Double-silver Low-E coated glass and preparation method thereof

Abstract

The invention provides double-silver Low-E coated glass and a preparation method thereof. In the double-silver Low-E coated glass, a Low-E film layer sequentially comprises a first dielectric layer, a first seed layer, an absorption layer, a first silver layer, a first protective layer, a second dielectric layer, a second seed layer, a second silver layer, a second protective layer, a third dielectric layer and an outermost protective layer from one surface of glass serving as a substrate; wherein the second dielectric layer is a metal oxide thin film; the third dielectric layer comprises a metal oxide film adjacent to the second protective layer; the first protection layer and the second protection layer are pure metal or alloy films in a complete oxidation state; the first seed layer is composed of a ZnAlO thin film adjacent to the first dielectric layer and a non-peroxy-state AZO thin film between the ZnAlO thin film and the absorption layer; and the absorption layer is a NiCr film, a Ti film, a Ni film, a Cr film or a ZnAl film in a metal state. The preparation method of the double-silver Low-E coated glass is used for preparing the double-silver Low-E coated glass disclosed by the invention.

Description

Technical Field

[0001] The present disclosure relates to coated glass for buildings, and more particularly to a double-silver Low-E coated glass and a method for preparing the same. Background Art

[0002] Low-E (low-emissivity) coated glass is a film system product with multiple layers of metals or other compounds coated on the glass surface. Its coating layer has the characteristics of high transmittance to visible light and high reflectivity to mid- and far-infrared rays, making it have excellent heat insulation effect and good light transmittance compared with ordinary glass and traditional building coated glass (including glass used in residences and curtain walls). In practical applications, Low-E coated glass and uncoated glass form a hollow structure, for example, as Figure 1 shown. With the increasing demand, it is necessary to further research and improve the optical and heat insulation properties of Low-E coated glass and single hollow structures. Summary of the Invention

[0003] In view of the problems existing in the background art, an object of the present disclosure is to provide a double-silver Low-E coated glass and a method for preparing the same, which can improve the optical and heat insulation properties of Low-E coated glass and single hollow structures.

[0004] Accordingly, a double-silver Low-E coated glass is provided, wherein the Low-E film layer sequentially includes a first dielectric layer, a first seed layer, an absorption layer, a first silver layer, a first protective layer, a second dielectric layer, a second seed layer, a second silver layer, a second protective layer, a third dielectric layer, and an outermost protective layer starting from one surface of the glass as the substrate; wherein, the second dielectric layer is a metal oxide thin film; the third dielectric layer includes a metal oxide thin film adjacent to the second protective layer; the first protective layer and the second protective layer are each a thin film in a completely oxidized state of a pure metal or an alloy; the first seed layer is composed of a ZnAlO thin film adjacent to the first dielectric layer and a non-peroxide AZO thin film between the ZnAlO thin film and the absorption layer; the absorption layer is a metallic NiCr thin film, Ti thin film, Ni thin film, Cr thin film, or ZnAl thin film.

[0005] Provided is a method for preparing a double-silver Low-E coated glass. The method for preparing the double-silver Low-E coated glass is used to prepare the aforementioned double-silver Low-E coated glass. The method for preparing the double-silver Low-E coated glass includes the steps of: S1, feeding the glass as a substrate into a horizontal vacuum magnetron sputtering coating continuous line, so as to sequentially sputter and coat a first dielectric layer, a first seed layer, an absorption layer, a first silver layer, a first protective layer, a second dielectric layer, a second seed layer, a second silver layer, a second protective layer, a third dielectric layer, and an outermost protective layer of the Low-E film layer from one surface of the glass as a substrate at room temperature. Among them, the ZnAlO thin film adjacent to the first dielectric layer in the first seed layer is sputter-coated using a ZnAl target in an argon-oxygen mixed atmosphere, the AZO thin film in the first seed layer is magnetron sputter-coated using a ceramic AZO target in a pure argon and oxygen-free atmosphere, the absorption layer is sputter-coated using a NiCr, Ti, Ni, or Cr target in a pure argon and oxygen-free atmosphere, the first protective layer and the second protective layer are magnetron sputter-coated using a pure metal or alloy target in a pure argon and oxygen-free atmosphere, the second dielectric layer is magnetron sputter-coated using a pure metal or alloy target in an argon-oxygen mixed atmosphere, and the metal oxide thin film adjacent to the second protective layer included in the third dielectric layer is magnetron sputter-coated using a pure metal or alloy target in an argon-oxygen mixed atmosphere; S2, tempering the glass on which the Low-E film layer has been coated.

[0006] The beneficial effects of the present disclosure are as follows: In the double-silver Low-E coated glass and the preparation method thereof of the present disclosure, the optical properties and heat insulation properties of the Low-E coated glass and the single insulating structure can be improved. Description of the Drawings

[0007] Figure 1 is a schematic diagram of a single insulating structure composed of a double-silver Low-E coated glass and ordinary glass.

[0008] Figure 2 Schematic structural diagram of the double-silver Low-E coated glass according to the present disclosure.

[0009] Figure 3 Shows Figure 2 the principle of the scattering of incident light when the first protective layer and the second protective layer in

[0010] Figure 4 Schematic structural diagram of the double-silver Low-E coated glass used in Comparative Example 1-2.

[0011] Figure 5 is at Figure 4 Based on the above, the specific materials used in Comparative Example 1-2 for the test process are given, where the materials of the first protective layer and the second protective layer are represented in the metal state during magnetron sputtering coating.

[0012] Figure 6 It is based on Figure 2 to give the specific materials used in Examples 1-2 of the test process. Among them, the materials of the first protective layer and the second protective layer are represented in the metallic state during magnetron sputtering coating.

[0013] Figure 7 The graph of the transmittance of the double-silver Low-E coated glass after tempering in the preparation methods of Examples 1-2 and Comparative Examples 1-2 is given. Detailed implementation manners

[0014] The accompanying drawings illustrate embodiments of the present disclosure, and it will be understood that the disclosed embodiments are merely examples of the present disclosure, and the present disclosure can be implemented in various forms. Therefore, the specific details disclosed herein should not be construed as limiting, but only as the basis of the claims and as a representative basis for teaching those of ordinary skill in the art to implement the present disclosure in various ways.

[0015] [Double-silver Low-E coated glass]

[0016] Referring to Figure 2 , in the double-silver Low-E coated glass according to the present disclosure, the Low-E film layer sequentially includes a first dielectric layer, a first seed layer, an absorption layer, a first silver layer, a first protective layer, a second dielectric layer, a second seed layer, a second silver layer, a second protective layer, a third dielectric layer, and an outermost protective layer starting from one surface of the glass as the substrate. Among them, the second dielectric layer is a metal oxide thin film; the third dielectric layer includes a metal oxide thin film adjacent to the second protective layer; the first protective layer and the second protective layer are each a thin film in the fully oxidized state of a pure metal or an alloy; the first seed layer is composed of a ZnAlO thin film adjacent to the first dielectric layer and a non-peroxide AZO thin film between the ZnAlO thin film and the absorption layer; the absorption layer is a metallic NiCr thin film, Ti thin film, Ni thin film, Cr thin film, or ZnAl thin film.

[0017] Referring to Figure 3, when the first protective layer and the second protective layer are films in a non-fully oxidized state of pure metal or alloy, since the pure metal or alloy of the first protective layer and the second protective layer has not been fully oxidized, there may be three states in the same layer, namely the metallic state, the sub-oxidized state, and the fully oxidized state. Since the three states exist in the same film and are unevenly distributed, the stresses of the first protective layer and the second protective layer on the first silver layer and the second silver layer below them are inconsistent, resulting in poor growth morphology at the interfaces between the first protective layer and the first silver layer and between the second protective layer and the second silver layer. The first silver layer and the second silver layer are damaged to a certain extent, and the flatness of the first silver layer and the second silver layer becomes worse. In this way, the interfaces between the second protective layer and the second silver layer and between the first protective layer and the first silver layer are relatively rough, and the scattering of light reaching the interfaces is large. From the visual effect, the haze of the product (such as forming Figure 1 hollow structure) becomes larger, and fog-like defects of different colors will be generated when observed under strong light. In addition, the damage to the first silver layer and the second silver layer to a certain extent will affect the quality of the first silver layer and the second silver layer, reducing the performance of the Low-E glass.

[0018] In the double-silver Low-E coated glass according to the present disclosure, the first protective layer and the second protective layer in the Low-E film layer are each a film in a fully oxidized state of pure metal or alloy. The stresses of the first protective layer and the second protective layer on the first silver layer and the second silver layer below them are consistent. The growth morphology at the interfaces between the first protective layer and the first silver layer and between the second protective layer and the second silver layer is good. The first silver layer and the second silver layer are not damaged, and the flatness of the second silver layer and the first silver layer is relatively good. In this way, the interfaces between the second protective layer and the second silver layer and between the first protective layer and the first silver layer are relatively smooth, and the scattering of light reaching the interfaces is small. From the visual effect, the haze of the product (such as forming Figure 1 hollow structure) is smaller, and fog-like defects of different colors will not be generated when observed under strong light. In addition, if the first silver layer and the second silver layer are not damaged, it will not affect the quality of the first silver layer and the second silver layer, nor will it affect the performance of the Low-E glass.

[0019] In the double-silver Low-E coated glass according to the present disclosure, the second dielectric layer is a metal oxide film. The second dielectric layer is adjacent to the first protective layer. Oxygen in the argon-oxygen mixed atmosphere during the deposition of the metal oxide film of the second dielectric layer will enter the already deposited first protective layer to oxidize the pure metal or alloy of the first protective layer. Excessive oxygen in the second dielectric layer will free from the second dielectric layer into the first protective layer during the tempering process of the double-silver Low-E coated glass, further oxidizing the pure metal or alloy of the first protective layer. Thus, finally, the first protective layer is embodied as a completely oxidized film of pure metal or alloy in the double-silver Low-E coated glass. Similarly, the third dielectric layer includes a metal oxide film adjacent to the second protective layer. Oxygen in the argon-oxygen mixed atmosphere during the deposition of the metal oxide film included in the third dielectric layer will enter the already deposited second protective layer to oxidize the pure metal or alloy of the second protective layer. Excessive oxygen in the metal oxide film included in the third dielectric layer will free from the metal oxide film included in the third dielectric layer into the second protective layer during the tempering process of the double-silver Low-E coated glass, further oxidizing the pure metal or alloy of the second protective layer. Thus, finally, the second protective layer is embodied as a completely oxidized film of pure metal or alloy in the double-silver Low-E coated glass.

[0020] In the double-silver Low-E coated glass according to the present disclosure, since the first silver layer and the second silver layer in the Low-E film layer are not damaged and have good quality, the double-silver Low-E coated glass and the products forming a hollow structure thereof have good heat insulation performance.

[0021] In the double-silver Low-E coated glass according to the present disclosure, the metallic absorption layer in the Low-E film layer can improve the light absorption of the film stack of the Low-E film layer, reduce the light transmittance (i.e., lower haze, better permeability, and more neutral transmitted color), and at the same time increase the reflectivity of a certain glass surface (i.e., make the appearance of the building using the double-silver Low-E coated glass brighter, ensuring the aesthetic effect of the building using the double-silver Low-E coated glass). The non-peroxo AZO film in the first seed layer of the Low-E film layer is located between the ZnAlO film and the absorption layer, separating the ZnAlO film from the absorption layer. Excessive oxygen elements formed in the ZnAlO film during the deposition of the ZnAlO film and free oxygen elements from the ZnAlO film during the tempering process of the double-silver Low-E coated glass will enter the oxygen-deficient AZO film deposited in a pure argon and oxygen-free atmosphere and be absorbed, finally forming a non-peroxo AZO film, and the free oxygen elements from the ZnAlO film will not reach the absorption layer, thus keeping the absorption layer in a metallic state.

[0022] In the double-silver Low-E coated glass according to the present disclosure, due to the first protective layer and the second protective layer in the Low-E film layer being films in a fully oxidized state of pure metal or alloy, and the absorption layer in the metal state in the Low-E film layer, the haze of the double-silver Low-E coated glass under light is extremely reduced, greatly improving the transparency of the double-silver Low-E coated glass.

[0023] In the double-silver Low-E coated glass according to the present disclosure, as verified during the testing process, the single-pane transmittance of the double-silver Low-E coated glass is above 54%, the reflectance outside the room can reach above 20%, and the light-to-heat ratio of the single-pane structure can reach above 1.8, thereby achieving good aesthetic effects outdoors and indoors, while significantly enhancing the heat insulation ability of sunlight.

[0024] In summary, in short, the double-silver Low-E coated glass according to the present disclosure can improve the optical properties and heat insulation properties of the Low-E coated glass and the single-pane structure.

[0025] For example, the glass as the substrate is ordinary clear glass. The thickness of the glass can be determined according to actual needs. For example, 6 mm can be selected.

[0026] The main function of the first dielectric layer is to prevent sodium ions in the glass from precipitating out of the glass during the tempering process, which would damage the structure of the first silver layer, resulting in defects such as white spots, film peeling, and performance degradation in the tempered glass. For example, the first dielectric layer is a metal nitride film, a metal oxide film, or a combination thereof. Further, the first dielectric layer is a ZnSnO film, a SiAlN film, a TiO 2 film, a SiAlO film, or a combination thereof. In one example, the thickness of the first dielectric layer is 10 - 30 nm. More specifically, in one example, the first dielectric layer is a SiAlN film, and the thickness of the first dielectric layer is 20 - 23 nm.

[0027] The second dielectric layer is a metal oxide film. The structure of the metal oxide film is dense and has relatively low intrinsic stress compared to nitrides. During the tempering process, the stress release is small, and the microstructural change of the second dielectric layer has little impact on the first silver layer, which can reduce the absorption of the composite film stack. At the same time, the thickness value range of the second dielectric layer is relatively wide, which can effectively regulate the optical parameters of the second dielectric layer to meet different aesthetic requirements. For example, the second dielectric layer is a ZnSnO film, a TiO 2 film, a SiAlO film, or a combination thereof. In one example, the thickness of the second dielectric layer is 60 - 80 nm. More specifically, in one example, the second dielectric layer is a ZnSnO film, and the thickness of the second dielectric layer is 78 - 80 nm.

[0028] For example, the third dielectric layer is a metal oxide thin film, or the third dielectric layer is composed of a metal oxide thin film and a metal nitride thin film adjacent to the second protective layer. Specifically, the third dielectric layer is a ZnSnO thin film, a ZnAlO thin film, a SnO 2 thin film, a ZnO thin film, a TiO 2 thin film, a SiAlN thin film, or a combination thereof. In one example, the thickness of the third dielectric layer is 20 - 40 nm. More specifically, in one example, the third dielectric layer is a ZnSnO thin film and a ZnAlO thin film. The ZnSnO thin film is adjacent to the outermost protective layer, the thickness of the ZnSnO thin film is 20 - 23 nm, and the thickness of the ZnAlO thin film is 10 nm.

[0029] The main purpose of the outermost protective layer is to improve the physical and chemical properties of the double - silver Low - E coated glass during subsequent processing, handling, and storage, such as scratch resistance, acid - alkali resistance, and water - vapor resistance. For example, the outermost protective layer is a metal or alloy oxide or nitride thin film. Specifically, the outermost protective layer is a ZnSnO thin film, a ZnAlO thin film, a SnO 2 thin film, a ZnO thin film, a TiO 2 thin film, a SiAlZrO thin film, a SiAlN thin film, or a combination thereof. In one example, the thickness of the outermost protective layer is 10 - 30 nm. More specifically, in one example, the outermost protective layer is a SiAlZrO thin film, and the thickness of the outer protective layer is 15 nm.

[0030] For example, the first protective layer and the second protective layer are NiCr thin films, Ti thin films, or Cr thin films in a fully oxidized state. For example, the thickness of the first protective layer and the thickness of the second protective layer are each 1.5 - 2.5 nm. More specifically, in one example, the first protective layer and the second protective layer are NiCr thin films in a fully oxidized state, and the thickness of the first protective layer and the thickness of the second protective layer are each 1.9 - 2 nm.

[0031] The first silver layer and the second silver layer are the main functional layers of the double - silver Low - E coated glass. They have better transmittance in the visible light range, can ensure daily lighting, and at the same time have a high reflection effect on solar radiation and mid - and far - infrared radiation, which can play a role in heat insulation. In one example, the sum of the thickness of the first silver layer and the thickness of the second silver layer is greater than 30 nm. In one example, the thickness of the first silver layer and the thickness of the second silver layer are each 15 - 20 nm. More specifically, in one example, the thickness of the first silver layer is 15 - 17 nm, and the thickness of the second silver layer is 14 - 16 nm.

[0032] For example, the thickness of the ZnAlO thin film in the first seed layer is 8 - 12 nm. More specifically, in one example, the thickness of the ZnAlO thin film in the first seed layer is 8 - 10 nm. For example, the thickness of the non-peroxo AZO thin film is 3 - 6 nm. More specifically, in one example, the thickness of the non-peroxo AZO thin film in the first seed layer is 4 - 5 nm.

[0033] In one example, the thickness of the absorption layer is 0.5 nm - 5 nm. More specifically, in one example, the absorption layer is a metallic NiCr thin film, and the thickness of the absorption layer is 1.4 nm - 1.5 nm.

[0034] In one example, the second seed layer is a ZnAlO thin film. The ZnAlO thin film has a dense structure, and the crystal structure and crystal phase have a very high degree of matching with silver, which is beneficial to the growth of the second silver layer. In one example, the thickness of the second seed layer is 5 - 20 nm. More specifically, in one example, the second seed layer is a ZnAlO thin film, and the thickness of the second seed layer is 10 nm.

[0035] [Preparation Method of Double-Silver Low-E Coated Glass]

[0036] The preparation method of the double-silver Low-E coated glass according to the present disclosure is used to prepare the aforementioned double-silver Low-E coated glass, and the preparation method of the double-silver Low-E coated glass includes steps;

[0037] S1, making the glass as the substrate enter a horizontal vacuum magnetron sputtering coating continuous line, so as to sequentially sputter coat a first dielectric layer, a first seed layer, an absorption layer, a first silver layer, a first protective layer, a second dielectric layer, a second seed layer, a second silver layer, a second protective layer, a third dielectric layer, and an outermost protective layer of the Low-E film layer from one surface of the glass as the substrate at room temperature,

[0038] Among them,

[0039] The ZnAlO thin film adjacent to the first dielectric layer in the first seed layer is magnetron sputter coated using a ZnAl target in an argon-oxygen mixed atmosphere,

[0040] The AZO thin film in the first seed layer is magnetron sputter coated using a ceramic AZO target in a pure argon and oxygen-free atmosphere,

[0041] The absorption layer is magnetron sputter coated using a NiCr, Ti, Ni, or Cr target in a pure argon and oxygen-free atmosphere;

[0042] The first protective layer and the second protective layer are magnetron sputter coated using a pure metal or alloy target in a pure argon and oxygen-free atmosphere,

[0043] The second dielectric layer is magnetron sputtered and coated with a pure metal or alloy target in an argon-oxygen mixed atmosphere.

[0044] The metal oxide film adjacent to the second protective layer included in the third dielectric layer is magnetron sputtered and coated with a pure metal or alloy target in an argon-oxygen mixed atmosphere.

[0045] S2, temper the glass on which the Low-E film layer has been coated.

[0046] In the method for preparing the double-silver Low-E coated glass of the present disclosure, in step S1, the AZO film in the first seed layer is magnetron sputtered and coated with a ceramic AZO target in a pure argon and oxygen-free atmosphere to form an oxygen-deficient AZO film. When magnetron sputtering and coating with a ZnAl target in an argon-oxygen mixed atmosphere, an excessive amount of oxygen elements are formed in the ZnAlO film in the first seed layer. During the tempering process in step S2, the excessive oxygen elements from the ZnAlO film dissociate into the pure argon and oxygen-free atmosphere and are absorbed by the oxygen-deficient AZO film formed by deposition, and finally form the non-peroxide state AZO film of the aforementioned double-silver Low-E coated glass, and the free oxygen elements from the ZnAlO film will not reach the absorption layer, so that the absorption layer of the metal state NiCr film, Ti film, Ni film or Cr film of the aforementioned double-silver Low-E coated glass is finally formed.

[0047] In the method for preparing the double-silver Low-E coated glass of the present disclosure, in step S1, the second dielectric layer is magnetron sputtered and coated with a pure metal or alloy target in an argon-oxygen mixed atmosphere to form a metal oxide film. The oxygen in the argon-oxygen mixed atmosphere will enter the first protective layer in the form of a deposited pure metal or alloy film to oxidize the pure metal or alloy in the first protective layer. In step S2, the excessive oxygen in the second dielectric layer will dissociate from the second dielectric layer into the first protective layer during the tempering process of the double-silver Low-E coated glass to further oxidize the pure metal or alloy in the first protective layer, so that finally the first protective layer in the double-silver Low-E coated glass is a completely oxidized state film of pure metal or alloy. Similarly, in step S1, the metal oxide film adjacent to the second protective layer included in the third dielectric layer is magnetron sputtered and coated with a pure metal or alloy target in an argon-oxygen mixed atmosphere to form a metal oxide film. The oxygen in the argon-oxygen mixed atmosphere will enter the second protective layer in the form of a deposited pure metal or alloy film to oxidize the pure metal or alloy in the second protective layer. In step S2, the excessive oxygen in the third dielectric layer will dissociate from the third dielectric layer into the second protective layer during the tempering process of the double-silver Low-E coated glass to further oxidize the pure metal or alloy in the second protective layer, so that finally the second protective layer in the double-silver Low-E coated glass is a completely oxidized state film of pure metal or alloy.

[0048] The effects of the double-silver Low-E coated glass prepared by the preparation method of the double-silver Low-E coated glass of the present disclosure are as described above and will not be repeated here.

[0049] In step S1, for example, the first dielectric layer is formed by magnetron sputtering coating with a metal target in an argon-nitrogen mixed atmosphere to form a metal nitride film, and / or the first dielectric layer is formed by magnetron sputtering coating with a metal target in an argon-oxygen mixed atmosphere to form a metal oxide film. For example, the metal target is a ZnSn, SiAl or Ti target. In one example, the thickness of the first dielectric layer is 10-30 nm. More specifically, in one example, the target of the first dielectric layer is SiAl, the atmosphere is an argon-nitrogen mixed atmosphere and the volume flow ratio of argon gas is 45%, and the working pressure is 2.5×10 -3 mbar, the target power is 70-80 kW, and the thickness of the first dielectric layer is 20-23 nm.

[0050] In step S1, for example, the thickness of the ZnAlO film in the first seed layer is 8-12 nm. More specifically, in one example, the thickness of the ZnAlO film in the first seed layer is 8-10 nm, the volume flow ratio of argon gas in the argon-oxygen mixed atmosphere is 45%, and the working pressure is 2.5×10 -3 mbar, and the target power is 20 kW.

[0051] In step S1, for example, the thickness of the AZO film in the first seed layer is 3-6 nm. More specifically, in one example, the thickness of the AZO film in the first seed layer is 4-5 nm. For example, the AZO target uses the AZO ceramic target produced by Pilot Thin Film Materials (Guangdong) Co., Ltd. This target is made by mixing and pressing Al 2 O 3 and ZnO powders, and the weight ratio of Al 2 O 3 in the target is 2%. More specifically, in one example, when magnetron sputtering the AZO film in the first seed layer, the working pressure is 3×10 - 3 mbar, and the target power is 20-22 kW.

[0052] In step S1, for example, the thickness of the absorption layer is 0.5 nm - 5 nm. More specifically, in one example, the absorption layer uses a NiCr target, the working pressure is 1.6×10 -3 mbar, the target power is 4-4.2 kW, and the thickness of the absorption layer is 1.4 nm - 1.5 nm.

[0053] In step S1, for example, the first silver layer and the second silver layer are magnetron sputtered and coated with a silver target in a pure argon atmosphere. In one example, the sum of the thicknesses of the first silver layer and the second silver layer is greater than 30 nm. In one example, the thicknesses of the first silver layer and the second silver layer are each 15 - 20 nm. More specifically, in one example, when magnetron sputtering the first silver layer, the atmosphere is a pure argon atmosphere, the working pressure is 1.2×10 -3 mbar, the target power is 15 - 16.5 kW, and the thickness of the first silver layer is 15 - 17 nm. More specifically, in one example, when magnetron sputtering the second silver layer, the atmosphere is a pure argon atmosphere, the working pressure is 1.2×10 -3 mbar, the target power is 13 - 14 kW, and the thickness of the second silver layer is 14 - 16 nm.

[0054] In step S1, for example, the pure metal or alloy target for magnetron sputtering and coating the first protective layer and the second protective layer is made of NiCr, Ti, or Cr. For example, the thicknesses of the first protective layer and the second protective layer are each 1.5 - 2.5 nm. More specifically, in one example, the pure metal or alloy target for magnetron sputtering and coating the first protective layer and the second protective layer is NiCr, the working pressure is 1.6×10 -3 mbar, the target power is 5 - 5.5 kW, and the thicknesses of the first protective layer and the second protective layer are each 1.9 - 2 nm.

[0055] In step S1, for example, the target of the second dielectric layer is made of ZnSn or Ti. In one example, the thickness of the second dielectric layer is 60 - 80 nm. More specifically, in one example, the target of the second dielectric layer is ZnSn, the volume flow rate ratio of argon in the argon-oxygen mixed atmosphere is 36%, the working pressure is 2.3×10 -3 mbar, the target power is 205 - 210 kW, and the thickness of the second dielectric layer is 78 - 80 nm.

[0056] In step S1, for example, the second seed layer is magnetron sputtered and coated with a ZnAl target in an argon-oxygen mixed atmosphere. For example, the thickness of the second seed layer is 5 - 20 nm. More specifically, in one example, when magnetron sputtering the second seed layer, a ZnAl target is used, the atmosphere is an argon-oxygen mixed atmosphere and the volume flow rate ratio of argon is 45%, the working pressure is 2.5×10 - 3 mbar, the target power is 28 - 30 kW, and the thickness of the second seed layer is 10 nm.

[0057] In step S1, for example, the target materials for magnetron sputtering coating of the third dielectric layer are ZnSn, ZnAl, Sn, Zn, Ti, or SiAl target materials. In one example, the thickness of the third dielectric layer is 20 - 40 nm. More specifically, in one example, the third dielectric layer is a ZnSnO thin film and a ZnAlO thin film. The ZnSnO thin film is adjacent to the outermost protective layer. The target material of the ZnAlO thin film is ZnAl. In an argon-oxygen mixed atmosphere, the volume flow ratio of argon gas is 45%, and the working pressure is 2.5×10 -3 mbar, the target power is 28 kW, the thickness of the ZnAlO thin film is 10 nm. The target material of the ZnSnO thin film is ZnSn. In an argon-oxygen mixed atmosphere, the volume flow ratio of argon gas is 36%, and the working pressure is 2.3×10 -3 mbar, the target power is 54 - 60 kW, and the thickness of the ZnSnO thin film is 20 - 23 nm.

[0058] In step S1, for example, the target materials for magnetron sputtering coating of the outermost protective layer are ZnSn, ZnAl, Sn, Zn, Ti, SiAlZr, or SiAl. The corresponding atmosphere is an argon-oxygen mixed atmosphere or an argon-nitrogen mixed atmosphere. In one example, the thickness of the outermost protective layer is 10 - 30 nm. More specifically, in one example, when magnetron sputtering coating the outermost protective layer, the target material is SiAlZr, the atmosphere is an argon-oxygen mixed atmosphere and the volume flow ratio of argon gas is 36%, and the working pressure is 3.2×10 -3 mbar, the target power is 40 kW, and the thickness of the outer protective layer is 15 nm.

[0059] In step S1, for example, when magnetron sputtering coating the first dielectric layer, the first seed layer, the absorption layer, the first silver layer, the first protective layer, the second dielectric layer, the second seed layer, the second silver layer, the second protective layer, the third dielectric layer, and the outermost protective layer of the Low-E film layer, it is all coated at room temperature. The working air pressure is in the range of (1.2 - 3.2)×10 -3 mbar, and the sputtering power is in the range of (4 - 210) kW.

[0060] In step S1, for example, when magnetron sputtering coating the first dielectric layer, the first seed layer, the absorption layer, the first silver layer, the first protective layer, the second dielectric layer, the second seed layer, the second silver layer, the second protective layer, the third dielectric layer, and the outermost protective layer of the Low-E film layer, if the atmosphere used is an argon-oxygen mixed atmosphere, then the volume flow ratio of argon gas is 36% - 45%. If the atmosphere used is an argon-nitrogen mixed atmosphere, the volume flow ratio of argon gas is 36% - 45%.

[0061] In one example, the toughening process in step S2 is as follows: The glass is conveyed into a fully automatic toughening furnace. Among them, the set temperature of the heating furnace is 670 °C, the heating time is 420 s, the glass is heated evenly in a reciprocating manner in the heating furnace, and then the glass leaves the heating furnace and enters the air-cooling section. The glass is rapidly air-cooled evenly in a reciprocating manner in the air-cooling section. The wind pressure of the rapid air-cooling is 1 bar, and the time is 30 s. Then, the reciprocating movement of the glass is maintained until the temperature drops to room temperature, and the toughening is completed.

[0062] [Test]

[0063] Comparative Example 1

[0064] The preparation method of the double-silver Low-E coated glass in Comparative Example 1 adopts the following steps;

[0065] Sa, Make the glass used as the substrate enter a horizontal vacuum magnetron sputtering coating continuous line, so that starting from one surface of the glass used as the substrate, a first dielectric layer, a first seed layer, a first silver layer, a first protective layer, a second dielectric layer, a second seed layer, a second silver layer, a second protective layer, a third dielectric layer, and an outermost protective layer of the Low-E film layer are sequentially sputtered and coated at room temperature. The glass used as the substrate is 6 mm thick ordinary white glass.

[0066] For the magnetron sputtering coating parameters of the first dielectric layer, the first seed layer, the first silver layer, the first protective layer, the second dielectric layer, the second seed layer, the second silver layer, the second protective layer, the third dielectric layer, and the outermost protective layer of the Low-E film layer, refer to Table 1 and refer to Figure 4 and Figure 5 ;

[0067] Sb, Temper the glass on which the Low-E film layer coating is completed. The toughening process is as follows: The glass is conveyed into a fully automatic toughening furnace. Among them, the set temperature of the heating furnace is 670 °C, the heating time is 420 s, the glass is heated evenly in a reciprocating manner in the heating furnace, and then the glass leaves the heating furnace and enters the air-cooling section. The glass is rapidly air-cooled evenly in a reciprocating manner in the air-cooling section. The wind pressure of the rapid air-cooling is 1 bar, and the time is 30 s. Then, the reciprocating movement of the glass is maintained until the temperature drops to room temperature, and the toughening is completed.

[0068] Table 1 Magnetron sputtering coating parameters of Comparative Example 1

[0069]

[0070] Comparative Example 2

[0071] Except that the thicknesses of the respective film layers formed by the first dielectric layer, the first seed layer, the first silver layer, the first protective layer, the second dielectric layer, the second seed layer, the second silver layer, the second protective layer, the third dielectric layer, and the outermost protective layer of the Low-E film layer in step Sa are different, the rest are the same as Comparative Example 1.

[0072] For the magnetron sputtering coating parameters of the first dielectric layer, the first seed layer, the first silver layer, the first protective layer, the second dielectric layer, the second seed layer, the second silver layer, the second protective layer, the third dielectric layer, and the outermost protective layer of the Low-E film layer of Comparative Example 2, refer to Table 2 and refer to Figure 4 and Figure 5 。

[0073] Table 2 Magnetron Sputtering Coating Parameters of Comparative Example 2

[0074]

[0075] Example 1

[0076] The preparation method of the double-silver Low-E coated glass of Example 1 adopts the following steps;

[0077] S1, making the glass as the substrate enter a horizontal vacuum magnetron sputtering coating continuous line, so that starting from one surface of the glass as the substrate, the first dielectric layer, the first seed layer, the absorption layer, the first silver layer, the first protective layer, the second dielectric layer, the second seed layer, the second silver layer, the second protective layer, the third dielectric layer, and the outermost protective layer of the Low-E film layer are sputtered and coated in sequence at room temperature. The glass as the substrate is 6 mm thick ordinary white glass. For the magnetron sputtering coating parameters of the first dielectric layer, the first seed layer, the absorption layer, the first silver layer, the first protective layer, the second dielectric layer, the second seed layer, the second silver layer, the second protective layer, the third dielectric layer, and the outermost protective layer of the Low-E film layer, refer to Table 3 and refer to Figure 6 , wherein, the AZO target is an AZO ceramic target produced by Pilot Thin Film Materials (Guangdong) Co., Ltd. This target is made by mixing and pressing Al 2 O 3 and ZnO powders, and the weight ratio of Al 2 O 3 in the target is 2%;

[0078] S2, tempering the glass after the Low-E film layer is coated. The tempering process is as follows: transporting the glass into a fully automatic tempering furnace. Among them, the set temperature of the heating furnace is 670 °C, the heating time is 420 s, the glass is heated evenly in a reciprocating manner in the heating furnace, and then the glass leaves the heating furnace and enters the air-cooling section. The glass is cooled rapidly and evenly in a reciprocating manner in the air-cooling section. The air pressure of the rapid air-cooling is 1 bar, and the time is 30 s. Then, keep the reciprocating movement of the glass until the temperature drops to room temperature, and the tempering is completed.

[0079] Table 3 Magnetron Sputtering Coating Parameters of Example 1

[0080]

[0081] Example 2

[0082] Except that the thicknesses of the first dielectric layer, the first seed layer, the absorption layer, the first silver layer, the first protective layer, the second dielectric layer, the second seed layer, the second silver layer, the second protective layer, the third dielectric layer and the outermost protective layer of the Low-E film layer in step S1 are different, the rest is the same as in Embodiment 1.

[0083] For the magnetron sputtering coating parameters of the first dielectric layer, the first seed layer, the absorption layer, the first silver layer, the first protective layer, the second dielectric layer, the second seed layer, the second silver layer, the second protective layer, the third dielectric layer and the outermost protective layer of the Low-E film layer in Embodiment 2, refer to Table 4 and Figure 6 .

[0084] Table 4 Magnetron Sputtering Coating Parameters of Embodiment 2

[0085]

[0086]

[0087] In the preparation method of double-silver Low-E coated glass, before and after performing step Sb of Comparative Example 1-2 and step S2 of Embodiment 1-2, the optical properties and surface resistance of the coated glass before and after annealing are characterized by an on-line spectrophotometer, and the characterized optical property parameters and surface resistance are recorded in Table 5.

[0088] Table 5 Optical Property Parameters and Surface Resistance of Glasses in Embodiments 1-2 and Comparative Examples 1-2 before and after Annealing

[0089]

[0090] In Table 5,

[0091] T: Average transmittance of the 380 - 780 nm spectrum of a single-piece coated glass;

[0092] Rg: Average reflectance of the non-coated surface of the 380 - 780 nm spectrum of a single-piece coated glass;

[0093] Rf: Average reflectance of the coated surface of the 380 - 780 nm spectrum of a single-piece coated glass;

[0094] a*: Red-green value describing the corresponding spectral color;

[0095] b*: Yellow-blue value describing the corresponding spectral color;

[0096] Rsq: Surface resistance of the coated glass.

[0097] As can be seen from Table 1-2 and Table 3-4, during magnetron sputtering coating, the thicknesses of the first protective layer and the second protective layer in Examples 1-2 were thinned to about half or half of the thicknesses of the first protective layer and the second protective layer in Comparative Examples 1-2. Comparative Examples 1-2 did not have the absorption layer in Examples 1-2, and the first seed layer in Comparative Examples 1-2 did not have the oxygen-deficient AZO thin film in Examples 1-2.

[0098] After tempering in the preparation methods of the double-silver Low-E coated glass in Comparative Examples 1-2 and Examples 1-2, the transmission spectrum of the double-silver Low-E coated glass was measured. Figure 7 Graphs of the transmittance of Examples 1-2 and Comparative Examples 1-2 are given, where the horizontal axis is the wavelength band with the unit of nm, and the vertical axis is the transmittance.

[0099] From Figure 7 it can be seen that Examples 1-2 had lower transmittance than Comparative Examples 1-2 in the red light to infrared wavelength band.

[0100] After tempering in the preparation methods of the double-silver Low-E coated glass in Comparative Examples 1-2 and Examples 1-2, the coated glass was placed in a single insulating structure, and the Low-E film layer was placed on the second side of the insulating structure, as Figure 1 shown, and the optical and heat insulation performance of the insulating structure was recorded in Table 6.

[0101] Table 6 Photothermal performance parameters of the single insulating structure of Examples 1-2 and Comparative Examples 1-2

[0102]

[0103] In Table 6:

[0104] Visible light

[0105] T: Average transmittance of the insulating glass in the 380 - 780 nm wavelength band;

[0106] R ex : Average outdoor-side reflectance of the insulating glass in the 380 - 780 nm wavelength band;

[0107] R in : Average indoor-side reflectance of the insulating glass in the 380 - 780 nm wavelength band;

[0108] Solar energy

[0109] T: Average transmittance of the insulating glass in the 300 - 2500 nm wavelength band;

[0110] R ex : Average outdoor-side reflectance of the insulating glass in the 300 - 2500 nm wavelength band;

[0111] Rin : The average indoor reflectance of the insulating glass in the 300 - 2500 nm band;

[0112] National standards and American standards

[0113] K / U respectively represent the heat transfer coefficients under national standards and American standards;

[0114] SC: Shading coefficient;

[0115] SHGC: Solar heat gain coefficient = 0.87 * SC;

[0116] LSG: Light - to - heat ratio, LSG = visible light transmittance / SHGC.

[0117] As can be seen from Table 6, the transmittance of the insulating structure composed of the double - silver Low - E coated glass in Examples 1 - 2 is above 54%, the average outdoor reflectance R ex is above 20% for visible light and above 40% for solar energy, and the average indoor - outdoor reflectance R in is above 19% for visible light and above 39% for solar energy, the light - to - heat ratio reaches above 1.8, the national standard heat transfer coefficient K is below 1.65, and the American standard heat transfer coefficient U is below 1.64. The insulating structures composed of the double - silver Low - E coated glass in Examples 1 - 2 are superior to the insulating structures composed of the double - silver Low - E coated glass in Comparative Examples 1 - 2 in both optical and heat - insulating properties.

[0118] Multiple exemplary embodiments are described using the detailed description above, but this document is not intended to be limited to the explicitly disclosed combinations. Thus, unless otherwise stated, the various features disclosed herein can be combined together to form multiple additional combinations not shown for the sake of brevity.

Claims

1. A double silver Low-E coated glass, characterized in that: The Low-E film layers are, starting from one surface of the glass substrate, a first dielectric layer, a first seed layer, an absorption layer, a first silver layer, a first protective layer, a second dielectric layer, a second seed layer, a second silver layer, a second protective layer, a third dielectric layer and an outermost protective layer. in, The second dielectric layer is a metal oxide film; The third dielectric layer includes a metal oxide film adjacent to the second protective layer; The first protective layer and the second protective layer are each a thin film of a pure metal or alloy in a completely oxidized state; The first seed layer is composed of a ZnAlO film adjacent to the first dielectric layer and a non-peroxidized AZO film between the ZnAlO film and the absorption layer; The absorption layer is a metallic NiCr film, a Ti film, a Ni film, a Cr film or a ZnAl film.

2. The double silver Low-E coated glass according to claim 1, characterized in that: The first dielectric layer is a metal nitride film, a metal oxide film or a combination thereof; and / or The first dielectric layer is a ZnSnO film, a SiAlN film, a TiO2 film, a SiAlO film or a combination thereof; and / or The thickness of the first dielectric layer is 10-30 nm.

3. The double silver Low-E coated glass according to claim 1, characterized in that: The second dielectric layer is a ZnSnO film, a TiO2 film, a SiAlO film or a combination thereof; and / or The thickness of the second dielectric layer is 60-80 nm.

4. The double silver Low-E coated glass according to claim 1, characterized in that: The third dielectric layer is a metal oxide film, or the third dielectric layer is composed of a metal oxide film and a metal nitride film adjacent to the second protective layer; and / or The third dielectric layer is a ZnSnO film, a ZnAlO film, a SnO2 film, a ZnO film, a TiO2 film, a SiAlN film or a combination thereof; and / or The thickness of the third dielectric layer is 20-40 nm.

5. The double silver Low-E coated glass according to claim 1, characterized in that: The outermost protective layer is a metal or alloy oxide or nitride film; and / or The outermost protective layer is a ZnSnO film, a ZnAlO film, a SnO2 film, a ZnO film, a TiO2 film, a SiAlZrO film, a SiAlN film or a combination thereof; and / or The thickness of the outermost protective layer is 10-30 nm.

6. The double silver Low-E coated glass according to claim 1, characterized in that: The first protective layer and the second protective layer are NiCr thin films, Ti thin films or Cr thin films; and / or The thickness of the first protective layer and the thickness of the second protective layer are respectively 1.5-2.5 nm.

7. The double silver Low-E coated glass according to claim 1, characterized in that: The sum of the thickness of the first silver layer and the thickness of the second silver layer is greater than 30 nm, and the thickness of the first silver layer and the thickness of the second silver layer are each 15-20 nm; and / or The thickness of the ZnAlO film in the first seed layer is 8-12 nm, and the thickness of the non-peroxidized AZO film is 3-6 nm; and / or The thickness of the absorption layer is 0.5nm-5nm; and / or The second seed layer is a ZnAlO thin film; and / or The thickness of the second seed layer is 5-20 nm.

8. The double silver Low-E coated glass according to claim 1, characterized in that: The first dielectric layer is a SiAlN film, and the thickness of the first dielectric layer is 20-23 nm; The thickness of the ZnAlO film in the first seed layer is 8-10 nm; The thickness of the non-peroxidized AZO film in the first seed layer is 4-5 nm; The absorption layer is a metallic NiCr film, and the thickness of the absorption layer is 1.4nm-1.5nm; The thickness of the first silver layer is 15-17nm; The first protective layer is a fully oxidized NiCr film, and the thickness of the first protective layer is 1.9-2nm; The second dielectric layer is a ZnSnO thin film, and the thickness of the second dielectric layer is 78-80nm; The second seed layer is a ZnAlO thin film, and the thickness of the second seed layer is 10 nm; The thickness of the second silver layer is 14-16nm; The second protective layer is a fully oxidized NiCr film, and the thickness of the second protective layer is 1.9-2nm; The third dielectric layer is a ZnAlO film and a ZnSnO film, the ZnSnO film is adjacent to the outermost protective layer, the thickness of the ZnAlO film is 10nm, and the thickness of the ZnSnO film is 20-23nm; The outermost protective layer is a SiAlZrO film, and the thickness of the outermost protective layer is 15 nm.

9. A method for preparing double silver Low-E coated glass, characterized in that: The method for preparing the double-silver Low-E coated glass is used to prepare the double-silver Low-E coated glass according to any one of claims 1 to 8, and the method for preparing the double-silver Low-E coated glass comprises the steps of: S1, making the glass as the substrate enter the horizontal vacuum magnetron sputtering coating continuous line, so that the first dielectric layer, the first seed layer, the absorption layer, the first silver layer, the first protective layer, the second dielectric layer, the second seed layer, the second silver layer, the second protective layer, the third dielectric layer and the outermost protective layer of the Low-E film layer are sputtered and coated in sequence at room temperature from one surface of the glass as the substrate, in, The ZnAlO thin film in the first seed layer adjacent to the first dielectric layer is sputtered by using a ZnAl target in an argon-oxygen mixed atmosphere. The AZO film in the first seed layer is magnetron sputtered in a pure argon oxygen-free atmosphere using a ceramic AZO target. The absorption layer is magnetron sputtered in a pure argon oxygen-free atmosphere using NiCr, Ti, Ni or Cr target materials. The first protective layer and the second protective layer are magnetron sputtered in a pure argon oxygen-free atmosphere using pure metal or alloy targets. The second dielectric layer is magnetron sputtered in an argon-oxygen mixed atmosphere using pure metal or alloy targets. The metal oxide film included in the third dielectric layer and adjacent to the second protective layer is magnetron sputtered in an argon-oxygen mixed atmosphere using a pure metal or alloy target; S2, tempering the glass coated with the Low-E film.

10. The method for preparing double silver Low-E coated glass according to claim 9, characterized in that: In step S1, The AZO film in the first seed layer is magnetron sputtered in a pure argon oxygen-free atmosphere using a ceramic AZO target, and the weight proportion of Al2O3 in the ceramic AZO target is 2%.

11. The method for preparing double silver Low-E coated glass according to claim 10, characterized in that: In step S1, The target material of the first dielectric layer is SiAl, the atmosphere is an argon-nitrogen mixed atmosphere with an argon volume flow rate of 45%, and the working pressure is 2.5×10 -3 mbar, the target power is 70-80kW, and the thickness of the first dielectric layer is 20-23nm; During magnetron sputtering of the ZnAlO film in the first seed layer, the volume flow rate of argon gas in the argon-oxygen mixed atmosphere was 45%, and the working pressure was 2.5×10 -3 mbar, the target power is 20 kW, and the thickness of the ZnAlO film in the first seed layer is 8-10 nm; When the AZO film in the first seed layer is magnetron sputtered, the working pressure is 3×10 -3 mbar, the target power is 20-22kW, and the thickness of the AZO film in the first seed layer is 4-5nm; The absorption layer uses NiCr target material, and the working pressure is 1.6×10 -3 mbar, target power is 4-4.2kW, and the thickness of the absorption layer is 1.4nm-1.5nm; During magnetron sputtering of the first silver layer, the atmosphere was pure argon and the working pressure was 1.2×10 -3 mbar, the target power is 15-16.5kW, and the thickness of the first silver layer is 15-17nm; The pure metal or alloy target material of the first protective layer magnetron sputtering coating is NiCr, and the working pressure is 1.6×10 -3 mbar, the target power is 5-5.5kW, and the thickness of the first protective layer is 1.9-2nm; The target material of the second dielectric layer is ZnSn. In the argon-oxygen mixed atmosphere, the volume flow rate of argon is 36%, and the working pressure is 2.3×10 -3 mbar, the target power is 205-210kW, and the thickness of the second dielectric layer is 78-80nm; During magnetron sputtering of the second seed layer, ZnAl target material was used, the atmosphere was an argon-oxygen mixed atmosphere with an argon volume flow rate of 45%, and the working pressure was 2.5×10 -3 mbar, the target power is 28-30kW, and the thickness of the second seed layer is 10nm; During magnetron sputtering of the second silver layer, the atmosphere was pure argon and the working pressure was 1.2×10 -3 mbar, the target power is 13-14kW, and the thickness of the second silver layer is 14-16nm; The pure metal or alloy target material of the second protective layer magnetron sputtering coating is NiCr, and the working pressure is 1.6×10 -3 mbar, the target power is 5-5.5kW, and the thickness of the second protective layer is 1.9-2nm; The third dielectric layer is a ZnSnO film and a ZnAlO film. The ZnSnO film is adjacent to the outermost protective layer. The target material of the ZnAlO film is ZnAl. In the argon-oxygen mixed atmosphere, the volume flow rate of argon gas accounts for 45%, and the working pressure is 2.5×10 -3 mbar, the target power is 28 kW, the thickness of the ZnAlO film is 10 nm, the target material of the ZnSnO film is ZnSn, the volume flow rate of argon gas in the argon-oxygen mixed atmosphere is 36%, and the working pressure is 2.3×10 -3 mbar, target power is 54-60kW, and the thickness of ZnSnO film is 20-23nm; The target material for magnetron sputtering coating of the outermost protective layer is SiAlZr, the atmosphere is an argon-oxygen mixed atmosphere with an argon volume flow rate of 36%, and the working pressure is 3.2×10 -3 mbar, the target power is 40kW, and the thickness of the outermost protective layer is 15nm.

12. The method for preparing double silver Low-E coated glass according to claim 9, characterized in that: The tempering process of step S2 is as follows: the glass is transferred into a fully automatic tempering furnace, wherein the heating furnace is set at a temperature of 670°C and a heating time of 420 seconds. The glass is uniformly heated in a reciprocating manner in the heating furnace, and then the glass leaves the heating furnace and enters an air cooling section, where the glass is uniformly and rapidly cooled in a reciprocating manner. The wind pressure of the rapid air cooling is 1 bar and the time is 30 seconds. Then the reciprocating motion of the glass is maintained until the temperature drops to room temperature and the tempering is completed.

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