CN115057628A - Neutral-color LOW-reflection LOW-E coated glass and preparation method thereof - Google Patents
Neutral-color LOW-reflection LOW-E coated glass and preparation method thereof Download PDFInfo
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- CN115057628A CN115057628A CN202210742156.1A CN202210742156A CN115057628A CN 115057628 A CN115057628 A CN 115057628A CN 202210742156 A CN202210742156 A CN 202210742156A CN 115057628 A CN115057628 A CN 115057628A
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- 239000011521 glass Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000010410 layer Substances 0.000 claims abstract description 621
- 230000004888 barrier function Effects 0.000 claims abstract description 110
- 239000002131 composite material Substances 0.000 claims abstract description 91
- 239000002346 layers by function Substances 0.000 claims abstract description 84
- 239000011241 protective layer Substances 0.000 claims abstract description 47
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001120 nichrome Inorganic materials 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims description 26
- 229910004205 SiNX Inorganic materials 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 229910007667 ZnOx Inorganic materials 0.000 claims description 16
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 14
- 229910004286 SiNxOy Inorganic materials 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910003087 TiOx Inorganic materials 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 24
- 230000007935 neutral effect Effects 0.000 abstract description 15
- 238000001579 optical reflectometry Methods 0.000 abstract description 4
- 238000004544 sputter deposition Methods 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000013077 target material Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 238000002310 reflectometry Methods 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 239000005344 low-emissivity glass Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3615—Coatings of the type glass/metal/other inorganic layers, at least one layer being non-metallic
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3626—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3639—Multilayers containing at least two functional metal layers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
- C03C17/366—Low-emissivity or solar control coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
-
- 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)
Abstract
The invention relates to a neutral-color LOW-reflection LOW-E coated glass and a preparation method thereof, wherein the coated glass comprises a glass substrate, an antireflection film layer, two or three composite film layers and a top protective layer, wherein the antireflection film layer, the two or three composite film layers and the top protective layer are sequentially plated on the surface of one side of the glass substrate from inside to outside, each composite film layer comprises a dielectric layer, a seed layer, a functional layer and a barrier layer which are sequentially arranged, the antireflection film layer is adjacent to the dielectric layer of the composite film layer adjacent to the antireflection film layer, the barrier layer of the composite film layer adjacent to the antireflection film layer is adjacent to the dielectric layer of the composite film layer adjacent to the antireflection film layer, the top protective layer is adjacent to the barrier layer of the composite film layer adjacent to the top protective layer, the barrier layer is a NiCrMo layer or a NiCr layer, and the barrier layer of at least one composite film layer is a NiCrMo layer. According to the coated glass provided by the invention, the antireflection film layer is added, so that the coated glass has extremely low visible light reflectivity, and the NiCrMo is used as the barrier layer of the functional layer, so that the coated glass has neutral transmission color.
Description
Technical Field
The invention belongs to the technical field of coated glass, and particularly relates to LOW-emissivity (LOW-E) coated glass with a neutral color and a preparation method thereof.
Background
As an energy-saving building material, in the prior art, low-radiation coated glass generally refers to a low-radiation functional layer deposited on the surface of float glass, so as to reflect near infrared rays in sunlight and far infrared rays in a living environment, and achieve the effect of reducing the absorption and radiation of the glass to the infrared rays, so the low-radiation coated glass is called as low-radiation coated glass.
The low-emissivity coated glass can be used for doors and windows of families, and can also be used for glass curtain walls of markets, office buildings and high-grade hotels and other required places. With the large-scale application of the traditional low-emissivity coated glass, the light pollution becomes a problem which puzzles urban residents and needs to be solved urgently because the reflectivity of the traditional low-emissivity coated glass to visible light is higher. In order to reduce the phenomenon of light pollution caused by the large-scale use of the glass curtain wall, governments in various places issue policy and regulations to limit the foreign reflection of the building glass.
The existing low-radiation coated glass has the following defects: 1. the visible light reflectivity is higher, so that light pollution is easily caused; 2. the product has the influence on the visual effect of people due to the color difference.
Disclosure of Invention
The invention aims to provide LOW-reflectivity LOW-E coated glass with neutral color and a preparation method thereof, and aims to solve the problems that the visible light reflectivity of the existing coated glass is higher, the product has poor transmission color and the visual effect is influenced.
In order to achieve the purpose, the invention adopts a technical scheme that:
the utility model provides a LOW anti-LOW-E coated glass of neutral color, LOW anti-LOW-E coated glass of neutral color include the glass substrate and from inside to outside plate in proper order locate glass substrate one side surface subtract reflection rete, two or three compound rete, top inoxidizing coating, each compound rete including dielectric layer, seed layer, functional layer, the barrier layer that sets gradually, subtract reflection rete and adjacent compound rete's dielectric layer adjacent with it, with subtract reflection rete adjacent compound rete the barrier layer with adjacent compound rete with it adjacent compound rete's dielectric layer adjacent, top inoxidizing coating with adjacent with it the barrier layer of compound rete adjacent, the barrier layer be NiCrMo layer or NiCr layer, and at least one compound rete the barrier layer be the NiCrMo layer.
Preferably, the thickness of the barrier layer of at least one of the composite film layers is greater than or equal to 1 nm.
Preferably, the antireflection film layer is a NiCr layer.
Preferably, the functional layer is an Ag layer or an Ag + Cu layer; if the functional layer is an Ag + Cu layer, the Ag layer is adjacent to the seed layer of the composite film layer adjacent to the Ag layer, and the Cu layer is adjacent to the barrier layer of the composite film layer adjacent to the Cu layer.
Preferably, the dielectric layer and the top protective layer are a combination of one or more layers of a SiNx layer, a SiOx layer, a SiNxOy layer and a TiOx layer.
Preferably, the seed layer is one or a combination of two of a ZnOx layer and a ZnSnOx layer.
Preferably, the number of the composite film layers is two, the composite film layer adjacent to the anti-reflection film layer comprises a first dielectric layer, a first seed layer, a first functional layer and a first barrier layer, the composite film layer adjacent to the top protective layer comprises a second dielectric layer, a second seed layer, a second functional layer and a second barrier layer, and the anti-reflection film layer, the first dielectric layer, the first seed layer, the first functional layer, the first barrier layer, the second dielectric layer, the second seed layer, the second functional layer, the second barrier layer and the top protective layer are sequentially deposited on the surface of one side of the glass substrate from inside to outside.
Preferably, the number of the composite film layers is three, the composite film layer adjacent to the anti-reflection film layer comprises a first dielectric layer, a first seed layer, a first functional layer and a first barrier layer, the middle composite film layer between the two composite film layers comprises a second dielectric layer, a second seed layer, a second functional layer and a second barrier layer, the composite film layer adjacent to the top protective layer comprises a third dielectric layer, a third seed layer, a third functional layer and a third barrier layer, and the anti-reflection film layer, the first dielectric layer, the first seed layer, the first functional layer, the first barrier layer, the second dielectric layer, the second seed layer, the second functional layer, the second barrier layer, the third dielectric layer, the third seed layer, the third functional layer, the third barrier layer and the top protective layer are sequentially deposited from inside to outside on one side surface of the glass substrate.
Preferably, in each of the composite film layers, the thickness of the functional layer is greater than or equal to 7 and less than or equal to 16 nm; if the functional layer is an Ag + Cu layer, the thickness of the Cu layer is more than or equal to 5 and less than 7 nm; the thickness of the barrier layer is more than 0 and less than or equal to 4 nm; the thickness of the antireflection film layer is more than 1.3 and less than or equal to 3 nm; the thickness range of the dielectric layer is 28-70 nm; the thickness range of the top protective layer is 25-43 nm; the thickness range of the seed layer is 5-10 nm.
The invention also aims to provide a method for preparing the neutral-color LOW-reflection LOW-E coated glass, which comprises the following steps: the method comprises the following steps of sequentially plating an antireflection film layer, a composite film layer and a top protective layer on the surface of one side of a glass substrate in a magnetron sputtering coating mode, wherein the number of the composite film layers is two or three, and the composite film layer comprises a dielectric layer, a seed layer, a functional layer and a barrier layer which are sequentially arranged; when the composite layer is plated, the antireflection film layer is adjacent to the dielectric layer of the composite film layer adjacent to the antireflection film layer, the functional layer of the composite film layer adjacent to the antireflection film layer is adjacent to the barrier layer of the composite film layer adjacent to the functional layer, and the top protective layer is adjacent to the barrier layer of the composite film layer adjacent to the top protective layer.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the LOW-reflectivity LOW-E coated glass with the neutral color, the antireflection film layer is added, so that the coated glass can have extremely LOW visible light reflectivity, and NiCrMo is used as the barrier layer of the functional layer, so that the coated glass has a neutral transmission color, and a more real impression when outdoor scenery is observed indoors is obtained; the visible light transmittance of the whole film system can be flexibly adjusted by adjusting the thickness of the barrier layer, the color transmission neutrality of the glass product is kept to the maximum extent, the perspective color adjusting range of the glass product is wide, and the requirements of customers in different regions are met; the NiCrMo is used as a barrier layer, so that the toughness and the hardness of the film layer can be increased, and the defects of scratch, abrasion, corrosion, oxidation and the like of the coated layer are prevented.
Detailed Description
The invention will be further described with reference to the examples shown below.
The LOW anti-LOW-E coated glass of neutral color includes glass substrate and plates in proper order from inside to outside and locates the antireflection rete on glass substrate one side surface, two or three compound rete, the top inoxidizing coating, each compound rete is including the dielectric layer that sets gradually, the seed layer, the functional layer, the barrier layer, it is adjacent with the dielectric layer of adjacent compound rete to subtract the antireflection rete, the barrier layer of the compound rete adjacent with the antireflection rete is adjacent with the dielectric layer of adjacent compound rete with it, the top inoxidizing coating is adjacent with the barrier layer of adjacent compound rete with it, wherein:
the main component of the anti-reflection film layer is NiCr, the material has high visible light absorption capacity, high hardness, high wear resistance and high chemical stability, provides strong anti-reflection capacity and simultaneously has a strong protection effect on the film layer, and the NiCr can have good adhesion with glass and good adhesion with a dielectric layer.
The barrier layer is a NiCrMo layer or a NiCr layer, the barrier layer of at least one composite film layer is the NiCrMo layer, the material NiCrMo of the barrier layer is used for enabling the glass product to be neutral in transmission color, the light transmittance of the glass product can be adjusted by adjusting the thickness of the glass product, the neutral in transmission color of the glass product is kept to the maximum extent, and the more real impression of outdoor scenery observed indoors is obtained; it is also possible to protect the functional layer from damage during thermal processing.
The conventional double-silver and triple-silver coated glass adopts NiCr as a barrier layer for adjusting the light transmittance of the product, but because of the inherent properties of the NiCr film layer material, the perspective color is greenish, and no new material replaces the defective barrier layer material for a long time, the NiCr film layer material is used.
If two composite film layers are arranged, the barrier layer of one of the two composite film layers is a NiCrMo layer, or the barrier layers of the two composite film layers are NiCrMo layers. If three composite film layers are arranged, the barrier layer in one composite film layer is a NiCrMo layer, or the barrier layers in two composite film layers are NiCrMo layers, or the barrier layers in the three composite film layers are NiCrMo layers.
The advantage of NiCrMo over NiCr is that the addition of Mo to the alloy improves the transmission colour of the product. Compared with a single Mo layer, NiCrMo has the advantages that the alloy can increase the toughness and hardness of a film layer, and has the main function of preventing the defects of scratch, abrasion, corrosion, oxidation and the like of the coated film layer.
The thickness of the barrier layer of at least one composite film layer is larger than or equal to 1nm, if the barrier layer is too thin, the light transmittance of the product is high, the reflection of the film is greatly influenced on the whole outdoor reflection of the product, and the reduction of the reflectivity of the product is not facilitated.
The dielectric layer is a combination of one or more layers of a SiNx layer, a SiOx layer, a SiNxOy layer and a TiOx layer, the SiNx layer is taken as the optimal layer, the SiNx layer has good bonding performance with glass, and has strong corrosion resistance, mechanical scratch resistance and high-temperature oxidation resistance, so that the material is an ultra-strength and ultra-hardness material with excellent chemical stability, can play a role in improving the adhesion of a functional silver layer to the surface of the glass, protecting the functional silver layer, adjusting color and improving the hardness of a film system, and can improve the machining performance of the film layer.
The seed layer is one or the combination of two of the ZnOx layer and the ZnSnOx layer, the ZnOx is taken as the best, the flatness of the film layer can be improved by taking the ZnOx as the seed layer, a clean surface without pollution is provided for the functional layer, the adhesive force of metal of the functional layer in the film layer is increased, and the functional layer can better exert performance.
The functional layer is an Ag layer or an Ag + Cu layer, and the metal Ag has very good conductivity, so that the surface resistance and the radiance of the whole film layer can be reduced, and the function of adjusting the color and the performance of the film layer is also realized. If the functional layer is an Ag + Cu layer, the Ag layer is adjacent to the seed layer of the adjacent composite film layer, and the Cu layer is adjacent to the barrier layer of the adjacent composite film layer.
The top protective layer is a combination of one or more layers of SiNx layers, SiOx layers, SiNxOy layers and TiOx layers, and the SiNx layer is the optimal layer, so that the top protective layer has strong corrosion resistance, mechanical scratch resistance and high-temperature oxidation resistance.
The thickness ranges of the above respective film layers are as follows: in each composite film layer, the thickness of the antireflection film layer is more than 1.3 and less than or equal to 3 nm; the thickness range of the dielectric layer is 28-70 nm; the thickness range of the seed layer is 5-10 nm; the thickness of the functional layer is more than or equal to 7 and less than or equal to 16 nm; the thickness of the barrier layer is more than 0 and less than or equal to 4 nm; the thickness of the top protective layer ranges from 25 nm to 43 nm.
According to different transmission color requirements, the number of the composite film layers can be two or three, when the number of the composite film layers is two, an antireflection film layer, two composite film layers and a top protective layer are sequentially plated inwards and outwards on one side surface of a glass substrate of the neutral-color LOW-reflection LOW-E coated glass, one composite film layer comprises a first dielectric layer, a first seed layer, a first functional layer and a first barrier layer, the other composite film layer comprises a second dielectric layer, a second seed layer, a second functional layer and a second barrier layer, the antireflection film layer, the first dielectric layer, the first seed layer, the first functional layer, the first barrier layer, the second dielectric layer, the second seed layer, the second functional layer, the second barrier layer and the top protective layer are sequentially deposited on the glass substrate from inside to outside, specifically:
the thickness of the antireflection film layer is more than 1.3 and less than or equal to 3 nm; the thickness range of the first dielectric layer is 28-35 nm; the thickness range of the first seed layer is 5-8 nm; the first functional layer is an Ag layer or an Ag + Cu layer; the thickness range of the first barrier layer is 0-2 nm; the thickness range of the second dielectric layer is 43-70 nm; the thickness range of the second seed layer is 5-10 nm; the second functional layer is an Ag layer or an Ag + Cu layer; the thickness range of the second barrier layer is 0-4 nm; the thickness range of the top protective layer is 25-43 nm.
The first functional layer is an Ag layer or an Ag + Cu layer, the thickness of the film layer is more than or equal to 7 and less than or equal to 16nm, if the functional layer is the Ag + Cu layer, the Ag layer is adjacent to the seed layer of the composite film layer adjacent to the Ag layer, the Cu layer is adjacent to the barrier layer of the composite film layer adjacent to the Cu layer, namely the Ag layer and the Cu layer are sequentially coated respectively, and at the moment, the thickness of the Cu layer is more than or equal to 5 and less than 7 nm; the second functional layer is an Ag layer or an Ag + Cu layer, the thickness range of the film layer is 10-15 nm, if the functional layer is the Ag + Cu layer, the Ag layer is adjacent to the seed layer of the composite film layer adjacent to the Ag layer, the Cu layer is adjacent to the barrier layer of the composite film layer adjacent to the Cu layer, namely the Ag layer and the Cu layer are sequentially coated with films respectively, and at the moment, the thickness range of the Cu layer is 5-7 nm.
When the composite film layers are three, an antireflection film layer, three composite film layers and a top protective layer are sequentially plated inwards and outwards on one side surface of a glass substrate of the medium-color LOW-reflection LOW-E coated glass, the composite film layer adjacent to the antireflection film layer comprises a first dielectric layer, a first seed layer, a first functional layer and a first barrier layer, the middle composite film layer between the two composite film layers comprises a second dielectric layer, a second seed layer, a second functional layer and a second barrier layer, the composite film layer adjacent to the top protective layer comprises a third dielectric layer, a third sublayer, a third functional layer and a third barrier layer, the antireflection film layer, the first dielectric layer, the first seed layer, the first functional layer, the first barrier layer, the second dielectric layer, the second seed layer, the second functional layer, the second barrier layer, the third dielectric layer, the third sublayer, the third functional layer, the third barrier layer, the antireflection film layer, the first seed layer, the second barrier layer, the third functional layer and the top protective layer, The top protective layer is deposited on the glass substrate from inside to outside in sequence.
The thickness range of the antireflection film layer is 1.3-3 nm; the thickness range of the first dielectric layer is 28-35 nm; the thickness range of the first seed layer is 5-8 nm; the first functional layer is an Ag layer or an Ag + Cu layer; the thickness range of the first barrier layer is 0-2 nm; the thickness range of the second dielectric layer is 43-70 nm; the thickness range of the second seed layer is 5-10 nm; the second functional layer is an Ag layer or an Ag + Cu layer; the thickness range of the second barrier layer is 0-4 nm; the thickness range of the third dielectric layer is 25-43 nm; the thickness range of the third sub-layer is 5-8 nm, the thickness range of the third functional layer is 12-17 nm, the thickness range of the third barrier layer is 0-2 nm, and the thickness range of the top protective layer is 25-43 nm.
The following description will be made specifically by taking two or three composite film layers as examples, and refer to examples 1 to 2.
Example 1
The neutral-color LOW-reflection LOW-E coated glass comprises a glass substrate, an antireflection coating, two composite coatings and a top protective layer, wherein the antireflection coating, the two composite coatings and the top protective layer are sequentially coated on the surface of one side of the glass substrate from inside to outside, the antireflection coating is a NiCr layer, and the thickness of the coatings is 1.3 nm; the first dielectric layer is a SiNx layer, and the film layer thickness is 29.5 nm; the first seed layer is a ZnOx layer, and the thickness of the film layer is 7 nm; the first functional layer is an Ag + Cu layer, and the thickness of the film layer is 7nm +5.2 nm; the first barrier layer is a NiCrMo layer, and the thickness of the film layer is 1.5 nm; the second dielectric layer is a SiNx layer, and the film layer thickness is 49 nm; the second seed layer is a ZnOx layer, and the thickness of the film layer is 7 nm; the second functional layer is an Ag layer, and the thickness of the film layer is 11.2 nm; the second barrier layer is a NiCrMo layer, and the thickness of the film layer is 2.7 nm; the top protective layer is a SiNx layer, and the film thickness is 35.5 nm.
The standard hollow chamber external reflectance and transmittance color data of the coated glass product provided in this example are as follows:
table 1 outdoor reflectance and transmission color data for example 1
| Outdoor reflectivity | Light transmittance | Transmission color a | Transmission color b | |
| Standard hollow | 7％ | 48％ | -1.1 | 0.8 |
As can be seen from Table 1, the coated glass product shown in this example has a reflectance as low as 7%, a neutral color in transmission color, and a color close to natural color.
Comparative example 1
The difference from example 1 is that: the antireflection film layer is not provided in this example.
In this example, the specific film structure and thickness are:
the first dielectric layer is a SiNx layer, and the film layer thickness is 29.5 nm; the first seed layer is a ZnOx layer, and the thickness of the film layer is 7 nm; the first functional layer is an Ag + Cu layer, and the thickness of the film layer is 7nm +5.2 nm; the first barrier layer is a NiCrMo layer, and the thickness of the film layer is 1.5 nm; the second dielectric layer is a SiNx layer, and the film layer thickness is 49 nm; the second seed layer is a ZnOx layer, and the thickness of the film layer is 7 nm; the second functional layer is an Ag layer, and the thickness of the film layer is 11.2 nm; the second barrier layer is a NiCrMo layer, and the thickness of the film layer is 2.7 nm; the top protective layer is a SiNx layer, and the film thickness is 35.5 nm.
The standard hollow chamber external reflectance and transmission color data for the coated glass product provided in this example are as follows:
table 2 outdoor reflectance and transmission color data for comparative examples
| Outdoor reflectivity | Light transmittance | Transmission color a | Transmission color b | |
| Standard hollow | 9％ | 52％ | -0.8 | 1.5 |
As can be seen from tables 1 and 2, the outdoor reflectivity of the coated glass of example 1 is less than that of the coated glass of the comparative example, and the NiCr layer of the antireflection film layer of example 1 can effectively reduce the outdoor reflectivity of the glass product.
Comparative example 2
The difference from example 1 is that: the first barrier layer and the second barrier layer are both NiCr layers.
In this example, the specific film structure and thickness are:
the antireflection film layer is a NiCr layer, and the thickness of the film layer is 1.3 nm; the first dielectric layer is a SiNx layer, and the film layer thickness is 29.5 nm; the first seed layer is a ZnOx layer, and the thickness of the film layer is 7 nm; the first functional layer is an Ag + Cu layer, the thickness of the Ag layer is 7nm, and the thickness of the Cu layer is 5.2 nm; the first barrier layer is a NiCr layer, and the thickness of the film layer is 1.5 nm; the second dielectric layer is a SiNx layer, and the film layer thickness is 49 nm; the second seed layer is a ZnOx layer, and the thickness of the film layer is 7 nm; the second functional layer is an Ag layer, and the thickness of the film layer is 11.2 nm; the second barrier layer is a NiCr layer, and the thickness of the film layer is 2.7 nm; the top protective layer is a SiNx layer, and the thickness of the film layer is 35.5 nm.
The standard hollow chamber external reflectance and transmission color data for the coated glass product provided in this example are as follows:
| outdoor reflectivity | Light transmittance | Transmission color a | Transmission color b | |
| Standard hollow | 7％ | 46％ | -2.5 | -1 |
As can be seen from the comparison between example 1 and comparative example 2, the use of the NiCrMo layer as the barrier layer in example 1 is effective in improving the transmission color of the product.
Example 2
Compound rete sets up threely, and the LOW anti-LOW-E coated glass of neutral colour includes the glass substrate and plates in proper order from inside to outside and locate antireflection rete, three compound rete, the top inoxidizing coating on glass substrate one side surface, and specific rete structure and thickness are: the antireflection film layer is a NiCr layer, and the thickness of the film layer is 1.3 nm; the first dielectric layer is a SiNx layer, and the film layer thickness is 24.5 nm; the first seed layer is a ZnOx layer, and the thickness of the film layer is 7 nm; the first functional layer is an Ag layer, and the thickness of the film layer is 8.1 nm; the first barrier layer is a NiCrMo layer, and the thickness of the film layer is 0.8 nm; the second dielectric layer is a SiNx layer, and the thickness of the film layer is 61 nm; the second seed layer is a ZnOx layer, and the thickness of the film layer is 7 nm; the second functional layer is an Ag + Cu layer, and the thickness of the film layer is 7nm +4.6 nm; the second barrier layer is a NiCrMo layer, and the thickness of the film layer is 1.3 nm; the third dielectric layer is a SiNx layer, and the film layer thickness is 66 nm; the third sublayer is a ZnOx layer, and the thickness of the film layer is 7 nm; the third functional layer is an Ag layer, and the thickness of the film layer is 12.6 nm; the third barrier layer is a NiCrMo layer, and the thickness of the film layer is 2.1 nm; the top protective layer is a SiNx layer, and the film thickness is 28.6 nm.
The standard hollow chamber external reflectance and transmission color data for the coated glass product provided in this example are as follows:
| outdoor reflectivity | Light transmittance | Transmission color a | Transmission color b | |
| Standard hollow | 7％ | 49％ | -1.1 | -0.8 |
The invention also provides a method for preparing the neutral-color LOW-reflection LOW-E coated glass, which comprises the following steps:
the method comprises the steps of adopting a magnetron sputtering coating mode, sequentially coating an antireflection film layer, a composite film layer and a top protective layer on the inner side surface of a glass substrate, wherein the composite film layer comprises two or three dielectric layers, a seed layer, a functional layer and a barrier layer which are sequentially arranged, when the composite film layer is coated, the antireflection film layer is adjacent to the dielectric layer of the composite film layer adjacent to the antireflection film layer, the functional layer of the composite film layer adjacent to the antireflection film layer is adjacent to the barrier layer of the composite film layer adjacent to the functional layer, and the top protective layer is adjacent to the barrier layer of the composite film layer adjacent to the top protective layer.
Taking the preparation of the LOW-reflection LOW-E coated glass with neutral color as an example, the preparation method is concretely illustrated, and comprises the following steps:
1. cleaning and drying a glass substrate to be coated;
2. carrying out vacuum transition;
3. sequentially forming the following sputtering layers from the glass substrate to the outside by vacuum magnetron sputtering, wherein the specific sputtering method comprises the following steps:
s1: the anti-reflection film layer is a NiCr layer, sputtering coating is carried out by adopting a magnetron sputtering process, and the thickness range of the film layer is 0-2 nm;
s2: the first dielectric layer is a SiNx layer, a magnetron sputtering process is adopted for sputtering coating, and the thickness range of the film layer is 28-35 nm;
s3: the first seed layer is a ZnOx layer, a magnetron sputtering process is adopted for sputtering coating, and the thickness range of the film layer is 5-8 nm;
s4: the first functional layer is an Ag + Cu layer (sequentially and respectively coated in sequence), sputtering coating is carried out by adopting a magnetron sputtering process, the total thickness range of the coating is 7-16 nm, and the thickness range of the Cu layer is 5-7 nm;
s5: the first barrier layer is a NiCrMo layer, a magnetron sputtering process is adopted for sputtering coating, and the thickness range of the coating is 0-2 nm;
s6: the second dielectric layer is a SiNx layer, a magnetron sputtering process is adopted for sputtering coating, and the thickness range of the film layer is 43-70 nm;
s7: the second seed layer is a ZnOx layer, a magnetron sputtering process is adopted for sputtering coating, and the thickness range of the film layer is 5-10 nm;
s8: the second functional layer is an Ag layer, sputtering coating is carried out by adopting a magnetron sputtering process, and the thickness range of the film layer is 10-15 nm;
s9: the second barrier layer is a NiCrMo layer, and is sputtered and coated by adopting a magnetron sputtering process, wherein the thickness of the film layer is 0-4 nm;
s10: the top protective layer is a SiNx layer, a magnetron sputtering process is adopted for sputtering coating, and the thickness range of the film layer is 25-43 nm;
the sputtering method of the antireflection film layer in the step S1 includes: the method adopts a direct current power supply, uses a NiCr target as a target material, has the purity of more than 99.99 percent, and performs sputtering in pure argon working gas.
The sputtering methods of the first dielectric layer, the second dielectric layer and the top protective layer in the steps S2, S6 and S10 all adopt: the sputtering target is formed by sputtering in a mixed gas of argon and nitrogen by adopting an alternating current medium-frequency power supply, using a SiAl target or a pure Si target as a target material, wherein the purity of the target material is more than 99.7% (if the SiAl target is adopted, the Al content in the SiAl target is 8-15 wt%, and Al doped in the SiAl material mainly plays a role in increasing the conductivity of a film layer material).
The sputtering method of the first seed layer and the second seed layer in the steps S3 and S7 is: the method is characterized in that an alternating current medium frequency power supply is adopted, a target material is a ZnAl target, the purity of the target material is more than 99.8 percent, the Al content in the target material is 1.5-2.5 wt percent, and the ZnAl target is formed by sputtering in a mixed gas of argon and oxygen.
The sputtering method of the first functional layer and the second functional layer in steps S4 and S8 is: the method adopts a direct current power supply, uses a target material which is Ag + Cu target or Ag target, has the purity of more than 99.99 percent, and carries out sputtering in pure argon working gas.
The sputtering method of the first barrier layer and the second barrier layer in the steps S5 and S9 is: a direct current power supply is adopted, a target material is a NiCrMo target, the purity of the target material is more than 99.9 percent, and the target material is sputtered in pure argon working gas. Wherein the thickness of at least one of the first barrier layer and the second barrier layer is more than or equal to 1 nm.
If the first barrier layer and the second barrier layer are NiCr layers, a target material NiCr target is used, the purity of the target material is more than 99.9 percent, and sputtering is carried out in pure argon working gas.
In the LOW-emissivity coated glass with the neutral color and LOW reflection provided by the invention, NiCrMo is used as a barrier layer of LOW-emissivity glass, and the produced product has the advantage of wide perspective color adjustment range, even can obtain the purpose of neutral transmission color under the condition of not using Cu with slightly poor machining resistance, and obtains more real impression when outdoor scenery is observed indoors; the material has the advantages that the NiCr is used as the antireflection film layer, the material has high visible light absorption capacity, high hardness, high abrasion resistance and high chemical stability, provides high antireflection capacity and simultaneously has a high protection effect on the film layer, and the NiCr can have good adhesion to glass and a used dielectric layer.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. The neutral-color LOW-reflection LOW-E coated glass is characterized in that: the neutral-color LOW-reflection LOW-E coated glass comprises a glass substrate, and an antireflection film layer, two or three composite film layers and a top protective layer which are sequentially plated from inside to outside and arranged on the surface of one side of the glass substrate, wherein each composite film layer comprises a dielectric layer, a seed layer, a functional layer and a barrier layer which are sequentially arranged, the antireflection film layer is adjacent to the dielectric layer of the composite film layer adjacent to the antireflection film layer, the barrier layer of the composite film layer adjacent to the antireflection film layer is adjacent to the dielectric layer of the composite film layer adjacent to the antireflection film layer, the top protective layer is adjacent to the barrier layer of the composite film layer adjacent to the top protective layer, the barrier layer is an NiCrMo layer or an NiCr layer, and at least one barrier layer of the composite film layer is an NiCrMo layer.
2. The LOW-emissivity coated glass of claim 1, wherein the glass comprises: the thickness of the barrier layer of at least one composite film layer is greater than or equal to 1 nm.
3. The LOW-emissivity coated glass of claim 1, wherein the glass comprises: the antireflection film layer is a NiCr layer.
4. The LOW-emissivity coated glass of claim 1, wherein the glass comprises: the functional layer is an Ag layer or an Ag + Cu layer; if the functional layer is an Ag + Cu layer, the Ag layer is adjacent to the seed layer of the composite film layer adjacent to the Ag layer, and the Cu layer is adjacent to the barrier layer of the composite film layer adjacent to the Cu layer.
5. The LOW-emissivity coated glass of claim 1, wherein the glass comprises: the dielectric layer and the top protective layer are a combination of one or more layers of SiNx layers, SiOx layers, SiNxOy layers and TiOx layers.
6. The LOW-emissivity coated glass of claim 1, wherein the glass comprises: the seed layer is one or the combination of two layers of a ZnOx layer and a ZnSnOx layer.
7. The LOW-emissivity coated glass of claim 1, wherein the glass comprises: the composite film layers are arranged in two, the composite film layers adjacent to the antireflection film layer comprise a first dielectric layer, a first seed layer, a first functional layer and a first barrier layer, the composite film layers adjacent to the top protective layer comprise a second dielectric layer, a second seed layer, a second functional layer and a second barrier layer, and the antireflection film layer, the first dielectric layer, the first seed layer, the first functional layer, the first barrier layer, the second dielectric layer, the second seed layer, the second functional layer, the second barrier layer and the top protective layer are deposited on one side surface of the glass substrate from inside to outside in sequence.
8. The LOW-emissivity coated glass of claim 1, wherein the glass comprises: the composite film layers adjacent to the antireflection film layer comprise a first dielectric layer, a first seed layer, a first functional layer and a first barrier layer, the middle composite film layer between the two composite film layers comprises a second dielectric layer, a second seed layer, a second functional layer and a second barrier layer, the composite film layer adjacent to the top protective layer comprises a third dielectric layer, a third seed layer, a third functional layer and a third barrier layer, and the antireflection film layer, the first dielectric layer, the first seed layer, the first functional layer, the first barrier layer, the second dielectric layer, the second seed layer, the second functional layer, the second barrier layer, the third dielectric layer, the third seed layer, the third functional layer, the third barrier layer and the top protective layer are sequentially deposited from inside to outside on one side surface of the glass substrate.
9. The LOW-emissivity coated glass of claim 1, wherein the glass comprises: in each composite film layer, the thickness of the functional layer is more than or equal to 7 and less than or equal to 16 nm; if the functional layer is an Ag + Cu layer, the thickness of the Cu layer is more than or equal to 5 and less than 7 nm; the thickness of the antireflection film layer is more than 1.3 and less than or equal to 3 nm; the thickness range of the dielectric layer is 28-70 nm; the thickness range of the seed layer is 5-10 nm; the thickness of the barrier layer is more than 0 and less than or equal to 4 nm; the thickness range of the top protective layer is 25-43 nm.
10. A method for preparing the neutral-color LOW-reflection LOW-E coated glass of any one of claims 1 to 9, wherein the method comprises the following steps: the method comprises the following steps: the method comprises the following steps of sequentially plating an antireflection film layer, a composite film layer and a top protective layer on the surface of one side of a glass substrate in a magnetron sputtering coating mode, wherein the number of the composite film layers is two or three, and the composite film layer comprises a dielectric layer, a seed layer, a functional layer and a barrier layer which are sequentially arranged; when the composite layer is plated, the antireflection film layer is adjacent to the dielectric layer of the composite film layer adjacent to the antireflection film layer, the functional layer of the composite film layer adjacent to the antireflection film layer is adjacent to the barrier layer of the composite film layer adjacent to the functional layer, and the top protective layer is adjacent to the barrier layer of the composite film layer adjacent to the top protective layer.
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| CN117510094A (en) * | 2023-10-31 | 2024-02-06 | 吴江南玻华东工程玻璃有限公司 | Low-emissivity coated glass |
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