CN113336452A

CN113336452A - Three-silver coated glass and manufacturing method thereof

Info

Publication number: CN113336452A
Application number: CN202110745570.3A
Authority: CN
Inventors: 唐燕军; 刘思睿; 陈阳; 钱万里; 张碧辉; 谢鹏程
Original assignee: Zhejiang Kibing Energy Saving Glass Co ltd; Changxing Qibin Energy Saving Glass Co ltd
Current assignee: Zhejiang Kibing Energy Saving Glass Co ltd; Changxing Qibin Energy Saving Glass Co ltd
Priority date: 2021-06-30
Filing date: 2021-06-30
Publication date: 2021-09-03

Abstract

The application relates to the technical field of glass products, and particularly provides three-silver coated glass and a manufacturing method thereof_xOne or more of the layers and the SiZr layer, the total thickness is 35-55 nm, and the manufacturing method is that the surface of the glass substrate is sputtered by vacuum magnetron sputtering in sequence by using a target material under a vacuum environment to form each layer. The method aims to solve the technical problems that the common three-silver Low-e glass film in the prior art is soft, has poor environmental adaptability and cannot be subjected to secondary treatment in the later period.

Description

Three-silver coated glass and manufacturing method thereof

Technical Field

The invention relates to the technical field of glass products, in particular to three-silver coated glass and a manufacturing method thereof.

Background

With the development of human society, global climate warming and carbon emission exceed standards, global carbon neutralization will greatly raise higher requirements for environmental protection and energy conservation, and single-double low-E glass has good energy-saving effect (the heat insulation and energy-saving effect of single-double low-E glass reaches about 90%), but in the face of the current environmental forms and energy-saving glass plates, better energy-saving products need to be developed.

The three-silver low-E glass is also named as infrared shielding glass, and is the building energy-saving glass with the best energy-saving property at present. Developed countries not only generally adopt high-performance low-E glass on public buildings, but also use the three-silver low-E glass with the best performance on residential buildings in a large quantity. The adoption of the high-efficiency energy-saving glass has low investment and high return, can be used for saving energy of buildings instantly, has great effects on saving energy and resources and has profound significance on the sustainable development of global economy.

The three-silver low-E glass has extremely low total transmittance of solar infrared heat energy; filtering the sun into a cold light source, and keeping the sun warm; the energy consumption of the air conditioner is reduced, and the investment of air conditioning equipment is reduced; the heat transfer coefficient K is low: the heat preservation performance is improved; the comfort is good: the indoor environment is cooler in summer and warmer in winter. Although the three-silver Low-E glass achieves a higher level in the aspects of heat insulation, sun shading, energy conservation and the like, the development of the three-silver Low-E glass is limited because the common three-silver Low-E glass has a soft film layer and poor environmental adaptability and cannot be subjected to secondary treatment in the later period.

Disclosure of Invention

In a first aspect, the invention aims to provide three-silver coated glass, and aims to solve the technical problems that a common three-silver Low-e glass in the prior art is soft in film layer, poor in environmental adaptability and incapable of performing secondary treatment in a later period.

In order to achieve the purpose, the invention adopts the technical scheme that: the utility model provides a three silver coated glass, includes glass base course and locates the coating film layer of glass base course one side, the coating film layer includes in proper order: the solar cell comprises a first dielectric layer, a first functional layer, a first protective layer, a second dielectric layer, a second functional layer, a second protective layer, a third dielectric layer, a third functional layer, a third protective layer and a fourth dielectric layer, wherein the fourth dielectric layer comprises one or more of an AZO layer, a SiNx layer and a SiZr layer which are sequentially arranged, and the total thickness of the fourth dielectric layer is 35-55 nm.

In one embodiment of the present invention, the first dielectric layer comprises SiN sequentially disposed_xLayer of ZnAlO_xOne or more of the layer and the AZO layer, the total thickness of which is 30-56 nm, if the first dielectric layer comprises SiN_xLayer of ZnAlO_xLayer and AZO layer, then SiN_xThickness of 10-21 nm, ZnAlO_xThe thickness of the layer is 15-25nm, and the thickness of the AZO layer is 5-10 nm.

In one embodiment of the present invention, the second dielectric layer includes an AZO layer and a ZnSnO layer sequentially disposed on the second dielectric layer_xLayer of ZnAlO_xThe thickness of the layer and the AZO layer is 55-85 nm in total, the thickness of the AZO layer in the second dielectric layer is 5-10nm, and ZnSnO is adopted_xThe layer thickness is 15-25nm, ZnAlO_xThe thickness of the layer is 30-40nm, and the thickness of the AZO layer is 5-10 nm.

In one embodiment of the invention, the third dielectric layer sequentially includes an AZO layer, a SiNx layer, and ZnSnO layer_xLayer and ZnAlO_xOne or more of the layers with a total thickness of 70-105 nm, and if the third dielectric layer comprises AZO layer and SiN layer_xLayer, ZnSnO_xLayer and ZnAlO_xA layer of AZO having a thickness of 5 to 10nm and SiN_xLayer thickness of 30-40nm, ZnSnO_xThe layer thickness is 15-25nm, ZnAlO_xThe layer thickness is 20-30 nm.

In one embodiment of the present invention, if the fourth dielectric layers all include AZO layers and SiN layers_xAnd SiZr layer with AZO layer thickness of 5-10nm and SiN layer_xThe thickness of the layer is 25-35 nm, and the thickness of the SiZr layer is 5-10 nm.

In one embodiment of the invention, the first functional layer, the second functional layer and the third functional layer are all Ag layers, the thickness of the Ag layer of the first functional layer is 6.5-8.5 nm, the thickness of the Ag layer of the second functional layer is 9-11 nm, and the thickness of the Ag layer of the third functional layer is 14.5-16.5 nm; the first protection layer and the second protection layer are both NiCr layers, the thickness of the NiCr layer of the first protection layer is 1.5-3.0 nm, the thickness of the NiCr layer of the second protection layer is 1.1-2.5 nm, the third protection layer comprises one or more of the NiCr layer and the Cr layer, and the thickness of the third protection layer is 1.1-2.5 nm.

The three-silver coated glass has the effect that the three-silver coated glass is provided with the fourth dielectric layer, and the fourth dielectric layer comprises an AZO layer and SiN_xAnd one or more SiZr layers, the AZO layer has the functions of improving the bonding force between the film layers and the structural stability of the whole film layer, and the SiN layer_xThe main role of the layer is due to SiN_xThe coating has the characteristics of high hardness and strong abrasion resistance, improves the mechanical property and the scratch resistance of the coating, ensures that a coated product is not easy to scratch, has stronger SiZr hardness and stronger corrosion resistance and oxidation resistance, and perfectly protects the glass from being damaged at 680 ℃ of the toughening furnace.

On the other hand, the invention also provides a manufacturing method of the three-silver coated glass, and the three-silver coated glass can be obtained by the method, has a toughening effect and can be subjected to secondary treatment.

The manufacturing method comprises the following steps: and performing vacuum magnetron sputtering on the surface of the glass base layer by using a target material in a vacuum environment to form a first dielectric layer, a first functional layer, a first protective layer, a second dielectric layer, a second functional layer, a second protective layer, a third dielectric layer, a third functional layer, a third protective layer and a fourth dielectric layer in sequence, thereby forming a coating layer.

In one embodiment of the present invention, during magnetron sputtering, the target materials used in the cathode are respectively a silicon aluminum target, a zinc aluminum target, an AZO metal oxide target, a silver target, a nickel chromium target, an AZO metal oxide target, a zinc tin target, a zinc aluminum target, an AZO metal oxide target, a silver target, a nickel chromium target, an AZO metal oxide target, a silicon aluminum target, a zinc aluminum target, a silver target, a nickel chromium target, an AZO metal oxide target, a silicon aluminum target, and a silicon zirconium target in sequence, wherein the AZO metal oxide target is formed by ZnO_x、AlO_xFired ceramic productThe purity of the metal oxide target material is more than or equal to 99.95 percent.

In one embodiment of the present invention, the silicon-aluminum target is a silicon-aluminum alloy target with a silicon-aluminum weight ratio of 9:1, the zinc-aluminum target is a zinc-aluminum alloy target with a zinc-aluminum weight ratio of 98:2, the zinc-tin target is a zinc-tin alloy target with a zinc-tin weight ratio of 50:50, the silver purity of the silver target is 99.99%, the nickel-chromium target is a nickel-chromium alloy target with a nickel-chromium weight ratio of 8:2, the AZO ceramic target material has a purity of 99.95%, the silver target and the nickel-chromium target are planar targets, and the silicon-aluminum target, the zinc-tin target and the AZO ceramic target are all rotary targets.

In one embodiment of the invention, the power of the silicon-aluminum target during magnetron sputtering is 0-60 Kw, and the ratio of high-purity argon and high-purity nitrogen in the sputtering process gas is 1: 1, sputtering gas pressure is 1-4 x 10-3 mbar; the power of the zinc-aluminum target is 0-50 Kw, the ratio of high-purity argon to high-purity oxygen in the sputtering process of the zinc-aluminum target is 1: 1.6, sputtering gas pressure is 1-4 x 10-3 mbar; the power of the zinc-tin target is 0-50 Kw, and the ratio of high-purity argon to high-purity nitrogen in the sputtering process gas is 1: 1.6, sputtering gas pressure is 1-4 x 10-3 mbar; the power of the silver target is 0-20 Kw, the power of the nickel-chromium target is 0-20 Kw, the power of the AZO ceramic target is 0-20 Kw, the sputtering process gas of the silver target, the nickel-chromium target and the AZO ceramic target is high-purity argon, and the sputtering pressure is 1-4 x 10-3 mbar.

The manufacturing method of the three-silver coated glass provided by the invention has the beneficial effects that: the three-silver coated glass prepared by the method provided by the invention overcomes the defect that the traditional three-silver film layer is fragile, can be used for tempering three-silver Low-E glass, can prolong the transportation and use time, can also be used for secondary treatment of tempering and bending tempering, and can be used for flat bending matching.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed for 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 invention, 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 three-silver coated glass provided in an embodiment of the present invention.

In the figure: 1. a glass substrate; 2. a first dielectric layer; 3. a first functional layer; 4. a first protective layer; 5. a second dielectric layer; 6. a second functional layer; 7. a second protective layer; 8. a third dielectric layer; 9. a third functional layer; 10. a third protective layer; 11. and a fourth dielectric layer.

Detailed Description

In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

It will be understood that when an element is referred to as being "secured to" or "disposed on" another element, it can be directly on the other element or be indirectly on the other element. When an element is referred to as being "connected to" another element, it can be directly connected to the other element or be indirectly connected to the other element.

Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise. The meaning of "a number" is one or more unless specifically limited otherwise.

In the description of the present invention, it is to be understood that the terms "center", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations and positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.

In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.

As shown in fig. 1, the present invention provides a specific embodiment of a three-silver coated glass, which includes a glass substrate 1 and a coating layer disposed on one side of the glass substrate 1, wherein the coating layer sequentially includes: the first dielectric layer 2, the first functional layer 3, the first protective layer 4, the second dielectric layer 5, the second functional layer 6, the second protective layer 7, the third dielectric layer 8, the third functional layer 9, the third protective layer 10, the fourth dielectric layer 11, and the fourth dielectric layer 11 comprise an AZO layer and an SiN layer which are sequentially arranged_xOne or more of the layers and the SiZr layer, and the total thickness is 35-55 nm.

The three-silver coated glass provided by the embodiment has four dielectric layers, three functional layers and three protective layers, compared with the prior art, the three-silver coated glass further has a fourth dielectric layer 11, and the fourth dielectric layer 11 comprises an AZO layer and a SiN layer which are sequentially arranged_xLayer and SiZr layer, wherein SiN_xThe main role of the layer is due to SiN_xThe coating has the characteristics of high hardness and strong abrasion resistance, improves the mechanical property and the scratch resistance of the coating, ensures that a coated product is not easy to scratch, has stronger SiZr hardness and stronger corrosion resistance and oxidation resistance, and perfectly protects the glass from being damaged at 680 ℃ of the toughening furnace. Therefore, the glass breaks the defect that the traditional three-silver film layer is fragile, the three-silver Low-E glass can be tempered, the transportation and use time can be prolonged, secondary treatment of tempering and bending tempering can be carried out, and the three-silver Low-E glass can be temperedMatched by flat bends.

In one embodiment of the present invention, the first dielectric layer 2 comprises a sequentially arranged underlying layer of SiN_xLayer of ZnAlO_xOne or more of a layer and an AZO layer. SiN_xThe layer is used as a priming layer and has the function of preventing elements such as Na +, K + and the like in the glass body from diffusing and migrating to the film layer to damage the functional layer and improve the adhesive force of the film layer; ZnAlO_xThe layer can be used as an adhesion layer of the first silver layer, and can be used as a seed layer to allow the Ag layer to grow uniformly on the seed layer, and the ZnO layer_xThe structure is smoother, a columnar structure can not be formed, the Ag layer can be uniformly attached to the Ag layer, and the film structure is more stable. The AZO layer is made of ZnO_x、AlO_xThe sintered ceramic target is plated, the purity of the AZO ceramic target is more than or equal to 99.95 percent, the film layer is uniform and compact, and the stability of the film layer structure is improved.

Wherein the total thickness of each layer is 30-56 nm, specifically, SiN_xThickness of 10-21 nm, ZnAlO_xThe thickness of the layer is 15-25nm, and the thickness of the AZO layer is 5-10 nm.

Further, the second dielectric layer 5 includes an AZO layer and a ZnSnO layer sequentially disposed thereon_xLayer of ZnAlO_xThe AZO layer is compact and uniform, so that the binding force between the metal NiCr layer and the dielectric layer can be improved, and the stability of the structure of the film layer is improved; ZnSnO_xLayer and ZnAlO_xThe layer is as the dielectric layer, can design the rete structure, through different rete materials of control and thickness, the colour value of adjustment coating film product satisfies the required colour requirement of design, and the rete microstructure that general medium magnetron sputtering coating film formed is the columnar body moreover, and the structure is loose not compact, and the rete hollow is hollow, and it is big to fluctuate, not smooth, ZnO_xAnd ZnSnO_xThe structure of the film layer is compact. AZO layer, ZnSnO_xLayer of ZnAlO_xThe total thickness of the layer and the AZO layer is 55-85 nm, specifically, the thickness of the AZO layer in the second dielectric layer 5 can be 5-10nm, and ZnSnO_xThe layer thickness may be 15-25nm, ZnAlO_xThe thickness of the layer is preferably 30-40nm, and the thickness of the AZO layer is preferably 5-10 nm. The medium layer has another function of film layer structure design, utilizes the optical interference principle, can adjust the reflectivity of the film layer, and reduces urban light pollutionAnd (5) dyeing and damaging.

In one embodiment of the present invention, the third dielectric layer 8 sequentially includes an AZO layer and SiN layer_xLayer, ZnSnO_xLayer and ZnAlO_xAnd the AZO layer can improve the binding force between the metal NiCr layer and the dielectric layer and improve the stability of the structure of the film layer due to the fact that the film layer is compact and uniform. SiN_xLayer, ZnSnO_xAnd ZnAlO_xThe layer is as the dielectric layer, can design the rete structure, through controlling different rete materials and thickness, adjusts the colour value of coating film product, satisfies the required colour requirement of design. The dielectric layer has another function of film layer structure design, and can adjust the reflectivity of the film layer and reduce the urban light pollution hazard by using the light interference principle. The total thickness of the third dielectric layer 8 is 70-105 nm, the thickness of the AZO layer is 5-10nm, and SiN_xLayer thickness of 30-40nm, ZnSnO_xThe layer thickness is 15-25nm, ZnAlO_xThe layer thickness is 20-30 nm.

In one embodiment of the present invention, the fourth dielectric layers 11 each include an AZO layer and SiN layer_xAnd SiZr layer with AZO layer thickness of 5-10nm and SiN layer_xThe thickness of the layer is 25-35 nm, and the thickness of the SiZr layer is 5-10 nm. The fourth dielectric layer 11 is arranged to have the effect that the AZO layer has the same function as the AZO layer of the second dielectric layer 5, thereby improving the binding force between the films and the structural stability of the whole film. SiN_xThe main role of the layer is due to SiN_xThe coating has the characteristics of high hardness and strong abrasion resistance, improves the mechanical property and the scratch resistance of the coating, ensures that a coated product is not easy to scratch, has stronger SiZr hardness and stronger corrosion resistance and oxidation resistance, and perfectly protects the glass from being damaged at 680 ℃ of the toughening furnace.

Furthermore, the first functional layer 3, the second functional layer 6 and the third functional layer 9 are all Ag layers, and the Ag layers are used for reducing the radiance of the coated glass by utilizing the low radiation performance of Ag, filtering sunlight into a cold light source and improving the transmission performance. The thickness of the Ag layer of the first functional layer 3 is 6.5-8.5 nm, the thickness of the Ag layer of the second functional layer 6 is 9-11 nm, and the thickness of the Ag layer of the third functional layer 9 is 14.5-16.5 nm.

In the present embodiment, the first protective layer 4 and the second protective layer 7 are both NiCr layers, the thickness of the NiCr layer of the first protective layer 4 is 1.5 to 3.0nm, the thickness of the NiCr layer of the second protective layer 7 is 1.1 to 2.5nm, and the third protective layer 10 includes one or more of an NiCr layer and a Cr layer, and has a thickness of 1.1 to 2.5 nm. The primary functions of the first protective layer 4, the second protective layer 7 and the third protective layer 10 are to protect the Ag layer from oxidation and to adjust the b value of the glass surface.

The three-silver coated glass provided by the embodiment has high light transmittance, good natural lighting and lighting energy consumption saving; the three-silver-layer toughened high-transmittance three-silver coated infrared shielding glass has the characteristics of light transmission, heat impermeability, excellent sun shading performance and the like, has higher sun shading performance and higher transmittance than common three-silver, is closer to zero transmission color, adopts a three-silver structure, has high transmittance after toughening through the structural design of a film layer, has extremely low radiance, strong bonding force of the film layer, stable color and good consistency, presents a bluish gray outdoors, has strong machinability, can be used for toughening hot bending processing, has small color change before and after toughening, and has excellent applicability and universality.

On the other hand, the invention also provides an embodiment of a manufacturing method of the three-silver coated glass.

Firstly, a target material is used for carrying out vacuum magnetron sputtering on the surface of a glass substrate 1 in a vacuum environment to form a first dielectric layer 2, a first functional layer 3, a first protective layer 4, a second dielectric layer 5, a second functional layer 6, a second protective layer 7, a third dielectric layer 8, a third functional layer 9, a third protective layer 10 and a fourth dielectric layer 11 in sequence, thereby forming a coating layer.

In the embodiment, the fourth dielectric layer 11 is protected from sputtering, and the formed coating layer comprises the fourth dielectric layer 11, so that the prepared product can be better tempered.

In one embodiment of the present invention, during magnetron sputtering, the target materials used in the cathode are respectively a silicon aluminum target, a zinc aluminum target, an AZO metal oxide target, a silver target, a nickel chromium target, an AZO metal oxide target, a zinc tin target, a zinc aluminum target, an AZO metal oxide target, a silver target, a nickel chromium target, an AZO metal oxide target, a silicon aluminum target, a zinc aluminum target, a silver target, a nickel chromium target, an AZO metal oxide targetTarget, silicon aluminum target, silicon zirconium target, wherein the AZO metal oxide target is made of ZnO_x、AlO_xThe fired metal oxide target with ceramic function has the target purity more than or equal to 99.95 percent. The film layer of the plated AZO is uniform and compact, the more compact the film layer is, the more difficult the film layer is to be damaged in a toughening furnace, and the smaller the color difference before and after toughening is.

Specifically, in the embodiment, the preparation method can be carried out by only adopting a conventional target material and utilizing a magnetron sputtering process, and has the advantages of low cost, controllable process, high stability and excellent energy-saving performance.

In one embodiment of the invention, the power of the silicon-aluminum target during magnetron sputtering is 0-60 Kw, and the ratio of high-purity argon and high-purity nitrogen in the sputtering process gas is 1: 1, sputtering gas pressure is 1-4 x 10-3 mbar; the power of the zinc-aluminum target is 0-50 Kw, the ratio of high-purity argon to high-purity oxygen in the sputtering process of the zinc-aluminum target is 1: 1.6, sputtering gas pressure is 1-4 x 10-3 mbar; the power of the zinc-tin target is 0-50 Kw, and the ratio of high-purity argon to high-purity nitrogen in the sputtering process gas is 1: 1.6, sputtering gas pressure is 1-4 x 10-3 mbar; the power of the silver target is 0-20 Kw, the power of the nickel-chromium target is 0-20 Kw, the power of the AZO ceramic target is 0-20 Kw, the sputtering process gas of the silver target, the nickel-chromium target and the AZO ceramic target is high-purity argon, and the sputtering pressure is 1-4 x 10-3 mbar. When the sputtering pressure is 1-4 x 10^ -3mbar, the molecular mean free path distance is relatively stable, the target sputtering is more stable, and the film layer is more compact.

The film system adopted by the invention has reasonable structure, excellent binding force and good heat insulation performance of the prepared product. The film layer has stable structure, difficult oxidation and strong machinability, meets the toughening requirement, and changes color after the toughening processSmall size, stable film layer, no cracking, oxidation, demoulding and other defects. The surface radiance of the toughened glass is as low as 0.03, and the toughened glass has the advantages of low U value, low sun-shading coefficient and the like, and the heat transfer coefficient K value is 1.60-1.70W/m²) The solar energy transmission is reduced, meanwhile, the visible light transmission rate of about 65 percent can be still kept, the glare effect is reduced, and the requirement on high-end three-silver coated glass is met.

The colors of the invention are described by L, a, b in Lab color space. The 6mm coated glass single sheet prepared by the method has the transmittance T of 50-60 percent before tempering, a is-5.54-6.68 percent, and b is 0.9-1.5 percent; the glass surface color L is 23-32, a is-0.9-2.0, b is 5.56-7.59. The transmittance T after tempering is 65-76%, a is-5.51 to-6.71, and b is-3.3 to-6.2; the color L of the glass surface is 24-34, a is 0.5-0.6, and b is 4.1-6.9. The color of the glass surface is blue-gray, and the color consistency is good.

The color difference delta E of the glass tempering room outside and at small angles is less than 1.5, the whole color is uniform when the glass tempering room is observed at different angles, and the whole attractiveness of the glass is improved.

The present invention also provides three specific embodiments within the numerical range,

example 1, the coating of the invention was applied in the following form:

the first dielectric layer 2 is sequentially composed of SiN_xLayer of ZnAlO_xThe layer and the AZO layer are respectively 17nm, 18nm and 8nm, and the total thickness is 43 nm.

The first functional layer 3 consists of an arranged Ag layer with a thickness of 6.81 nm.

The first protective layer 4 consists of an provided NiCr layer with a thickness of 2.04 nm.

The second dielectric layer 5 comprises an AZO layer and ZnSnO layer arranged in sequence_xLayer of ZnAlO_xAnd AZO layers with a total thickness of 68nm and a thickness of 8nm, 22nm, 30nm and 8nm respectively.

The second functional layer 6 consists of an arranged Ag layer with a thickness of 10.00 nm.

The second protective layer 7 consists of an NiCr layer arranged with a thickness of 1.83 nm.

The third dielectric layer 8 is composed of an AZO layer and SiN layer arranged in sequence_xLayer, ZnSnO_xLayer and ZnAlO_x8nm, 35nm, 16nm and 25nm respectively, and the total thickness is 84 nm.

The third functional layer 9 consists of an arranged Ag layer with a Ag thickness of 14.9 nm.

The third protective layer 10 consists of an provided layer of NiCr with a thickness of 1.65 nm.

The fourth dielectric layer 11 is composed of an AZO layer and SiN layer arranged in sequence_xThe layer and the SiZr layer are respectively 8nm, 30nm and 7nm, and the total thickness is 45 nm.

Example 2, the coating of the invention was applied in the following form:

the first dielectric layer 2 is sequentially composed of SiN_xLayer of ZnAlO_xThe layer and the AZO layer are respectively 15.6nm, 18.2nm and 8nm, and the total thickness is 41.8 nm.

The first functional layer 3 consists of an arranged Ag layer with a thickness of 7.3 nm.

The first protective layer 4 was composed of an NiCr layer provided to a thickness of 1.83 nm.

The second dielectric layer 5 comprises an AZO layer and ZnSnO layer arranged in sequence_xLayer of ZnAlO_xAnd AZO layers of 8nm, 18nm, 35nm and 8nm respectively, and the total thickness is 69 nm.

The second functional layer 6 consists of an arranged Ag layer with a thickness of 10.25 nm.

The second protective layer 7 consists of an NiCr layer arranged with a thickness of 1.63 nm.

The third dielectric layer 8 is composed of an AZO layer and SiN layer arranged in sequence_xLayer, ZnSnO_xLayer and ZnAlO_x8nm, 30nm, 18.5nm and 26.5nm respectively, and the total thickness is 83 nm.

The third functional layer 9 consists of an arranged Ag layer with a Ag thickness of 15.5 nm.

The third protective layer 10 consists of an provided layer of NiCr with a thickness of 1.35 nm.

The fourth dielectric layer 11 is composed of an AZO layer and SiN layer arranged in sequence_xThe layer and the SiZr layer are respectively 8nm, 28nm and 10nm, and the total thickness is 46 nm.

Example 3, the coating of the invention was applied in the following form:

the first dielectric layer 2 is sequentially composed of SiN_xLayer, ZThe nAlOx layer and the AZO layer are respectively 15nm, 22nm and 10nm, and the total thickness is 47 nm.

The first functional layer 3 consists of an arranged Ag layer with a thickness of 8 nm.

The first protective layer 4 consists of an NiCr layer arranged with a thickness of 1.56 nm.

The second dielectric layer 5 comprises an AZO layer and ZnSnO layer arranged in sequence_xLayer of ZnAlO_xAnd AZO layers of 9nm, 15nm, 40nm and 10nm respectively, and the total thickness is 74 nm.

The second functional layer 6 consists of an arranged Ag layer with a thickness of 10.5 nm.

The second protective layer 7 is composed of an NiCr layer provided to a thickness of 2.0 nm.

The third dielectric layer 8 is composed of an AZO layer and SiN layer arranged in sequence_xLayer, ZnSnO_xLayer and ZnAlO_x5nm, 31nm, 15nm and 22nm respectively, and the total thickness is 73 nm.

The third functional layer 9 consists of an arranged Ag layer with a Ag thickness of 16.2 nm.

The third protective layer 10 consists of an arranged NiCr layer with a thickness of 1.25 nm.

The fourth dielectric layer 11 is composed of an AZO layer and SiN layer arranged in sequence_xThe layer and the SiZr layer are respectively 10nm, 25nm and 9nm, and the total thickness is 44 nm.

In addition, the invention also provides two embodiments at the end of the numerical range:

example 4, the coating of the invention was applied in the following form:

the first dielectric layer 2 is sequentially composed of SiN_xLayer of ZnAlO_xThe layer and the AZO layer are respectively 10nm, 15nm and 5nm, and the total thickness is 30 nm.

The first functional layer 3 consists of an arranged Ag layer with a thickness of 6.5 nm.

The first protective layer 4 consists of an arranged NiCr layer with a thickness of 1.5 nm.

The second dielectric layer 5 comprises an AZO layer and ZnSnO layer arranged in sequence_xLayer of ZnAlO_xAnd AZO layers of 5nm, 15nm, 30nm and 5nm respectively, and the total thickness is 55 nm.

The second functional layer 6 consists of an arranged Ag layer with a thickness of 9 nm.

The second protective layer 7 is composed of an NiCr layer provided to a thickness of 1.1 nm.

The third dielectric layer 8 is composed of an AZO layer and SiN layer arranged in sequence_xLayer, ZnSnO_xLayer and ZnAlO_x5nm, 30nm, 15nm and 20nm respectively, and the total thickness is 70 nm.

The third functional layer 9 consists of an arranged Ag layer with a Ag thickness of 14.5 nm.

The third protective layer 10 consists of an arranged NiCr layer with a thickness of 1.1 nm.

The fourth dielectric layer 11 is composed of an AZO layer and SiN layer arranged in sequence_xThe layer and the SiZr layer are respectively 5nm, 25nm and 5nm, and the total thickness is 35 nm.

Example 5, the coating of the invention was applied in the following form:

the first dielectric layer 2 is sequentially composed of SiN_xLayer of ZnAlO_xThe layer and the AZO layer are respectively 21nm, 25nm and 10nm, and the total thickness is 56 nm.

The first functional layer 3 consists of an arranged Ag layer with a thickness of 8.5 nm.

The first protective layer 4 was composed of an NiCr layer provided to a thickness of 3.0 nm.

The second dielectric layer 5 comprises an AZO layer and ZnSnO layer arranged in sequence_xLayer of ZnAlO_xAnd AZO layers of 10nm, 25nm, 40nm and 10nm respectively, and the total thickness is 85 nm.

The second functional layer 6 consists of an arranged Ag layer with a thickness of 11 nm.

The second protective layer 7 consists of an NiCr layer arranged with a thickness of 2.5 nm.

The third dielectric layer 8 is composed of an AZO layer and SiN layer arranged in sequence_xLayer, ZnSnO_xLayer and ZnAlO_x10nm, 40nm, 25nm and 30nm respectively, and the total thickness is 105 nm.

The third functional layer 9 consists of an arranged Ag layer with a Ag thickness of 16.5 nm.

The third protective layer 10 consists of an arranged NiCr layer with a thickness of 2.5 nm.

The fourth dielectric layer 11 is composed of an AZO layer and SiN layer arranged in sequence_xLayer and SiZr layer of 10nm, 35nm and 10nm, and the total thickness is 55 nm.

According to the structure and the thickness of the film layer, the film is plated on a high-quality 6mm float glass substrate by using a vacuum magnetron sputtering technology, and after the detection and analysis of a professional optical instrument, the color parameters of a single sheet are as shown in the following table, and the single sheet is observed to be low-reflection blue gray outdoors.

The glass is further processed into hollow glass (6mm +12mmA +6mm), and the hollow glass has the characteristics of low sun-shading coefficient, low heat transfer coefficient U value, low solar heat radiation transmission and the like as shown in the following table, and the energy-saving performance after the steel is more excellent, so that the super heat insulation effect is achieved.

	Transmittance Tvis (%)	Shading coefficient Sc	Coefficient of heat transfer U	Solar Heat radiation Transmission Tsol (%)
					Before tempering	46～51	≤0.27	≤1.58	≤21.5
After tempering	62～67	≤0.34	≤1.49	≤26.5

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims

1. Three silver coated glass, its characterized in that includes glass basic unit and locates the coating film layer of glass basic unit one side, the coating film layer includes in proper order: the protective film comprises a first dielectric layer, a first functional layer, a first protective layer, a second dielectric layer, a second functional layer, a second protective layer, a third dielectric layer, a third functional layer, a third protective layer and a fourth dielectric layer, wherein the fourth dielectric layer comprises an AZO layer and an SiN layer which are sequentially arranged_xOne or more of the layers and the SiZr layer, and the total thickness is 35-55 nm.

2. The triple-silver coated glass according to claim 1, wherein the first dielectric layer comprises sequentially disposed SiN_xLayer of ZnAlO_xOne or more of the layer and the AZO layer, the total thickness of which is 30-56 nm, if the first dielectric layer comprises SiN_xLayer of ZnAlO_xLayer and AZO layer, then SiN_xThickness of 10-21 nm, ZnAlO_xThe thickness of the layer is 15-25nm, and the thickness of the AZO layer is 5-10 nm.

3. The three-silver coated glass according to claim 1, wherein the second dielectric layer comprises an AZO layer and a ZnSnO layer sequentially arranged_xLayer of ZnAlO_xThe thickness of the layer and the AZO layer is 55-85 nm in total, the thickness of the AZO layer in the second dielectric layer is 5-10nm, and ZnSnO is adopted_xThe layer thickness is 15-25nm, ZnAlO_xThe thickness of the layer is 30-40nm, and the thickness of the AZO layer is 5-10 nm.

4. The three-silver coated glass according to claim 1, wherein the third dielectric layer comprises an AZO layer and a SiN layer in sequence_xLayer, ZnSnO_xLayer and ZnAlO_xOne or more of the layers with a total thickness of 70-105 nm, and if the third dielectric layer comprises AZO layer and SiN layer_xLayer, ZnSnO_xLayer and ZnAlO_xA layer of AZO having a thickness of 5 to 10nm and SiN_xLayer thickness of 30-40nm, ZnSnO_xThe layer thickness is 15-25nm, ZnAlO_xThe layer thickness is 20-30 nm.

5. The three-silver coated glass according to claim 1, wherein if the fourth dielectric layers all comprise AZO layer and SiN layer_xAnd SiZr layer with AZO layer thickness of 5-10nm and SiN layer_xThe thickness of the layer is 25-35 nm, and the thickness of the SiZr layer is 5-10 nm.

6. The three-silver coated glass according to claim 1, wherein the first functional layer, the second functional layer and the third functional layer are all Ag layers, the thickness of the Ag layer of the first functional layer is 6.5-8.5 nm, the thickness of the Ag layer of the second functional layer is 9-11 nm, and the thickness of the Ag layer of the third functional layer is 14.5-16.5 nm; the first protection layer and the second protection layer are both NiCr layers, the thickness of the NiCr layer of the first protection layer is 1.5-3.0 nm, the thickness of the NiCr layer of the second protection layer is 1.1-2.5 nm, the third protection layer comprises one or more of the NiCr layer and the Cr layer, and the thickness of the third protection layer is 1.1-2.5 nm.

7. The manufacturing method of the three-silver coated glass is characterized by comprising the following steps: and performing vacuum magnetron sputtering on the surface of the glass base layer by using a target material in a vacuum environment to form a first dielectric layer, a first functional layer, a first protective layer, a second dielectric layer, a second functional layer, a second protective layer, a third dielectric layer, a third functional layer, a third protective layer and a fourth dielectric layer in sequence, thereby forming a coating layer.

8. The method of claim 7, wherein the magnetic layer is formed by a magnetic coating processWhen controlling sputtering, the target material used by the cathode position is respectively a silicon aluminum target, a zinc aluminum target, an AZO metal oxide target, a silver target, a nickel chromium target, an AZO metal oxide target, a zinc tin target, a zinc aluminum target, an AZO metal oxide target, a silver target, a nickel chromium target, an AZO metal oxide target, a silicon aluminum target, a zinc aluminum target, a silver target, a nickel chromium target, an AZO metal oxide target, a silicon aluminum target and a silicon zirconium target in sequence, wherein the AZO metal oxide target is ZnO_x、AlO_xThe fired metal oxide target with ceramic function has the target purity more than or equal to 99.95 percent.

9. The method for manufacturing the tri-silver coated glass according to claim 8, wherein the silicon-aluminum target is a silicon-aluminum alloy target with a weight ratio of silicon to aluminum of 9:1, the zinc-aluminum target is a zinc-aluminum alloy target with a weight ratio of zinc to aluminum of 98:2, the zinc-tin target is a zinc-tin alloy target with a weight ratio of zinc to tin of 50:50, the silver purity of the silver target is 99.99%, the nickel-chromium target is a nickel-chromium alloy target with a weight ratio of nickel to chromium of 8:2, the AZO ceramic target material has a purity of 99.95%, the silver target and the nickel-chromium target are planar targets, and the silicon-aluminum target, the zinc-tin target and the AZO ceramic target are all rotary targets.

10. The method for manufacturing the three-silver coated glass according to claim 9, wherein the power of the silicon-aluminum target during magnetron sputtering is 0-60 Kw, and the ratio of the high-purity argon and the high-purity nitrogen in the sputtering process gas is 1: 1, sputtering gas pressure is 1-4 x 10-3 mbar; the power of the zinc-aluminum target is 0-50 Kw, the ratio of high-purity argon to high-purity oxygen in the sputtering process of the zinc-aluminum target is 1: 1.6, sputtering gas pressure is 1-4 x 10-3 mbar; the power of the zinc-tin target is 0-50 Kw, and the ratio of high-purity argon to high-purity nitrogen in the sputtering process gas is 1: 1.6, sputtering gas pressure is 1-4 x 10-3 mbar; the power of the silver target is 0-20 Kw, the power of the nickel-chromium target is 0-20 Kw, the power of the AZO ceramic target is 0-20 Kw, the sputtering process gas of the silver target, the nickel-chromium target and the AZO ceramic target is high-purity argon, and the sputtering pressure is 1-4 x 10-3 mbar.