CN105015109A - Coated glass with top-layer transparent electric-conduction protection film structure - Google Patents
Coated glass with top-layer transparent electric-conduction protection film structure Download PDFInfo
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- CN105015109A CN105015109A CN201510505268.5A CN201510505268A CN105015109A CN 105015109 A CN105015109 A CN 105015109A CN 201510505268 A CN201510505268 A CN 201510505268A CN 105015109 A CN105015109 A CN 105015109A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—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
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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 discloses coated glass with a top-layer transparent electric-conduction protection film structure. Target material arc light stable sputtering is adopted for a top-layer protection film (1), the voltage fluctuation of the sputtering process is smaller than 1 V, and the sputtering speed is (0.5-1.0) nm*m/min; a coating film layer serves as a protection film and has good wear resistance, and therefore scratching and scraping in the subsequent machining process of the coated glass are effectively prevented. Meanwhile, the coating film layer has good weather resistance, film sticking protection is not needed after the glass is coated with the film, and oxidation of the film layer does not occur when the glass is exposed in air for 30 days. The good bonding force between the coating film layer of a target material and an adjacent film layer is achieved, after the Low-E coated glass is toughened, film disengaging cannot occur, scratches do not exist, the wear resistance and the scratch-preventing performance of the glass coating film layer are improved, and the scrap rate of the coated glass in the deep processing process is obviously reduced; the wear resistance of the coated glass is improved, the coated glass passes through a salt spray test of 600 hours and is not oxidized after being toughened at a high temperature, and the stable decoration performance and optical performance of the coated glass are ensured.
Description
Technical field
The present invention relates to IPC and classify the selection of H01B dielectric material or C23C to the plating structure improvement opportunity of metal material, especially there is the coated glass of top layer electrically conducting transparent diaphragm structure.
Background technology
Application target carries out having of sputter coating field: Low emissivity (Low-E) glass, antireflective (AR) glass and electrically conducting transparent (TCO) glass.Low emissivity glass also claims Low-E glass, and Low-E is the abbreviation of English Low-Emissivity.This coated glass is mainly used in, on door and window for building, cladding glass and windshield, both having maintained good visible light transmissivity, can effectively reduce ultrared heat radiation again, plays attractive in appearance, environmental protection and energy-conservation effect.The off-line Low-E coated glass that vacuum magnetic-control sputtering method is produced, can obtain the demand of multiple light thermal property adaptation Different climate different regions by the design of different retes.Market batch production, generally with metal A g for functional layer, can be individual layer Ag film, double-deck Ag film and multilayer Ag film, and at design barrier layer, Ag layer both sides and dielectric layer, barrier layer prevents Na in glass
+ooze out the oxidation with Ag, dielectric layer strengthens adhesion, and adjustment color and transmitance, top layer is usually with SnO
2or SiNx is as protective layer.After coating film on glass, usually need to carry out to cut, edging, tempering, several rework process in synthesis.The tempering of Low-E glass will be heated to 600 ~ 650 DEG C in annealing furnace, eliminates internal stress, blow high pressure chilled air cools to room temperature after coming out of the stove with bull nozzle to coated glass by the deformation of self.Experience variations in temperature, easily there is oxidation and come off in rete, makes the color of coated glass and optical property change and scrap.
Antireflective (Anti-Reflection) glass is the rete preparing different optical material on ultra-white float glass; the interference of the light principle that disappears mutually is utilized to make the light transmission rate of coated glass reach more than 95%; reflectivity, lower than 4%, is mainly used in display device protection screen such as LCD TV, PDP TV, computer display screen, high-grade instrument face plate, touch-screen, photo frame glass etc. and improves the electronic product that transmissivity reduces reflectivity.
Transparent conducting glass is also known as TCO glass, and TCO is the abbreviation of English Transparent Conductive Oxide, high permeability (Tavg > 80%) and high electric conductivity (R < 10
-3Ω cm) be the performance characteristics of TCO glass, it is widely used in the fields such as thin film solar, display and touch-screen.Main off-line coated technique is on ultra-white float glass, be coated with ITO, AZO rete, and the transparent conductivity of ITO is good, and hardness is high, but material expensive, cost is high; AZO cost is low, transparent conductivity good, be easy to realize doping causes and more and more pays close attention in the industry.Nesa coating (TCO) glass not only has electric conductivity, has light transmission simultaneously, is with a wide range of applications.
Film that current transparent conducting film glass covers is divided into three kinds of films: zno-based TCO thin film, polynary TCO thin film, high mobility TCO thin film.
1), the optical energy gap of zno-based TCO thin film: ZnO is about 3.2eV, and fine to the transparency of visible ray, containing of Zn is abundant, nontoxic, low price, easilier than ITO etches.Therefore, in recent ten years, ZnO has become the popular research material of TCO thin film, is expected to become the alternative materials of ito thin film in flat-panel monitor.
2), polynary TCO thin film: exploitation is applicable to the TCO thin film of specific use, is combined by various TCO material, prepares the TCO thin film that some have new feature.The polynary TCO thin film be made up of TCO combination of materials, can adjust the electricity of film, optics, chemistry and physical property, thus obtain the performance not available for single TCO material, meet the needs of some special occasions by changing component.
3), high mobility TCO thin film: when absorption is not very serious, the absorption of TCO thin film to visible ray increases along with the increase of free carrier concentration, but reduce along with the increase of carrier mobility, the transparent region wavelength upper limit of TCO thin film is determined primarily of carrier concentration, reduce along with its increase, therefore the resistivity adopting the method improving carrier mobility to reduce TCO thin film need not sacrifice its optical property.For electronic device or wire, carrier mobility is one of principal element determining its response speed and power consumption.
Low emissivity glass, anti reflection glass and TCO glass coated glass edge trimming as cutting and edging procedure in, coated surface is easy to scratch, scuffing are occurring in process, causes yield rate to decline to a great extent.According to some manufacturers statistics because glass face scratches the percent defective that causes more than 3%, monthly scrap the coated glass of several thousand square metres.
Because the most weatherability of existing sputter-coated glasses is poor, place rete in atmosphere and oxidation will occur or demoulding causes and scraps, therefore need after plated film, do pad pasting protection immediately, enter membrane removal before subsequent processing, and need to synthesize hollow in 7 days.Consider handling, transport and process time, cause difficulty to strange land deep processing.
Find by prior art documents, the people such as Kevin P.Musselman report the aluminium lamination being deposited thin titanium layer, tungsten and thicker (500nm) by magnetron sputtering on transparent conducting glass ITO at " AdvancedMaterials " (" advanced material ") the 20th volume (2008) 4470-5 page, then prepared the method for ordered porous aluminum oxide thin film-ito glass composite substrate by constant voltage anodic oxidation.But this method requires harsh to sputtering condition, produce stress unavoidably, and the thickness of aluminium film can not reach micron order in sputter procedure, otherwise can because internal stress is excessive in anode oxidation process aluminium film occur breaking, limit it and apply further.
Chinese patent application 201010230837.7 discloses a kind of ordered porous aluminum oxide thin film of conductive material technical field and the preparation method of transparent conducting glass composite substrate thereof, by magnetron sputtering method difference depositing layers of titanium, tungsten layer and aluminium lamination on transparent conducting glass, then annealing heat treatment and anodized is carried out to sputtering the aluminium lamination obtained, obtain porous anodic alumina films, finally porous anodic alumina films is carried out to the removal of reaming and oxidation barrier layer, prepare ordered porous aluminum oxide thin film.
Summary of the invention
The object of this invention is to provide the coated glass with top layer electrically conducting transparent diaphragm structure, application coating film on glass, strengthen wearability and the weatherability on coated glass surface.Comprise:
1. improve wearability and the adhesion strength of coating film on glass layer, reduce the scrappage in coated glass process.
2. strengthen the weatherability of coated glass, deposit in atmosphere and be not oxidized, toughening process is not oxidized, not demoulding, ensures the stable of the ornamental and optical property of coated glass.
Object of the present invention will be realized by following technical measures: comprise top layer diaphragm and glass substrate; there is top layer diaphragm the upside of interlayer film structure on the glass substrate; this top layer diaphragm transmitance Tavg>=90%, electric conductivity R < 10
-3Ω cm, thickness (10 ~ 30) nm, refractive index n=2.0 ~ 2.3, extinction coefficient k ≈ 0, microhardness HV=1000 ~ 1800, adopt target arc light to stablize sputter coating, sputter procedure voltage pulsation is no more than 1V, and sputtering rate is (0.5 ~ 1.0) nm*m/min; Form top layer target that diaphragm utilizes, main component is zirconio material, target density > 90%, sheet resistance < 2000 ohm.
Especially; one deck Ag film is had in the middle of top layer diaphragm and glass substrate; and in Ag film, outside has dielectric layer and barrier layer respectively, is namely followed successively by first medium layer, the first barrier layer, Ag film, the second barrier layer, second dielectric layer and glass substrate under top layer diaphragm.
Especially, dielectric layer is SiNx/TiOx/SnO
2strengthen the material of adhesion function, including but not limited to this material; Barrier layer is that NiCrOx/AZO stops Na in glass
+the material of migration and the oxidation of Ag layer, including but not limited to this material.
Especially; more than two layers and two layers Ag films are had in the middle of top layer diaphragm and glass substrate; and dielectric layer and barrier layer is had respectively outside every layer of Ag film, namely the structure of two Ag film system is: under top layer diaphragm, be followed successively by first medium layer, the first barrier layer, an Ag film, second dielectric layer, the second barrier layer, the 2nd Ag film, the 3rd barrier layer, the 3rd dielectric layer and glass substrate.
Especially, in the middle of top layer diaphragm and glass substrate, there are one deck tco layer and one deck dielectric layer, namely under top layer diaphragm, are followed successively by tco layer, dielectric layer and glass substrate.
Especially; at least two layers of low-index film and high refractive index layer is had in the middle of top layer diaphragm and glass substrate; namely under top layer diaphragm, the first low-index film and the first high refractive index layer is followed successively by; until the n-th low-index film and the n-th high refractive index layer; and glass substrate, wherein n > 1.
Advantage of the present invention and effect: adopt the stable sputtering of target arc light, sputter procedure voltage pulsation is less than 1V; Sputtering rate is (0.5 ~ 1.0) nm*m/min; The rete be coated with, as protecting film, has good wearability, effectively prevent the scuffing of coated glass in following process process and scraps.Meanwhile, the rete be coated with has good weatherability, does not need pad pasting to protect after coating film on glass, exposes 30 days in atmosphere, the oxidation of rete does not occur.Have good adhesion between the rete that described target is coated with and adjacent film layers, not demoulding after Low-e coated glass tempering, the optical property after tempering and color homogeneity meet the requirement of GB/T18915.2-2013 low radiation coated glass standard.Improve wearability and the adhesion strength of coated glass, reduce the scrappage in coated glass accumulating and process.Strengthen the weatherability of coated glass, deposit in atmosphere and be not oxidized, toughening process is not oxidized, not demoulding, ensures the stable of the ornamental and optical property of coated glass.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention.
Fig. 2 is the Low-e film structure list Ag film structure schematic diagram be coated with in the embodiment of the present invention 1.
Fig. 3 is the two Ag film structure schematic diagram of Low-e film structure be coated with in the embodiment of the present invention 2.
Fig. 4 is TCO glass-film architecture schematic diagram in the embodiment of the present invention 2.
Fig. 5 is one side AR glass-film architecture schematic diagram in the embodiment of the present invention 2.
Reference numeral comprises: top layer diaphragm 1, dielectric layer 2, barrier layer 3, Ag film 4, glass substrate 5, tco layer 6, low-index film 7, high refractive index layer 8.
Detailed description of the invention
The principle of the invention is, emphasis is by increasing layer of transparent conducting film on existing coated glass, is ensureing not affect on the basis of the photoelectric properties such as the transmitance of former film system and electric conductivity, solves the defect of the not corrosion-resistant and easy scuffing of former coated glass.Adopt the stable sputtering of target arc light, sputter procedure voltage pulsation is less than 1V; The rete be coated with, as protecting film, improves wearability and the adhesion strength of coating film on glass layer, reduces the scrappage in coated glass process.Strengthen the weatherability of coated glass, deposit in atmosphere and be not oxidized, toughening process is not oxidized, not demoulding, ensures the stable of the ornamental and optical property of coated glass.
As shown in Figure 1, the present invention includes: top layer diaphragm 1 and glass substrate 5.Namely there is top layer diaphragm 1 upside of interlayer film structure on a glass substrate 5, this top layer diaphragm 1 transmitance Tavg>=90%, electric conductivity R < 10
-3Ω cm, thickness (10 ~ 30) nm, refractive index n=2.0 ~ 2.3, extinction coefficient k ≈ 0, microhardness HV=1000 ~ 1800, adopt target arc light to stablize sputter coating, sputter procedure voltage pulsation is not more than 1V, and sputtering rate is (0.5 ~ 1.0) nm*m/min; Formed top layer diaphragm 1 utilize target, main component is zirconio material, target density > 90%, sheet resistance < 2000 ohm.
Wherein, top layer diaphragm 1 is the hard films of high refraction, low absorption extinction coefficient; there is good toughness simultaneously; and good resistance to oxidation and acid-proof alkaline; and energy and adjacent film layers have good combination, play the good result increasing coated glass wearability and strengthen weatherability at glass uper side surface.
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1: the single Ag film structure of the Low-e film system that coated glass is coated with as shown in Figure 2; one deck Ag film 4 is had in the middle of top layer diaphragm 1 and glass substrate 5; and in Ag film 4, outside has dielectric layer 2 and barrier layer 3 respectively, is namely followed successively by first medium layer 2, first barrier layer 3, Ag film 4, second barrier layer 3, second dielectric layer 2 and glass substrate 5 for 1 time at top layer diaphragm.
In aforementioned, dielectric layer 2 is SiNx/TiOx/SnO
2/ wait material, barrier layer 3 is NiCrOx/AZO.
Embodiment 2: the two Ag film structure of the Low-e film system that coated glass is coated with as shown in Figure 3; two layers of Ag film 4 are had in the middle of top layer diaphragm 1 and glass substrate 5; and dielectric layer 2 and barrier layer 3 is had respectively outside every layer of Ag film 4, be namely followed successively by first medium layer 2, first barrier layer 3, an Ag film 4, second dielectric layer 2, second barrier layer 3, the 2nd Ag film 4, the 3rd barrier layer 3, the 3rd dielectric layer 2 and glass substrate 5 for 1 time at top layer diaphragm.
Embodiment 3: coated glass TCO glass-film architecture as shown in Figure 4, has one deck tco layer 6 and one deck dielectric layer 2, is namely followed successively by tco layer 6, dielectric layer 2 and glass substrate 5 for 1 time at top layer diaphragm in the middle of top layer diaphragm 1 and glass substrate 5.
Embodiment 4: coated glass one side AR glass-film architecture as shown in Figure 5; at least two layers of low-index film 7 and high refractive index layer 8 is had in the middle of top layer diaphragm 1 and glass substrate 5; namely the first low-index film 7 and the first high refractive index layer 8 is followed successively by for 1 time at top layer diaphragm; until the n-th low-index film 7 and the n-th high refractive index layer 8; and glass substrate 5, wherein n > 1.
The present invention utilizes the feature of a kind of zirconio material high rigidity, high tenacity, extensive chemical stability, as the protective top layer of multiple coating films glass, there are excellent scratch resistance and decay resistance, pad pasting is not needed to protect after coating film on glass, edge membrane removal is avoided before closing sheet, can long term storage, significantly reduce the scuffing of coated glass in accumulating and various deep-processing process and oxidation is scrapped, improve yields, reduce costs; Further, this film layer has high refraction, low absorption and good adaptability, and the adhesion between the stable of former film system photoelectric properties and rete can be kept unaffected; This material has good electric conductivity, remains higher plated film rate stabilization sputtering in coating process.
Claims (6)
1. there is the coated glass of top layer electrically conducting transparent diaphragm structure, comprise top layer diaphragm (1) and glass substrate (5); It is characterized in that, there is top layer diaphragm (1) upside of the interlayer film structure on glass substrate (5), this top layer diaphragm transmitance Tavg>=90%, electric conductivity R < 10
-3Ω cm, thickness (10 ~ 30) nm, refractive index n=2.0 ~ 2.3, extinction coefficient k ≈ 0, microhardness HV=1000 ~ 1800, adopt target material magnetic sputtering to form film, sputter procedure is stablized, and voltage pulsation is no more than 1V, and sputtering rate is (0.5 ~ 1.0) nm*m/min; Form the target that top layer diaphragm (1) utilizes, main component is zirconio material, target density > 90%, sheet resistance < 2000 ohm.
2. there is the coated glass of top layer electrically conducting transparent diaphragm structure as claimed in claim 1; it is characterized in that; one deck Ag film (4) is had in the middle of top layer diaphragm (1) and glass substrate (5); and in Ag film (4), outside has dielectric layer (2) and barrier layer (3) respectively, is namely followed successively by first medium layer (2), the first barrier layer (3), Ag film (4), the second barrier layer (3), second dielectric layer (2) and glass substrate (5) under top layer diaphragm (1).
3. there is the coated glass of top layer electrically conducting transparent diaphragm structure as claimed in claim 1, it is characterized in that, the Ag film (4) of more than two layers and two layers is had in the middle of top layer diaphragm (1) and glass substrate (5), and have dielectric layer (2) and barrier layer (3) respectively in every layer of Ag film (4) outside, namely the structure of two Ag film system is: under top layer diaphragm (1), be followed successively by first medium layer (2), first barrier layer (3), one Ag film (4), second dielectric layer (2), second barrier layer (3), 2nd Ag film (4), 3rd barrier layer (3), 3rd dielectric layer (2) and glass substrate (5).
4. there is the coated glass of top layer electrically conducting transparent diaphragm structure as claimed in claim 1; it is characterized in that; in the middle of top layer diaphragm (1) and glass substrate (5), there are one deck tco layer (6) and one deck dielectric layer (2), namely under top layer diaphragm (1), are followed successively by tco layer (6), dielectric layer (2) and glass substrate (5).
5. the coated glass with top layer electrically conducting transparent diaphragm structure as described in claim 2,3 and 4, is characterized in that, dielectric layer (2) is SiNx/TiOx/SnO
2/ wait material, barrier layer (3) are NiCrOx/AZO.
6. there is the coated glass of top layer electrically conducting transparent diaphragm structure as claimed in claim 1; it is characterized in that; at least two layers of low-index film (7) and high refractive index layer (8) is had in the middle of top layer diaphragm (1) and glass substrate (5); namely under top layer diaphragm (1), the first low-index film (7) and the first high refractive index layer (8) is followed successively by; until the n-th low-index film (7) and the n-th high refractive index layer (8); and glass substrate (5), wherein n > 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510505268.5A CN105015109A (en) | 2015-08-17 | 2015-08-17 | Coated glass with top-layer transparent electric-conduction protection film structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510505268.5A CN105015109A (en) | 2015-08-17 | 2015-08-17 | Coated glass with top-layer transparent electric-conduction protection film structure |
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| CN105015109A true CN105015109A (en) | 2015-11-04 |
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| CN201510505268.5A Pending CN105015109A (en) | 2015-08-17 | 2015-08-17 | Coated glass with top-layer transparent electric-conduction protection film structure |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110914211A (en) * | 2017-03-10 | 2020-03-24 | 佳殿玻璃有限公司 | IG window unit having triple silver and dielectric coatings on opposite sides of a glass substrate |
| CN111362590A (en) * | 2020-03-25 | 2020-07-03 | 四川猛犸半导体科技有限公司 | Thin film device |
| CN114105490A (en) * | 2021-12-16 | 2022-03-01 | 福耀玻璃工业集团股份有限公司 | Low-emissivity coated glass |
-
2015
- 2015-08-17 CN CN201510505268.5A patent/CN105015109A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 中国南玻集团工程玻璃事业部: "《建筑玻璃加工技术 玻璃镀膜工艺技术内容》", 31 March 2010 * |
| 白振中等: "《工程玻璃深加工技术手册》", 30 April 2014 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110914211A (en) * | 2017-03-10 | 2020-03-24 | 佳殿玻璃有限公司 | IG window unit having triple silver and dielectric coatings on opposite sides of a glass substrate |
| US11168023B2 (en) | 2017-03-10 | 2021-11-09 | Guardian Glass, LLC | IG window unit having triple silver coating and dielectric coating on opposite sides of glass substrate |
| CN111362590A (en) * | 2020-03-25 | 2020-07-03 | 四川猛犸半导体科技有限公司 | Thin film device |
| CN114105490A (en) * | 2021-12-16 | 2022-03-01 | 福耀玻璃工业集团股份有限公司 | Low-emissivity coated glass |
| CN114105490B (en) * | 2021-12-16 | 2022-11-29 | 福耀玻璃工业集团股份有限公司 | Low-emissivity coated glass |
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Inventor after: Huang Xiaojun Inventor after: Zhu Bin Inventor after: Zhuang Zhijie Inventor before: Wen Yanling Inventor before: Huang Xiaojun Inventor before: Zhu Bin Inventor before: Zhuang Zhijie |
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Application publication date: 20151104 |