of the CVD coating comprises SiO2And at least one of magnesium fluoride, the materials have good film forming performance, low refractive index, low cost and good stability of the formed film layer.
In some embodiments, the thickness of the CVD coating is 80-130 nm, the coating with the thickness has a good matching effect with the PVD coating, and the transmittance and the environmental tolerance of the composite coated glass are comprehensively improved. In some embodiments, the CVD coating may have a thickness of 80-90 nm, 90-110 nm, 110-130 nm, etc.
As shown in fig. 1, a second aspect of the embodiments of the present application provides a composite coated glass, which includes a glass substrate, a PVD coating layer attached to at least one side surface of the glass substrate, and a CVD coating layer attached to a surface of the PVD coating layer facing away from the glass substrate.
The composite coated glass that this application embodiment second aspect provided includes that the glass substrate that the laminating set up in proper order is laminated the PVD cladding material that sets up at glass ground substrate one side surface at least to and the laminating setting deviates from the CVD cladding material on glass substrate surface at the PVD cladding material. The PVD coating has high adhesion with the surface of the glass substrate, and the coating has high density, can effectively defend external water vapor micromolecules from attacking the glass substrate, prevents the surface of the glass substrate from being corroded, and reduces the risks of color difference and power reduction of a photovoltaic module. The CVD coating is a closed porous film, so that the transmittance of the composite coated glass can be effectively improved, and the anti-reflection effect is good. The composite coated glass provided by the embodiment of the application has the advantages that the transmittance and the environmental durability of the composite coated glass are improved simultaneously through the synergistic effect of the PVD coating and the CVD coating, the film surface chromatic aberration is small, the optical power is high, the anti-aging capability is strong, and the application requirements of high-end photovoltaic modules can be met.
In some embodiments, the PVD coating has a refractive index of 1.45-2.30;
in some embodiments, the material of the PVD coating comprises SiO2At least one of titanium oxide and niobium oxide;
in some embodiments, the PVD coating has a thickness of 50-100 nm.
In some embodiments, the CVD coating has a refractive index of 1.26 to 1.33;
in some embodiments, the material of the CVD coating comprises SiO2At least one of magnesium fluoride;
in some embodiments, the CVD coating has a thickness of 80-130 nm.
The beneficial effects of the above embodiments of the present application are discussed in detail in the foregoing, and are not described herein again.
In some embodiments, the composite coated glass has a b value of-1 to-4, a transmittance of 93.8 to 94.3 percent and a pencil hardness of not less than 3H. The composite coated glass disclosed by the embodiment of the application has the advantages of high transmittance, large b value, light blue film surface, small integral chromatic aberration, high color consistency and small chromatic aberration influence on the surface color of an application assembly. And the composite coated glass has high hardness and excellent dirt resistance.
In order to make the above implementation details and operations of the present application clearly understood by those skilled in the art and to make the advanced performance of the composite coated glass and the preparation method thereof obviously appear in the embodiments of the present application, the above technical solutions are illustrated by a plurality of examples.
Example 1
A composite coated glass is prepared by the following steps:
firstly, cleaning an ultra-white embossed glass substrate, and enabling the smooth surface to face upwards and enter a vacuum degree of 10-3In a Pa stainless steel sealed cavity, a magnetron sputtering double-rotating cathode is utilized, a target material is silicon with the purity of 5N, a working gas is Ar, and a reaction gas is O2Power 20KW, voltage 400V, uniform deposition thickness of 65nm SiO2Forming a thin film to form a PVD coating; the thickness is 65 nm;
secondly, sucking diluted SiO by utilizing an electro-optical roller and a rubber roller under the conditions that the temperature of a coating chamber is 25 ℃ and the humidity is 50 percent2Sol liquid, the rotation speed of the roller is matched with the linear speed of the belt and is 9m/min, the belt bears an ultra-white embossed glass substrate, and the suede of the substrate is plated with dense SiO by a PVD process2A PVD coating layer, and then a layer of SiO is uniformly coated on the surface of the PVD coating layer by a rubber roller2Sol liquid; SiO is coated completely2The glass substrate of sol liquid is first dried at 180 deg.c to obtain SiO2Drying the sol liquid completely, tempering in a tempering furnace at 700 deg.c to sinter SiO2The sol and the glass are completely sintered into a whole to form a CVD coating with the thickness of 130 nm; finally obtaining the composite coated glass.
Example 2
A composite coated glass is prepared by the following steps:
firstly, cleaning an ultra-white embossed glass substrate, and enabling the smooth surface to face upwards and enter a vacuum degree of 10-3In a Pa stainless steel sealed cavity, a magnetron sputtering double-rotating cathode is utilized, a target material is silicon with the purity of 5N, a working gas is Ar, and a reaction gas is O2Power 20KW, voltage 400V, uniform deposition thickness of 75nm SiO2Film formation ofPVD coating; the thickness is 75 nm;
secondly, sucking diluted SiO by utilizing an electro-optical roller and a rubber roller under the conditions that the temperature of a coating chamber is 25 ℃ and the humidity is 50 percent2Sol liquid, the rotation speed of the roller is matched with the linear speed of the belt and is 9m/min, the belt bears an ultra-white embossed glass substrate, and the suede of the substrate is plated with dense SiO by a PVD process2A PVD coating layer, and then a layer of SiO is uniformly coated on the surface of the PVD coating layer by a rubber roller2Sol liquid; SiO is coated completely2The glass substrate of sol liquid is first dried at 180 deg.c to obtain SiO2Drying the sol liquid completely, tempering in a tempering furnace at 700 deg.c to sinter SiO2The sol and the glass are completely sintered into a whole to form a CVD coating with the thickness of 115 nm; finally obtaining the composite coated glass.
Comparative example 1
A coated glass is prepared by the following steps:
sucking diluted SiO with an electro-optical roller and a rubber roller under the conditions that the temperature of a coating chamber is 25 ℃ and the humidity is 50%2Sol liquid, the rotating speed of the roller is matched with the linear speed of the belt, the speed is 9m/min, the belt bears an ultra-white embossed glass substrate, and a layer of SiO is uniformly coated on the surface of the substrate by a rubber roller2Sol liquid; SiO is coated completely2The glass substrate of sol liquid is first dried at 180 deg.c to obtain SiO2Drying the sol liquid completely, tempering in a tempering furnace at 700 deg.c to sinter SiO2The sol and the glass are completely sintered into a whole to form a CVD coating with the thickness of 125 nm; and obtaining the coated glass.
Comparative example 2
A coated glass is prepared by the following steps:
cleaning an ultra-white patterned glass substrate, and putting the substrate with the smooth surface facing upwards into a vacuum degree of 10-3In a Pa stainless steel sealed cavity, a magnetron sputtering double-rotating cathode is utilized, a target material is silicon with the purity of 5N, a working gas is Ar, and a reaction gas is O220KW power, electricityPressing 400V, and uniformly depositing SiO with the thickness of 180nm2Forming a thin film to form a PVD coating; the thickness is 180nm, and the coated glass is obtained.
Comparative example 3
A composite coated glass is prepared by the following steps:
firstly, absorbing diluted SiO by utilizing an electro-optical roller and a rubber roller under the conditions that the temperature of a film coating chamber is 25 ℃ and the humidity is 50 percent2Sol liquid, the rotating speed of the roller is matched with the linear speed of the belt, the speed is 9m/min, the belt bears an ultra-white embossed glass substrate, and a layer of SiO is uniformly coated on the surface of the substrate by a rubber roller2Sol liquid; SiO is coated completely2The glass substrate of sol liquid is first dried at 180 deg.c to obtain SiO2Drying the sol liquid completely, tempering in a tempering furnace at 700 deg.c to sinter SiO2The sol and the glass are completely sintered into a whole to form a first CVD coating with the thickness of 80 nm;
secondly, preparing a second CVD coating with the thickness of 90nm by adopting the same method of the step I to obtain the composite coated glass.
Comparative example 4
A composite coated glass is prepared by the following steps:
firstly, cleaning an ultra-white embossed glass substrate, and enabling the smooth surface to face upwards and enter a vacuum degree of 10-3In a Pa stainless steel sealed cavity, a magnetron sputtering double-rotating cathode is utilized, a target material is silicon with the purity of 5N, a working gas is Ar, and a reaction gas is O2Power 20KW, voltage 400V, uniform deposition thickness of 60nm SiO2A film forming a first PVD coating; the thickness is 60 nm;
secondly, utilizing a double-rotating cathode of magnetron sputtering on the surface of the first PVD coating in the step I, wherein the target material is silicon with the purity of 5N, the working gas is Ar, and the reaction gas is O2Power 20KW, voltage 400V, uniform deposition thickness of 65nm SiO2Forming a second PVD coating; the thickness is 65nm, and the composite coated glass is obtained.
Further, in order to verify the advancement of the composite coated glass in the examples of the present application, the light transmittance, color b value, environmental resistance, hardness, and the like of the coated glass prepared in examples 1 to 3 and comparative examples 1 to 4 were respectively tested, and the test results are shown in table 1 below:
TABLE 1
According to the test results, the PVD coating and the CVD coating are sequentially prepared on the surface of the glass substrate in the embodiments 1 and 2, and meanwhile, the light transmittance, the environmental durability (small attenuation amplitude of transmittance after aging) and the pencil hardness of the composite coated glass are improved, the color b value is high, the surface of the composite coated glass is light blue, the integral chromatic aberration is small, the color consistency is high, and the chromatic aberration influence on the surface color of the application component is small.
The comparative example 1 only adopts a CVD method to prepare the coating, the comparative example 2 only adopts a PVD method to prepare the coating, the comparative example 3 adopts a CVD method to prepare two CVD coatings, and the comparative example 4 adopts PVD to prepare two coatings, both of which show lower light transmittance and reduce the transmittance by 0.7 percent compared with the transmittance of the examples 1 and 2; and the b value of the coated glass is small and is as low as-7.5, the surface is dark blue, the surface chromatic aberration is large, and the chromatic aberration influence on the surface color of the application component is large. In addition, the composite coated glass containing the CVD coating (comparative examples 1 and 3) has a high attenuation rate after aging and a low pencil hardness; on the other hand, the composite coated glass (comparative examples 2 and 4) containing only the PVD coating had a low transmittance and a small b value, although the attenuation ratio was low and the hardness was high.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The preparation method of the composite coated glass is characterized by comprising the following steps:
obtaining a glass substrate, and preparing a PVD coating on at least one side surface of the glass substrate by adopting a vacuum magnetron sputtering method;
and preparing a CVD coating on the surface of the PVD coating, which is far away from the glass substrate, by adopting a chemical vapor deposition method to obtain the composite coated glass.
2. The method for preparing composite coated glass according to claim 1, wherein the refractive index of the PVD coating is 1.45-2.30;
and/or the material of the PVD coating comprises SiO2At least one of titanium oxide and niobium oxide;
and/or the thickness of the PVD coating is 50-100 nm.
3. The method for preparing the composite coated glass according to claim 1 or 2, wherein the refractive index of the CVD coating is 1.26-1.33;
and/or the material of the CVD coating comprises SiO2At least one of magnesium fluoride;
and/or the thickness of the CVD coating is 80-130 nm.
4. The method for preparing composite coated glass according to claim 3, wherein the conditions of the vacuum magnetron sputtering method include: under the vacuum degree of not more than 10-3Pa, working gas is inert gas, reaction gas is oxygen, the purity of the target is not lower than 5N, the power is 10-30 KW, and the voltage is 200-400V.
5. The method for preparing a composite coated glass according to claim 1 or 4, wherein the conditions of the chemical vapor deposition method comprise: and depositing coating sol on the surface of the PVD coating under the conditions that the temperature is 20-40 ℃ and the humidity is 40-70%, and curing to form the CVD coating.
6. The method for preparing a composite coated glass according to claim 5, wherein the curing treatment step comprises: and after the plating sol is deposited on the surface of the PVD coating, drying at the temperature of 150-200 ℃ to remove the solvent in the sol, and then sintering at the temperature of 680-720 ℃ at high temperature to form the CVD coating, thereby obtaining the composite coated glass.
7. The composite coated glass is characterized by comprising a glass substrate, a PVD coating at least attached to one side surface of the glass substrate, and a CVD coating attached to the surface of the PVD coating, which is deviated from the glass substrate.
8. The composite coated glass according to claim 7, wherein the PVD coating has a refractive index of 1.45-2.30;
and/or the material of the PVD coating comprises SiO2At least one of titanium oxide and niobium oxide;
and/or the thickness of the PVD coating is 50-100 nm.
9. The composite coated glass according to claim 7 or 8, wherein the refractive index of the CVD coating is 1.26-1.33;
and/or the material of the CVD coating comprises SiO2At least one of magnesium fluoride;
and/or the thickness of the CVD coating is 80-130 nm.
10. The composite coated glass according to claim 9, wherein the composite coated glass has a b value of-1 to-4, a transmittance of 93.8 to 94.3%, and a pencil hardness of not less than 3H.
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Application publication date: 20210910 |