Low-emissivity film, coated laminated glass and coated hollow glass

Abstract

The present invention provides a low-emissivity film, a coated laminated glass and a coated hollow glass, wherein the low-emissivity film comprises a first composite layer, a second composite layer, a third composite layer, a fourth composite layer, and an outermost protective layer; the first composite layer, the second composite layer, the third composite layer, and the fourth composite layer respectively comprise a dielectric layer, a functional layer, and a transition layer; the first dielectric layer is configured to block diffusion of destructive atoms into the first functional layer during heat treatment, and the second dielectric layer, the third dielectric layer, and the fourth dielectric layer are configured to increase an optical path of visible light; the first functional layer and the fourth functional layer are made of a silver-indium alloy material, and the second functional layer and the third functional layer are made of a silver material; the transition layer is made of a mixture material of a zinc- aluminum alloy and a zinc-tin alloy; the outermost protective layer comprises a third sub-layer prepared according to a single-rotating magnetron sputtering cathode equipped with a Hipims power supply, which can improve the surface mechanical properties and thermal stability of the film layers.

Description

SPECIFICATIONLOW-EMISSIVITY FILM, COATED LAMINATED GLASS AND COATED HOLLOW GLASSTECHNICAL FIELD

[0001] The present invention relates to the field of glass coating, and in particular, to a low-emissivity film, a coated laminated glass, and a coated hollow glass.BACKGROUND

[0002] Currently, conventional low-emissivity film stacks use elemental silver layers for functional layers and conventional argon as the process gas, resulting in prepared film layers with poor performance and weak processability. Transition layers are formed by superimposing two materials, leading to insufficient overall film layer bonding force. Protective layers are prepared using medium-frequency sputtering technology, which results in low film-forming hardness and poor film layer compactness, leading to insufficient protective performance. Therefore, film stacks prepared in this way are not conducive to the use of coated products.SUMMARY

[0003] In view of the above technical problems, the technical solution adopted by the present invention is as follows:According to one aspect of the present application, a low-emissivity film is provided, comprising a first composite layer, a second composite layer, a third composite layer, a fourth composite layer, and an outermost protective layer which are sequentially stacked; whereinthe first composite layer comprises a first dielectric layer, a first functional layer, and a first transition layer which are sequentially stacked;the second composite layer comprises a second dielectric layer, a second functional layer, and a second transition layer which are sequentially stacked; the third composite layer comprises a third dielectric layer, a third functional layer, and a third transition layer which are sequentially stacked;the fourth composite layer comprises a fourth dielectric layer, a fourth functional layer, and a fourth transition layer which are sequentially stacked; the first dielectric layer is configured to block diffusion of destructive atoms into the first functional layer during heat treatment, and the second dielectric layer, the third dielectric layer, and the fourth dielectric layer are configured to increase an optical path of visible light;the first functional layer, the second functional layer, the third functional layer, and the fourth functional layer are configured to reflect infrared rays, the first functional layer and the fourth functional layer are made of a silver-indium alloy material, and the second functional layer and the third functional layer are made of a silver material;the first transition layer, the second transition layer, the third transition layer, and the fourth transition layer are configured to improve thermal stability of the low-emissivity film and a mutual bonding force among the first composite layer, the second composite layer, the third composite layer, the fourth composite layer, and the outermost protective layer; the first transition layer, the second transition layer, the third transition layer, and the fourth transition layer are made of a mixture material of a zinc-aluminum alloy and a zinc-tin alloy, and the first transition layer, the second transition layer, the third transition layer, and the fourth transition layer are prepared according to a dual-rotating medium-frequency alternating current magnetron sputtering cathode;the outermost protective layer comprises a first sub-layer, a second sub-layer, and a third sub-layer, the first sub-layer is made of an oxide material of a zinctin alloy, the second sub-layer is made of a silicon nitride material, the third sub-layer is made of a mixture material of zirconium oxide and titanium oxide, and the third sub-layer is prepared according to a single-rotating magnetron sputtering cathode equipped with a Hipims power supply; the outermost protective layer is configured to provide chemical stability and mechanicaldurability during transportation and storage, and to improve the thermal stability of the low-emissivity film.

[0004] In an exemplary embodiment of the present application, a first seed layer is disposed between the first dielectric layer and the first functional layer; a second seed layer is disposed between the second dielectric layer and the second functional layer;a third seed layer is disposed between the third dielectric layer and the third functional layer;a fourth seed layer is disposed between the fourth dielectric layer and the fourth functional layer;the first seed layer, the second seed layer, the third seed layer, and the fourth seed layer are respectively bedding layers for the first functional layer, the second functional layer, the third functional layer, and the fourth functional layer;the first seed layer, the second seed layer, the third seed layer, and the fourth seed layer are made of a zinc oxide film layer or a zinc oxide film layer doped with a target element, wherein the target element is one of aluminum, gallium, indium, tin, molybdenum, yttrium, boron, silicon, germanium, titanium, hafnium, zirconium, fluorine, and scandium.

[0005] In an exemplary embodiment of the present application, a first protective layer is disposed between the first functional layer and the first transition layer;a second protective layer is disposed between the second functional layer and the second transition layer;a third protective layer is disposed between the third functional layer and the third transition layer;a fourth protective layer is disposed between the fourth functional layer and the fourth transition layer;the first protective layer, the second protective layer, the third protective layer, and the fourth protective layer are respectively configured to protect the firstfunctional layer, the second functional layer, the third functional layer, and the fourth functional layer from damage during processing.

[0006] In an exemplary embodiment of the present application, the optical thickness of the first protective layer, the second protective layer, the third protective layer, and the fourth protective layer is 0.3-3 nm;the material of the first protective layer, the second protective layer, the third protective layer, and the fourth protective layer is a single metal or an alloy of multiple metals selected from zinc, titanium, nickel, chromium, zirconium, molybdenum, tantalum, germanium, and tin, or at least one of oxides, nitrides, oxynitrides, incomplete oxides, incomplete nitrides, and incomplete oxynitrides of the above metals and alloys thereof.

[0007] In an exemplary embodiment of the present application, the optical thickness of the first functional layer, the second functional layer, the third functional layer, and the fourth functional layer is 8-20 nm;the mass fraction ratio of silver to indium in the silver-indium alloy material used for the first functional layer and the fourth functional layer is 98 to 2.

[0008] In an exemplary embodiment of the present application, the first functional layer, the first functional layer, the second functional layer, the third functional layer, and the fourth functional layer are prepared by deposition via direct current magnetron sputtering technology at a background vacuum degree lower than 6x1 O’6mbar and in a mixed atmosphere with an argon to krypton gas flow ratio ranging from 10:1 to 5:1.

[0009] In an exemplary embodiment of the present application, the first dielectric layer, the second dielectric layer, the third dielectric layer, and the fourth dielectric layer are made of a material having an extinction coefficient, as an optical constant, ranging from 0 to 0.05 in a visible light region.

[0010] In an exemplary embodiment of the present application, the optical thickness of the first sub-layer is 5-20 nm, the optical thickness of the second sub-layer is 10-30 nm, and the optical thickness of the third sub-layer is 3-11 nm;the mass fraction ratio of zirconium oxide to titanium oxide in the mixture material used for the third sub-layer is 9 to 1.

[0011] According to one aspect of the present application, a coated laminated glass is further provided, comprising a first glass layer, an intermediate layer, and a second glass layer; whereinthe intermediate layer is disposed between the first glass layer and the second glass layer;the forgoing low-emissivity film is coated on the surface of the first glass layer close to the intermediate layer and / or on the surface of the second glass layer close to the intermediate layer.

[0012] According to one aspect of the present application, a coated hollow glass is further provided, comprising a first glass layer, a connecting frame, and a second glass layer;the connecting frame is a frame body with two opposing open faces, and the first glass layer and the second glass layer are connected via the connecting frame, so that the connected first glass layer, second glass layer, and connecting frame constitute an internally hollow structure;the forgoing low-emissivity film is coated on the surface of the first glass layer close to the second glass layer and / or on the surface of the second glass layer away from the first glass layer.

[0013] The present invention has at least the following beneficial effects:

[0014] In the low-emissivity film of the present invention, the outermost protective layer prepared according to a single-rotating magnetron sputtering cathode equipped with a Hipims power supply can improve the surfacemechanical properties and thermal stability of the film layers, giving the entire film layers higher hardness, improving product processability, reducing requirements for downstream processing equipment, and saving production costs. Furthermore, the design of each transition layer can further improve the thermal stability of the film layers. Compared to conventional film stacks, it exhibits lower haze change after treatment at 600-700°C. The silver layers in the prepared low-emissivity film have lower sheet resistance compared to film stacks prepared by conventional methods at the same thickness. Moreover, silver-indium alloy is selected as the material source for the first and fourth functional layers. With this alloy material in combination with the argon-krypton mixed atmosphere and by deposition method utilizing direct current magnetron sputtering, the corrosion resistance of the silver layers can be effectively enhanced. It can also improve the film formation mode in which elemental silver material accumulates in an island-like manner, thereby resulting in a flatter surface of the functional layers and resulting in lower sheet resistance compared to silver layers of existing film stacks of the same thickness.BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For one of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0016] FIG. 1 is a schematic structural diagram of film layers of a low-emissivity film according to an embodiment of the present invention.DETAILED DESCRIPTION

[0017] The following clearly and completely describes the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Apparently, the described embodiments are some but not all of the embodiments of the present invention. All other embodiments obtained by persons of ordinary skill in the art on the basis of the embodiments of the present invention without the exercise of inventive effort shall fall within the scope of protection of the present invention.

[0018] In one aspect, the present application provides a first embodiment of a low-emissivity film. The low-emissivity film includes a first composite layer and an outermost protective layer which are sequentially stacked.

[0019] The first composite layer includes a first dielectric layer, a first seed layer, a first functional layer, a first protective layer, and a first transition layer which are sequentially stacked.

[0020] The first dielectric layer is used to block diffusion of destructive atoms (such as sodium ions, oxygen atoms, sulfur ions, etc., from a film application surface of a glass substrate) into the first functional layer during heat treatment, which can prevent the first functional layer from being contaminated and damaged, and can also reduce reflection of visible light by the low-emissivity film. The first dielectric layer is made of a material having an extinction coefficient, as an optical constant, ranging from 0 to 0.05 in a visible light region, so as not to reduce transmittance in the visible light region. The geometric thickness of the first dielectric layer is 20-45 nm.

[0021] The first seed layer is a bedding layer for the first functional layer. The first seed layer is made of a zinc oxide film layer or a zinc oxide film layer doped with a target element (the target element can be one of aluminum, gallium, indium, tin, molybdenum, yttrium, boron, silicon, germanium, titanium, hafnium, zirconium, fluorine, scandium, etc.). Based on the inherentcharacteristics of the zinc oxide film layer, doping other elements in the zinc oxide film layer helps improve sputtering stability and reduce film layer defects, and it has good bonding force with the first functional layer. The geometric thickness of the first seed layer is 8-15 nm.

[0022] The first functional layer is used to reflect infrared rays and reduce transmission of infrared rays through the low-emissivity film. Therefore, the first functional layer can be made of a material capable of reflecting infrared energy, such as silver, gold, copper, aluminum, etc. In the present application, silver or a silver-containing alloy is preferred. The silver-containing alloy in the present invention is preferably an alloy of silver with at least one of gold, aluminum, copper, and indium. In the present application, the first functional layer is preferably made of a silver-indium alloy material, and the mass fraction ratio of silver to indium in the silver-indium alloy material used for the first functional layer is 98 to 2. This can effectively reduce emissivity and improve thermal insulation performance. By using a silver-indium alloy with a mass fraction ratio of 98:2, the anti-contamination property of silver can also be effectively improved. The optical thickness of the first functional layer is 8-20 nm, and the geometric thickness of the first functional layer is 8-15 nm. The first functional layer is prepared by deposition via direct current magnetron sputtering technology at a background vacuum degree lower than 6x1 O’6mbar and in a mixed atmosphere with an argon to krypton gas flow ratio ranging from 10:1 to 5:1.

[0023] The first protective layer is used to protect the first functional layer from damage during processing. The material of the first protective layer is a single metal or an alloy of multiple metals selected from zinc, titanium, nickel, chromium, zirconium, molybdenum, tantalum, germanium, and tin, or at least one of oxides, nitrides, oxynitrides, incomplete oxides, incomplete nitrides, and incomplete oxynitrides of the above metals and alloys thereof. The optical thickness of the first protective layer is 0.3-3 nm, and the geometric thickness of the first protective layer is 0.3-2 nm.

[0024] The first transition layer is used to improve the thermal stability of the low-emissivity film and the mutual bonding force between the first composite layer and the outermost protective layer. The first transition layer is made of a mixture material of a zinc-aluminum alloy and a zinc-tin alloy. The first transition layer is prepared according to a dual-rotating medium-frequency alternating current magnetron sputtering cathode. Its main characteristic is that the two material sources of dual-rotating use different materials for cosputtering doping (for example, when using zinc, aluminum, tin metal oxides as the first transition layer, the zinc-based target material is first doped with a small amount of aluminum and tin, and finally becomes zinc-tin oxide when joining with the next film layer), causing its film layer material to form a progressive change, increasing the thermal stability and bonding force of the film layers. The geometric thickness of the first transition layer is 10-15 nm.

[0025] The outermost protective layer, as the outermost layer of the low-emissivity film in the present application, is disposed on top of the outermost transition layer. It is used to provide additional chemical stability and mechanical durability during transportation and storage, and to improve the thermal stability of the low-emissivity film, thereby enhancing the overall product stability of the low-emissivity film. The outermost protective layer includes a first sub-layer, a second sub-layer, and a third sub-layer which are sequentially stacked.

[0026] The present invention does not limit the types of film layer materials selected for the outermost protective layer, such as titanium dioxide (TiC ), silicon nitride (SisN4), zirconium dioxide (ZrC ), titanium (Ti), silicon dioxide (SiC>2), carbon (C), etc., known to those skilled in the art. The thickness of the outermost protective layer should be within a range that provides sufficient protection.

[0027] Preferably, the first sub-layer is made of an oxide material of a zinc-tin alloy, and the optical thickness of the first sub-layer is 5-20 nm.

[0028] Preferably, the second sub-layer is made of a silicon nitride material, and the optical thickness of the second sub-layer is 10-30 nm.

[0029] Preferably, the third sub-layer is made of a mixture material of zirconium oxide (ZrOx) and titanium oxide (TiOx), and the mass fraction ratio of zirconium oxide to titanium oxide in the mixture material used for the third sublayer is 9 to 1. The optical thickness of the third sub-layer is 3-11 nm. The third sub-layer is prepared according to a single-rotating magnetron sputtering cathode equipped with a Hipims power supply.

[0030] When coating the low-emissivity film of the first embodiment of the present application onto a glass substrate using a coating process (existing vacuum coating methods can be used), the first dielectric layer is close to the glass substrate. That is, on the coated surface of the glass substrate, the first dielectric layer, first seed layer, first functional layer, first protective layer, first transition layer, first sub-layer, second sub-layer, and third sub-layer are sequentially provided.

[0031] In another aspect, the present application provides a second embodiment of the low-emissivity film. The low-emissivity film includes a first composite layer, a second composite layer, and an outermost protective layer which are sequentially stacked. The functions, composition structures, material selection, optical thicknesses, and preparation methods of the first composite layer and the outermost protective layer are the same as those in the first embodiment of the low-emissivity film, and thus are not repeated in this embodiment.

[0032] The second composite layer includes a second dielectric layer, a second seed layer, a second functional layer, a second protective layer, and a second transition layer which are sequentially stacked.

[0033] The second dielectric layer is used to increase the optical path of visible light, enhance interference of visible light, and reduce reflection in the visible light region. The second dielectric layer is made of a material having an extinction coefficient, as an optical constant, ranging from 0 to 0.05 in a visible light region, so as not to reduce transmittance in a visible light region. The second dielectric layer is made of an oxide of zinc-tin alloy. The geometric thickness of the second dielectric layer is 50-80 nm.

[0034] The second seed layer is a bedding layer for the second functional layer. The second seed layer is made of a zinc oxide film layer or a zinc oxide film layer doped with a target element (the target element can be one of aluminum, gallium, indium, tin, molybdenum, yttrium, boron, silicon, germanium, titanium, hafnium, zirconium, fluorine, scandium, etc.). Based on the inherent characteristics of the zinc oxide film layer, doping other elements in the zinc oxide film layer helps improve sputtering stability and reduce film layer defects, and it has good bonding force with the second functional layer. The geometric thickness of the second seed layer is 8-15 nm.

[0035] The second functional layer is used to reflect infrared rays and reduce transmission of infrared rays through the low-emissivity film. Therefore, the second functional layer can be made of a material capable of reflecting infrared energy, such as silver, gold, copper, aluminum, etc. In the present application, silver or a silver-containing alloy is preferred. The silver-containing alloy in the present invention is preferably an alloy of silver with at least one of gold, aluminum, copper, and indium. In the present invention, the second functional layer is preferably made of a silver material. The optical thickness of the second functional layer is 8-20 nm, and the geometric thickness of the second functional layer is 12-18 nm. The second functional layer is prepared bydeposition via direct current magnetron sputtering technology at a background vacuum degree lower than 6x1 O’6mbar and in a mixed atmosphere with an argon to krypton gas flow ratio ranging from 10:1 to 5:1.

[0036] The second protective layer is used to protect the second functional layer from damage during processing. The material of the second protective layer is a single metal or an alloy of multiple metals selected from zinc, titanium, nickel, chromium, zirconium, molybdenum, tantalum, germanium, and tin, or at least one of oxides, nitrides, oxynitrides, incomplete oxides, incomplete nitrides, and incomplete oxynitrides of the above metals and alloys thereof. The optical thickness of the second protective layer is 0.3-3 nm, and the geometric thickness of the second protective layer is 0.3-2 nm.

[0037] The second transition layer is used to improve the thermal stability of the low-emissivity film and the mutual bonding force between the second composite layer and the outermost protective layer. The second transition layer is made of a mixture material a of zinc-aluminum alloy and a zinc-tin alloy. The second transition layer is prepared according to a dual-rotating mediumfrequency alternating current magnetron sputtering cathode. Its main characteristic is that the two material sources of dual-rotating use different materials for co-sputtering doping (for example, when using zinc, aluminum, tin metal oxides as the second transition layer, the zinc-based target material is first doped with a small amount of aluminum and tin, and finally becomes zinc-tin oxide when joining with the next film layer), causing its film layer material to form a progressive change, increasing the thermal stability and bonding force of the film layers. The geometric thickness of the second transition layer is 10-15 nm.

[0038] When coating the low-emissivity film of the second embodiment of the present application onto a glass substrate using a coating process, the first dielectric layer is close to the glass substrate. That is, on the coated surface of the glass substrate, the first dielectric layer, first seed layer, first functionallayer, first protective layer, first transition layer, second dielectric layer, second seed layer, second functional layer, second protective layer, second transition layer, first sub-layer, second sub-layer, and third sub-layer are sequentially provided.

[0039] In another aspect, the present application provides a third embodiment of the low-emissivity film. The low-emissivity film includes a first composite layer, a second composite layer, a third composite layer, and an outermost protective layer which are sequentially stacked. The functions, composition structures, material selection, optical thicknesses, and preparation methods of the first composite layer, the second composite layer, and the outermost protective layer are the same as those in the second embodiment of the low-emissivity film, and thus are not repeated in this embodiment.

[0040] The third composite layer includes a third dielectric layer, a third seed layer, a third functional layer, a third protective layer, and a third transition layer which are sequentially stacked.

[0041] The third dielectric layer is used to increase the optical path of visible light, enhance interference of visible light, and reduce reflection in the visible light region. The third dielectric layer is made of a material having an extinction coefficient, as an optical constant, ranging from 0 to 0.05 in a visible light region, so as not to reduce transmittance in the visible light region. The third dielectric layer is made of an oxide of zinc-tin alloy. The geometric thickness of the third dielectric layer is 50-80 nm.

[0042] The third seed layer is a bedding layer for the third functional layer. The third seed layer is made of a zinc oxide film layer or a zinc oxide film layer doped with a target element (the target element can be one of aluminum, gallium, indium, tin, molybdenum, yttrium, boron, silicon, germanium, titanium, hafnium, zirconium, fluorine, scandium, etc.). Based on the inherent characteristics of the zinc oxide film layer, doping other elements in the zincoxide film layer helps improve sputtering stability and reduce film layer defects, and it has good bonding force with the third functional layer. The geometric thickness of the third seed layer is 8-15 nm.

[0043] The third functional layer is used to reflect infrared rays and reduce transmission of infrared rays through the low-emissivity film. Therefore, the third functional layer can be made of a material capable of reflecting infrared energy, such as silver, gold, copper, aluminum, etc. In the present application, silver or a silver-containing alloy is preferred. The silver-containing alloy in the present invention is preferably an alloy of silver with at least one of gold, aluminum, copper, and indium. In the present invention, the third functional layer is made of a silver material. The optical thickness of the third functional layer is 8-20 nm, and the geometric thickness of the third functional layer is 12-20 nm. The third functional layer is prepared by deposition via direct current magnetron sputtering technology at a background vacuum degree lower than 6x1 O’6mbar and in a mixed atmosphere with an argon to krypton gas flow ratio ranging from 10:1 to 5:1.

[0044] The third protective layer is used to protect the third functional layer from damage during processing. The material of the third protective layer is a single metal or an alloy of multiple metals selected from zinc, titanium, nickel, chromium, zirconium, molybdenum, tantalum, germanium, and tin, or at least one of oxides, nitrides, oxynitrides, incomplete oxides, incomplete nitrides, and incomplete oxynitrides of the above metals and alloys thereof. The optical thickness of the third protective layer is 0.3-3 nm, and the geometric thickness of the third protective layer is 0.3-2 nm.

[0045] The third transition layer is used to improve the thermal stability of the low-emissivity film and the mutual bonding force between the third composite layer and the outermost protective layer. The third transition layer is made of a mixture material of a zinc-aluminum alloy and a zinc-tin alloy. The third transition layer is prepared according to a dual-rotating medium-frequencyalternating current magnetron sputtering cathode. Its main characteristic is that the two material sources of dual-rotating use different materials for cosputtering doping (for example, when using zinc, aluminum, tin metal oxides as the third transition layer, the zinc-based target material is first doped with a small amount of aluminum and tin, and finally becomes zinc-tin oxide when joining with the next film layer), causing its film layer material to form a progressive change, increasing the thermal stability and bonding force of the film layers. The geometric thickness of the third transition layer is 10-15 nm.

[0046] When coating the low-emissivity film of the third embodiment of the present application onto a glass substrate using a coating process, the first dielectric layer is close to the glass substrate. That is, on the coated surface of the glass substrate, the first dielectric layer, first seed layer, first functional layer, first protective layer, first transition layer, second dielectric layer, second seed layer, second functional layer, second protective layer, second transition layer, third dielectric layer, third seed layer, third functional layer, third protective layer, third transition layer, first sub-layer, second sub-layer, and third sub-layer are sequentially provided.

[0047] In another aspect, the present application provides a fourth embodiment of the low-emissivity film, as shown in FIG. 1. The low-emissivity film includes a first composite layer, a second composite layer, a third composite layer, a fourth composite layer, and an outermost protective layer which are sequentially stacked. The functions, composition structures, material selection, optical thicknesses, and preparation methods of the first composite layer, the second composite layer, the third composite layer, and the outermost protective layer are the same as those in the third embodiment of the low-emissivity film, and thus are not repeated in this embodiment.

[0048] The fourth composite layer includes a fourth dielectric layer, a fourth seed layer, a fourth functional layer, a fourth protective layer, and a fourth transition layer which are sequentially stacked.

[0049] The fourth dielectric layer is used to increase the optical path of visible light, enhance interference of visible light, and reduce reflection in the visible light region. The fourth dielectric layer is made of a material having an extinction coefficient, as an optical constant, ranging from 0 to 0.05 in a visible light region, so as not to reduce transmittance in the visible light region. The fourth dielectric layer is made of an oxide of zinc-tin alloy. Therefore, the first, second, third, and fourth dielectric layers can be a single material film layer or a superimposed film layer composed of sub-layers deposited from multiple different materials. The geometric thickness of the fourth dielectric layer is SOSO nm.

[0050] The fourth seed layer is a bedding layer for the fourth functional layer. The fourth seed layer is made of a zinc oxide film layer or a zinc oxide film layer doped with a target element (the target element can be one of aluminum, gallium, indium, tin, molybdenum, yttrium, boron, silicon, germanium, titanium, hafnium, zirconium, fluorine, scandium, etc.). Based on the inherent characteristics of the zinc oxide film layer, doping other elements in the zinc oxide film layer helps improve sputtering stability and reduce film layer defects, and it has good bonding force with the fourth functional layer. The geometric thickness of the fourth seed layer is 8-15 nm.

[0051] The fourth functional layer is used to reflect infrared rays and reduce transmission of infrared rays through the low-emissivity film. Therefore, the fourth functional layer can be made of a material capable of reflecting infrared energy, such as silver, gold, copper, aluminum, etc. In the present application, silver or a silver-containing alloy is preferred. The silver-containing alloy in the present invention is preferably an alloy of silver with at least one of gold, aluminum, copper, and indium. In the present invention, the fourth functional layer is made of a silver-indium alloy material, and the mass fraction ratio of silver to indium in the silver-indium alloy material used for the fourth functional layer is 98 to 2. This can effectively reduce emissivity and improve thermalinsulation performance. By using a silver-indium alloy with a mass fraction ratio of 98:2, the anti-contamination property of silver can also be effectively improved. The optical thickness of the fourth functional layer is 8-20 nm, and the geometric thickness of the fourth functional layer is 15-22 nm. The fourth functional layer is prepared by deposition via direct current magnetron sputtering technology at a background vacuum degree lower than 6x1 O’6mbar and in a mixed atmosphere with an argon to krypton gas flow ratio ranging from 10:1 to 5:1. When the krypton gas flow constitutes 10% to 20% of the total gas flow, the optimal film-forming quality from sputtered silver atoms is achieved.

[0052] The fourth protective layer is used to protect the fourth functional layer from damage during processing. The material of the fourth protective layer is a single metal or an alloy of multiple metals selected from zinc, titanium, nickel, chromium, zirconium, molybdenum, tantalum, germanium, and tin, or at least one of oxides, nitrides, oxynitrides, incomplete oxides, incomplete nitrides, and incomplete oxynitrides of the above metals and alloys thereof. The optical thickness of the fourth protective layer is 0.3-3 nm, and the geometric thickness of the fourth protective layer is 0.3-2 nm.

[0053] The fourth transition layer is used to improve the thermal stability of the low-emissivity film and the mutual bonding force between the fourth composite layer and the outermost protective layer. The fourth transition layer is made of a mixture material of a zinc-aluminum alloy and a zinc-tin alloy. The fourth transition layer is prepared according to a dual-rotating medium-frequency alternating current magnetron sputtering cathode. Its main characteristic is that the two material sources of dual-rotating use different materials for cosputtering doping (for example, when using zinc, aluminum, tin metal oxides as the fourth transition layer, the zinc-based target material is first doped with a small amount of aluminum and tin, and finally becomes zinc-tin oxide when joining with the next film layer), causing its film layer material to form aprogressive change, increasing the thermal stability and bonding force of the film layers. The geometric thickness of the fourth transition layer is 10-15 nm.

[0054] When coating the low-emissivity film of the fourth embodiment of the present application onto a glass substrate using a coating process, the first dielectric layer is close to the glass substrate. That is, on the coated surface of the glass substrate, the first dielectric layer, first seed layer, first functional layer, first protective layer, first transition layer, second dielectric layer, second seed layer, second functional layer, second protective layer, second transition layer, third dielectric layer, third seed layer, third functional layer, third protective layer, third transition layer, fourth dielectric layer, fourth seed layer, fourth functional layer, fourth protective layer, fourth transition layer, first sublayer, second sub-layer, and third sub-layer are sequentially provided.

[0055] Furthermore, to further improve the mechanical properties and thermal stability of the low-emissivity film described in the present application, a protective layer (this protective layer is different from the first, second, third, and fourth protective layers) can also be provided between the first seed layer and the first functional layer, between the second seed layer and the second functional layer, between the third seed layer and the third functional layer, and between the fourth seed layer and the fourth functional layer. The optical thickness of the provided protective layer is between 0.3-3 nm. The material of the protective layer can be a single metal or an alloy of multiple metals selected from zinc, titanium, nickel, chromium, zirconium, molybdenum, tantalum, germanium, and tin, or at least one of oxides, nitrides, oxynitrides, incomplete oxides, incomplete nitrides, and incomplete oxynitrides of the above metals and alloys thereof. In the present invention, a protective layer is only provided above the first, second, third, and fourth functional layers. It is understood that the present invention is not limited thereto; the number of protective layers is set according to specific situations. Therefore, the present invention also encompasses any situation that meets the requirements, such as one protective layer, two protective layers, three protective layers, four protectivelayers, five protective layers, six protective layers, seven protective layers, eight protective layers, etc.

[0056] Further, in any of the above embodiments of the low-emissivity film, the materials that may be selected for the first, second, third, and fourth dielectric layers are at least one of oxides of metals such as zinc, tin, magnesium, titanium, niobium, bismuth, zirconium, silicon, aluminum and alloys thereof, or at least one of nitrides and oxynitrides of metals such as silicon, aluminum, titanium, thallium, zirconium, niobium and alloys thereof.

[0057] The materials that are selected for the first, second, third, and fourth functional layers are at least one of silver, copper, gold, aluminum, silverindium alloy, copper-indium alloy, and silver-copper alloy.

[0058] The materials that are selected for the first, second, third, and fourth protective layers are at least one of metals such as nickel, titanium, zinc, aluminum, chromium, zirconium, germanium, tungsten, molybdenum and alloys thereof, or at least one of incomplete oxides thereof.

[0059] The materials that are selected for the first, second, third, and fourth transition layers are at least one of oxides of metals such as zinc, aluminum, tin, titanium, niobium, thallium, zirconium, magnesium, bismuth and alloys thereof.

[0060] The materials that are selected for the outermost protective layer are at least one of oxides or nitrides of metals such as titanium, zinc, tin, aluminum, silicon, zirconium and alloys thereof.

[0061] To describe in more detail and provide more persuasive support for the inventive points of the present invention, some specific examples are now listed for auxiliary proof:

[0062] In terms of mechanical properties, the ability of the film layers of the low-emissivity film to withstand friction loss and the adhesion between film layers are mainly investigated. For the manual friction assessment, a clean cotton cloth dipped in alcohol is used, with fingers pressing on the film surface and rubbing back and forth. One round trip of rubbing is recorded as 1 time, continuously rubbing 30 times. Scoring is based on the damage condition of the film surface as follows: Level 5 - film detachment upon light wiping; Level 4 - film detachment upon forceful wiping; Level 3 - slight film detachment; Level 2 - no film detachment with only slight scratches; Level 1 - good film appearance with no visible damage to the naked eye. The pencil hardness test mainly investigates the hardness of the outermost layer of the film layers. A selected standard hardness pencil is pressed against the surface under a 500-gram load and slowly dragged. Tests are conducted sequentially using pencils with progressively increasing estimated hardness, from softer to harder grades. The film hardness is determined at the first instance where the pencil leaves no scratch on the surface. The hardness grades, from softest to hardest, are as follows: 6B, 5B, 4B, 3B, 2B, HB, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H.

[0063] In terms of thermal stability, the film appearance is primarily observed to determine whether the silver layer has been contaminated or damaged after heat treatment of the film layers of the low-emissivity film. Based on the observations, it is classified into the following five grades: Level 5 - high-density white spots all over the panel under strong light; Level 4 - medium-density white spots all over the panel; Level 3 - low-density white spots all over the panel; Level 2 - individual slight white spots; Level 1 - no white spots. Further considering the haze value, the smaller the haze value, the less the silver layer is affected during the heat treatment, and the more stable the entire film layers are._ Example 1 _Layer Power Target Sputterinsequence supply / material g gas2 mm cathode Process Film pressure Film layer Glass type atmosphere layer (mBar) thickness substrate ratio material (nm) First AC dualSilicondielectric rotating aluminum Ar:N2=8:9 SiNx 3.50E-03 38 layer cathode targetFirst seed AC duallayer rotating AZO Ar:O2=20:1 ZnAIOx 3.00E-03 8 cathodeFirst DC dual- functional planar Ag Ar Ag 4.00E-03 13 layer cathodeFirst DC single- protective planar Ti Ar Ti 3.70E-03 2 layer cathodeFirst AC dual- ZnAI ZnAIOxtransition rotating Zn88Sn1 Ar:O2=1 :1.5 Zn88Sn 4.90E-03 8 layer cathode 2 12OxAC dualrotating Zn51Sn4 Ar:O2=1 :1.7 Zn51Sn9 5 4.70E-03 10 cathode 490xOutermost AC dualSiliconprotective rotating aluminum Ar:N2=1 :1.2 SiNx 3.90E-03 15 layer cathode targetHipimssinglerotating ZrTiOx Ar:O2=20:1 ZrTiOx 4.70E-03 8cathodeComparativeExample 1Layersequence Powersupply / Target Process Film Sputteringgas Film layer 2 mm cathode material atmosphere layer pressure thickness Glass material (mB (nm) substrate type ar)First AC dualSilicondielectric rotating aluminum Ar:N2=8:9 SiNx 3.50E-03 38 layer cathode targetFirst seed AC duallayer rotating AZO Ar:O2=20:1 ZnAIOx 3.00E-03 8 cathodeFirst DC dual- functional planar Ag Ar Ag 4.00E-03 13 layer cathodeFirst DCprotective single- plana Ti Ar Ti 3.70E-03 2 layer rcathodeFirst AC dualtransition rotating ZnAI Ar:O2=1 :1.5 ZnAIOx 4.90E-03 8 layer cathodeOutermost AC dualSiliconprotective rotating aluminum Ar:N2=1 :1.2 SiNx 3.30E-03 35layer cathode targetExample 2Layersequence Power Sputteringsupply / Target Process Film layer gas Film layer 2 mm cathode material atmosphere material pressure thickness Glass ratio (mBar) (nm) substrate typeFirst AC dualSilicondielectric rotating aluminum Ar:N2=8:9 SiNx 3.50E-03 38 layer cathode targetFirst seed AC duallayer rotating AZO Ar:O2=20:1 ZnAIOx 3.00E-03 8 cathodeFirst DC dual- functional planar Ar:Kr=9:1 4.00E-03 13 Ag Aglayer cathodeFirst DC single- protective planar Ti Ar Ti 3.70E-03 2 layer cathodeZnAI ZnAIOx First AC dual- transition rotating Ar:O2=1 :1.Zn88Sn1 4.90E-03 8 la e 5 Zn88Sn1y r cathode 2 2OxAC dualZn51Sn4 Ar:O2=1 :1. Zn51Sn4 rotating 4.70E-03 109 75 9Ox cathodeAC dualSilicon¬utermost Ar:N2=1 :1. rotating aluminum SiNx 3.90E-03 15 protective 2 cathode target layerHipimssingleZrTiOx Ar:O2=20:1 ZrTiOx 4.70E-03 8 rotatingcathodeExample 3LayerPower Sputtering sequence Process Film Film layer supply / Target gas atmosphere layer thickness 2 mm cathode material pressure ratio material (nm) Glass (mBar) type substrateFirst AC dualSilicondielectric rotating aluminum Ar:N2=8:9 SiNx 3.50E-03 38 layer cathode targetAC dualFirst seed rotating AZO Ar:O2=20:1 ZnAIOx 3.00E-03 8 layer cathodeFirst DC dual- functional planar Agin Ar:Kr=9:1 Agin 4.00E-03 13 layer cathodeFirst DC single- protective planar Ti Ar Ti 3.70E-03 2 layer cathodeZnAI ZnAIOx First AC dual- Ar:O2=1 :1. transition rotating 4.90E-03 8 Zn88Sn 5 Zn88Sn12 layer cathode 12OxAC dualrotating Zn51Sn49 Ar:O2=1 :1. Zn51Sncathode 75 490x 4.70E-03 10 Outermost AC dualSiliconAr:N2=1 :1.protective rotating aluminum SiNx 3.90E-03 15 layer cathode target 2Hipimssinglerotating ZrTiOx Ar:O2=20:1 ZrTiOx 3.60E-03 8cathodeComparative Example Example Example State ItemExample 1 1 2 3 Alcohol wiperesistance 3 1 1 1 testSheet4.9 4.9 4.7 4.6 Before heat resistancetreatment Visible lighttransmittance 75 75 75 75 T (%)Pencil3B HB HB HB hardness testAlcohol wiperesistance 3 1 1 1 testSheet3.9 3.7 3.5 3.4 resistanceAfter heat Visible lighttreatment transmittance 83 83 83 83 T (%)PencilHB 9H 9H 9H hardness testAppearance 3 2 2 1Haze (%) 0.65 0.4 0.2 0.19

[0064] From the comparison of the experimental results of Comparative Example 1 and Example 1 above, it can be seen that the outermost protective layer contributes significantly to both the mechanical properties and thermal stability of the entire film layers of the low-emissivity film. From the comparison of Example 1 with Examples 2 and 3, it can be seen that the preparation method of the functional layer adopted in Examples 2 and 3 significantly improves the sheet resistance of the film layers.Example 4Layersequence Powersupply / Target Process Film layer Sputtering Film layer 2 mmGlass cathode material atmosphere material gas pressure thickness (mBar) (nm) substrate typeFirst AC dualSilicondielectric rotating aluminum Ar:N2=1:1 SiNx 3.50E-03 38 layer cathode targetAC dualFirst seed rotating AZO Ar: 02=20:1 ZnAIOx 3.20E-03 10 layer cathodeFirst DC dual- functional planar Agin Ar:Kr=9:1 Agin 3.40E-03 8 layer cathodeDC First single- protective Ti Ar Ti 4.00E-03 1 planar layer cathodeZnAI ZnAIOx First AC dual- transition rotating Ar: 02=1: 1.5 4.50E-03 10 Zn88Sn1 Zn88Sn12Ox layer cathode 2Second AC dualZn51Sn4 Ar: 02=1: 1.7 dielectric rotating Zn51Sn49Ox 4.70E-03 70 9 5 layer cathodeSecond AC dualseed rotating AZO Ar: 02=20:1 ZnAIOx 3.80E-03 10 layer cathodeDC Second single- functional Agin Ar:Kr=9:1 Agin 3.50E-03 17 planar layer cathodeDC Second single- protective Ti Ar Ti 3.70E-03 1 planar layer cathodeZnAI ZnAIOx Second AC dual- transition rotating Ar: 02=1: 1.5 4.90E-03 8 Zn88Sn1 Zn88Sn12Ox layer cathode 2AC dualZn51Sn4 Ar: 02=1: 1.7 rotating Zn51Sn49Ox 4.70E-03 10 9 5 cathodeOutermos AC dualSilicont rotating aluminum Ar:N2=1:1 SiNx 3.90E-03 15 protective cathode targetlayer HipimssingleZrTiOx Ar: 02=20:1 ZrTiOx 4.70E-03 5 rotatingcathodeComparative Example 2LayerPower Sputtering Film sequencesupply / Target Process Film layer gas layer 2 mmcathode material atmosphere material pressure thickness Glass(mBar) (nm) type substrateFirst AC dualSilicondielectric rotating aluminum Ar:N2=1:1 SiNx 3.50E-03 38 layer cathode targetFirst seed AC duallayer rotating AZO Ar:O2=20:1 ZnAIOx 3.20E-03 10 cathodeFirst DC dual- functional planar Ag Ar Agin 3.40E-03 8 layer cathodeFirst DCprotective single- Ti Ar Ti 4.00E-03 1 layer planarcathodeSecond AC dualdielectric rotating Zn51Sn49 Ar:O2=1 :1. Zn51Sn49 4.70E-03 80 layer cathode 75 OxSecond AC dualseed layer rotating AZO Ar:O2=20:1 ZnAIOx 3.80E-03 10 cathodeSecond DCfunctional single- Ar Agin 3.50E-03 17 layer planar AgcathodeSecond DCprotective single- planar Ti Ar Ti 3.70E-03 1 layer cathodeSecond AC dualtransition rotating ZnAI Ar:O2=1 :1. ZnAIOx 4.90E-03 8 layer cathode 5Outermost AC dualSiliconprotective rotating aluminum Ar:N2=1 :1 SiNx 3.90E-03 38layer cathode targetExample 5Layersequence Power Sputtering Film supply / Target Process Film layer gas layer 2 mm cathode material atmosphere material pressure thickness Glass (mBar) (nm) substrate typeFirst ACdualSilicondielectric aluminum Ar:N2=1 :1 SiNx 3.50E-03 38 layer rotatingcathode targetACFirst seed duallayer rotating AZO Ar:O2=20:1 ZnAIOx 3.20E-03 10 cathodeFirst DCfunctional dual- Agin Ar:Kr=9:1 Agin 3.40E-03 8 layer planarcathodeFirst DCprotective single- Ti Ar Ti 4.00E-03 1 layer planarcathodeZnAI Ar:O2=1 :1.5 ZnAIOx 4.50E-03 10ACFirstdualZn88Sn12transition Zn88Sn12rotating OxlayercathodeACSeconddualAr:O2=1:1.7 Zn51Sn49dielectric Zn51Sn49 4.70E-03 70 rotating 5 OxlayercathodeACSecond dualAZO Ar:O2=20:1 ZnAIOx 3.80E-03 10 seed layer rotatingcathodeDCSecondsingle- functional Ar:Kr=9:1 3.50E-03 17 planar Ag AglayercathodeDCSecondsingle- protective Ti Ar Ti 3.70E-03 1 planarlayercathodeAC ZnAI ZnAIOxSeconddualtransition Ar:O2=1:1.5 Zn88Sn12 4.90E-03 8 rotating Zn88Sn12layer OxcathodeACdualAr:O2=1:1.7 Zn51Sn49Zn51Sn49 4.70E-03 10 rotating 5 OxcathodeACOutermost Silicondualprotective aluminum Ar:N2=1:1 SiNx 3.90E-03 15 rotatinglayer targetcathodeHipimssingleZrTiOx Ar:O2=20:1 ZrTiOx 4.70E-03 5 rotatingcathodeComparativeState Item Example 4 Example 5Example 2Alcohol wipe3 1 1 resistance testSheet resistance 3.2 3 3 Before heat Visible lighttreatment transmittance T 69.8 70.4 70.2(%)Pencil hardness3B HB HB testAlcohol wipe3 1 1 resistance testSheet resistance 2.2 1.9 2.1 After heat Visible lighttreatment transmittance T 75.8 76.9 76.4(%)Pencil hardness2B 9H 9HtestAppearance 2 1 1Haze (%) 0.8 0.27 0.4

[0065] From the comparison of the conventional film stack Comparative Example 2 with Examples 4 and 5 above, it can be seen that at similar film layer thicknesses, Examples 4 and 5 have superior thermal performance and better mechanical properties and thermal stability, and have greater error tolerance in production. From the comparison between Example 4 and Example 5, it can be seen that in the double-silver film stack, using silverindium alloy as the material source for both functional layers provides higher stability during heat treatment and more product advantages.Example 6Layer Sputtering sequence Power supply / Target Process Film Film layer l gasayer thickness cathode type material atmosphere pressure 2 mm Glass material (nm) (mBar) substrateSiliconFirst dielectric AC dualaluminum Ar:N2=1:1 SiNx 3.50E-03 45.8 layer rotating cathode targetFirst seed AC dualAZO Ar: 02=20:1 ZnAIOx 3.00E-03 10 layer rotating cathodeFirst DC dual-planar functional Agin Ar:Kr=9:1 Agin 3.00E-03 10 cathode layerFirst DC single- protective Ti Ar Ti 4.00E-03 1.5 planar cathode layerZnAI ZnAIOx First AC dualtransition 4.50E-03 8 Ar: 02=1: 1.5 Zn88Sn1 rotating cathode Zn88Sn12 layer 2OxSecond AC dualZn51Sn4 Ar: 02=1: 1.7 dielectric Zn51Sn49 4.30E-03 72.1 rotating cathode 5 9Ox layerSecond seed AC dualAZO Ar: 02=20:1 ZnAIOx 3.80E-03 10 layer rotating cathodeSecond DC single- functional Ar:Kr=9:1 3.40E-03 15 Ag Ag planar cathode layerSecond DC single- protective Ti Ar Ti 4.30E-03 2 planar cathode layerZnAI ZnAIOx Second AC dual- transition 4.40E-03 8 Ar: 02=1: 1.5 Zn88Sn1 rotating cathode Zn88Sn12 layer 2OxThird AC dualZn51Sn4 Ar: 02=1: 1.7 dielectric Zn51Sn49 4.70E-03 74.2 rotating cathode 5 9Ox layerThird seed AC dualAZO Ar: 02=20:1 ZnAIOx 3.80E-03 8 layer rotating cathodeThirdfunctional DC single- Agin Ar:Kr=9:1 Agin 3.50E-03 16 layer planar cathodeThirdprotective DC single- Ti Ar Ti 3.lay planar cathode 70E-03 1.5 erThirdt AC dualZnAI ZnAIOxransition Ar: 02=1 4.90E-03 8 layer rotating cathode Zn88Sn12 : 1.5 Zn88Sn12OxAC dualZn51Sn49 Ar: 02=1: 1.7 Zn51Sn4rotating cathode 4.70E-03 10 5 9OxOutermostprotective AC dualSiliconlayer rotating cathode aluminum Ar:N2=1:1 SiNx 3.90E-03 23 composite targetHipims singleZrTiOx Ar: 02=20:1 ZrTiOx 4.70E-03 5rotating cathodeExample 7Layer Power Fi Sputtering Film sequence supply / Target Process lm gamatera layer s layer i l atmosphere pressure thickness 2 mm Glass cathode type material (mBar) (nm) substrateAC dualSiliconFirst dielectric rotating aluminum SiNx 3.50E-03 45.8 Ar:N2=1:1 layer cathode targetAC dualFirst seed rotating AZO Ar: 02=20:1 ZnAIOx 3.00E-03 10 layer cathodeFirst DC dual- functional planar Agin Ar:Kr=9:1 Agin 3.00E-03 10 layer cathodeFirst DC single- protective planar Ti Ar Ti 4.00E-03 1.5 layer cathodeZnAI ZnAIOx First AC dual- transition rotating 4.50E-03 8 Ar: 02=1: 1.5 Zn88Sn1 Zn88Sn12 layer cathode 2OxSecond AC dualZn51Sn4 dielectric rotating Zn51Sn49 4.30E-03 72.1 Ar: 02=1: 1.75 9Ox layer cathodeAC dualSecond seed rotating AZO Ar: 02=20:1 ZnAIOx 3.80E-03 10 layer cathodeSecond DC single- functional planar Agin Ar:Kr=9:1 Agin 3.40E-03 15 layer cathodeSecond DC single- protective planar Ti Ar Ti 4.30E-03 2 layer cathodeZnAI ZnAIOx Second AC dual- transition rotating 4.40E-03 8 Ar: 02=1: 1.5 Zn88Sn1 Zn88Sn12 layer cathode 2OxThird AC dualZn51Sn4 dielectric rotating Zn51Sn49 4.70E-03 74.2 Ar: 02=1: 1.75 9Ox layer cathodeAC dualThird seed rotating AZO Ar: 02=20:1 ZnAIOx 3.80E-03 8 layer cathodeThird DC single- functional planar Agin Ar:Kr=9:1 Agin 3.50E-03 16 layer cathodeThird DC single- protective planar Ti Ar Ti 3.70E-03 1.5 layer cathodeThird AC dual- ZnAI ZnAIOxtransition rotating Zn88S Ar: 02=1: 1.5 Zn88Sn1 4.90E-03 8 layer cathode n12 2OxAC dualrotating Zn51Sn49 Ar: 02=1: 1.75 Zn51Sn4 4.70E-03 10 cathode 9OxOutermost AC dualSiliconprotective rotating aluminum Ar:N2=1:1 SiNx 3.90E-03 23 layer cathode targetcomposite Hipimssinglerotating ZrTiOx Ar: 02=20:1 ZrTiOx 4.70E-03 5cathodeComparative Example 3Layer Sputtering sequence Power Target Process Film layer gas Film layer mm Glass supply / material atmosphere material pressure thickness substrate cathode type (mBar) (nm) First AC dualSilicondielectric rotating aluminum Ar:N2=1:1 SiNx 3.50E-03 45.8 layer cathode targetFirst seed AC duallayer rotating AZO Ar: 02=20:1 ZnAIOx 3.00E-03 10 cathodeFirst DC dual- functional planar Ag Ar Ag 3.00E-03 10 layer cathodeFirst DC single- protective planar Ti Ar Ti 4.00E-03 1.5 layer cathodeFirst AC dual- ZnAI ZnAIOxtransition rotating Ar:O2=1:1. 4.50E-03 8 layer c Zn88Sn12 5 Zn88Sn12athode OxSecond AC dualdielectric rotating Zn51Sn49 Ar:O2=1:1. Zn51Sn49 4.30E-03 72.1 layer cathode 75 OxSecond AC dualseed layer rotating AZO Ar: 02=20:1 ZnAIOx 3.80E-03 10 cathodeSecond DC single- functional planar Ag Ar Ag 3.40E-03 15 layer cathodeSecond DC single- protective planar Ti Ar Ti 4.30E-03 2 layer cathodeSecond AC dual- ZnAI ZnAIOxtransition rotating Ar:O2=1:1. 4.40E-03 8 layer c Zn88Sn12 5 Zn88Sn12athode OxThird AC dualdielectric rotating Zn51Sn49 Ar:O2=1:1. Zn51Sn49 4.70E-03 74.2 layer cathode 75 OxThird seed AC duallayer rotating AZO Ar: 02=20:1 ZnAIOx 3.80E-03 8 cathodeThird DC single- functional planar Ag Ar Ag 3.50E-03 16layer cathodeThird DC single- protective planar Ti Ar Ti 3.70E-03 1.5 layer cathodeThird AC dual- ZnAI ZnAIOtransition rotating Ar:O2=1:1. xZn88Sn12 5 Zn88Sn12 4.90E-03 8 layer cathode OxOutermost AC dualSilicondielectric rotating aluminum Ar:N2=1:1 SiNx 3.90E-03 38layer cathode targetComparativeState Item Example 6 Example 7 Example 3Alcohol wipe3 1 1 resistance testSheet1.9 1.8 1.8 resistanceBefore heatVisible lighttreatmenttransmittance T 69 69.4 69.2 (%)Pencil3B HB HB hardness testAlcohol wipe3 1 1 resistance testSheet1.3 1.22 1.2 resistanceVisible lightAfter heattransmittance T 76.2 77.1 76.7 treatment(%)PencilHB 9H 9H hardness testAppearance 3 1 1Haze (%) 0.78 0.3 0.28

[0066] From the comparison of the Comparative Example 3 with Examples 6 and 7 above, it can be seen that at similar film layer thicknesses, Examples 6 and 7 have superior thermal performance and better mechanical properties and thermal stability, and have greater error tolerance in production. From the comparison between Example 6 and Example 7, it can be seen that in the triple-silver film stack, using silver-indium alloy as the material source for all three functional layers provides higher stability during heat treatment and more product advantages.Example 8Layersequence Power supply / Target Film Sputtering Process Film layer hode type material atmosphere layer gascat pressure thickness 2 mm Glass material (nm) (mBar) substrateSiliconFirst dielectric AC dualaluminum Ar:N2=1:1 SiNx 3.50E-03 44 layer rotating cathode targetFirst seed AC dualAZO Ar: 02=20:1 ZnAIOx 3.00E-03 8 layer rotating cathodeFirst DC dual-planar functional Agin Ar:Kr=9:1 Agin 3.00E-03 8 cathode layerFirst DC single- protective Ti Ar Ti 4.00E-03 1.3 planar cathode layerZnAI ZnAIOx First AC dual- transition Ar: 02=1: 1.5 4.50E-03 8 Zn88Sn1 rotating cathode Zn88Sn12 layer 2OxSecond AC dualAr: 02=1: 1.7 Zn51Sn4 dielectric Zn51Sn49 4.00E-03 78.6 rotating cathode 5 9Ox layerSecond seed AC dualAZO Ar: 02=20:1 ZnAIOx 3.30E-03 8 layer rotating cathodeSecond DC single- functional Ar:Kr=9:1 3.40E-03 10 Ag Ag planar cathode layerSecond DC single- protective Ti Ar Ti 4.30E-03 1.3 planar cathode layerZnAI ZnAIOx Second AC dual- transition Ar: 02=1: 1.5 4.80E-03 8 Zn88Sn1 rotating cathode Zn88Sn12 layer 2OxThird AC dualAr: 02=1: 1.7 Zn51Sn4 dielectric Zn51Sn49 4.30E-03 76.2 rotating cathode 5 9Ox layerThird seed AC dualAZO Ar: 02=20:1 ZnAIOx 3.80E-03 8 layer rotating cathodeThird DC single- functional Ar:Kr=9:1 3.40E-03 12 Ag Ag planar cathode layerThird DC single- protective Ti Ar Ti 4.30E-03 1.2 planar cathode layerZnAI ZnAIOx Third AC dualtransition Ar: 02=1: 1.5 4.40E-03 8 Zn88Sn1 rotating cathode Zn88Sn12 layer 2OxFourth AC dualAr: 02=1: 1.7 Zn51Sn4 dielectric Zn51Sn49 4.70E-03 74.6 rotating cathode 5 9Ox layerFourth seed AC dualAZO Ar: 02=20:1 ZnAIOx 3.80E-03 8 layer rotating cathodeFourth DC single- functional Agin Ar:Kr=9:1 Agin 3.50E-03 14 planar cathode layerFourth DC single- protective Ti Ar Ti 3.70E-03 2 planar cathode layerZnAI ZnAIOx Fourth AC dualtransition Ar: 02=1: 1.5 4.90E-03 8 Zn88Sn1 rotating cathode Zn88Sn12 layer 2OxOutermost AC dualAr: 02=1: 1.7 Zn51Sn4 Zn51Sn49 4.70E-03 10 protective rotating cathode 5 9Oxlayerc AC dualSiliconomposite rotating cathode aluminum Ar:N2=1:1 SiNx 3.90E-03 15 targetHipims dualZrTiOx Ar: 02=20:1 ZrTiOx 4.70E-03 5rotating cathodeExample 9Layersequence Power Sputteringsupply / Target Process Film layer gas Film layer 2 mm cathode material atmosphere material pressure thickness Glass (nm) substr type (mBar)ateFirst AC dualSilicondielectric rotating aluminum Ar:N2=1 :1 SiNx 3.50E-03 44 layer cathode targetFirst seed AC duallayer rotating AZO Ar:O2=20:1 ZnAIOx 3.00E-03 8 cathodeFirst DC dual- functional planar Agin Ar:Kr=9:1 Agin 3.00E-03 8 layer cathodeFirst DC single- protective planar Ti Ar Ti 4.00E-03 1.3 layer cathodeZnAI ZnAIOx First AC dual- transition rotating Ar:02=1 :1.Zn88Sn1 4.50E-03 8 la e c 5 Zn88Sn1y r athode 2 20xSecond AC dualZn51Sn4 Ar:02=1 :1. Zn51Sn4 dielectric rotating 4.00E-03 78.69 75 90x layer cathodeAC dualSecond rotating AZO Ar:O2=20:1 ZnAIOx 3.30E-03 8eed layer cathodeSecond DC single- functional planar Agin Ar:Kr=9:1 Agin 3.40E-03 10 layer cathodeSecond DC single- protective planar Ti Ar Ti 4.30E-03 1.3 layer cathodeZnAI ZnAIOx Second AC dual- Ar:02=1 :1. transition rotating 4.80E-03 8 Zn88Sn1 Zn88Sn1 5 layer cathode 2 20xThird AC dualZn51Sn4 Ar:02=1 :1. Zn51Sn4 dielectric rotating 4.30E-03 76.29 75 90x layer cathodeAC dual¬hird seed rotating AZO Ar:O2=20:1 ZnAIOx 3.80E-03 8 layer cathodeThird DC single- functional planar Agin Ar:Kr=9:1 Agin 3.40E-03 12 layer cathodeThird DC single- protective planar Ti Ar Ti 4.30E-03 1.2 layer cathodeZnAI ZnAIOx 4.40E-03 8Third AC dualtransition rotating Zn88Sn1 Ar:O2=1 :1. Zn88Sn1layer cathode 2 5 2OxFourth AC dualdielectric rotating Zn51Sn4 Ar:O2=1 :1. Zn51Sn4 4.70E-03 74.6 layer cathode 9 75 9OxFourth AC dualrotating AZO Ar:O2=20:1 ZnAIOx 3.80E-03 8 seed layer cathodeFourth DC single- functional planar Agin Ar:Kr=9:1 Agin 3.50E-03 14 layer cathodeFourth DC single- protective planar Ti Ar Ti 3.70E-03 2 layer cathodeZnAI ZnAIOx Fourth AC dual- transition rotating Ar:O2=1 :1.Zn88Sn1 4.90E-03 8 la e c 5 Zn88Sn1y r athode 2 2OxAC dualZn51Sn4 Ar:O2=1 :1. Zn51Sn4 rotating 4.70E-03 10 9 75 9Ox cathodeOutermost AC dualSiliconprotective rotating aluminum Ar:N2=1 :1 SiNx 3.90E-03 15 layer cathode targetcomposite HipimsdualZrTiOx Ar:O2=20:1 ZrTiOx 4.70E-03 5 rotatingcathodeComparative Example 4Layer Sputtering Film layer sequence Power supply Target Process Film layer gas thickness / cathode type material atmosphere material pressure 2 mm Glass (nm) (mBar) substrateFirst AC dualSilicondielectric rotating aluminum Ar:N2=1:1 SiNx 3.50E-03 44 layer cathode targetAC dualFirst seed rotating AZO Ar: 02=20:1 ZnAIOx 3.00E-03 8 layer cathodeFirst DC dual- functional planar Ar 3.00E-03 8 Ag Aglayer cathodeFirst DC single- protective planar Ti Ar Ti 4.00E-03 1.3 layer cathodeFirst AC dualtransition rotating ZnAI Ar: 02=1:1.5 ZnAIOx 4.50E-03 8 layer cathodeSecond AC dualZn51Sn4 Ar: 02=1:1.7 Zn51Sn49O dielectric rotating 4.00E-03 78.6 9 5 X layer cathodeAC dualSecond rotating AZO Ar: 02=20:1 ZnAIOx 3.30E-03 8 seed layer cathodeSecond DC single- functional planar Ar 3.40E-03 10 Ag Aglayer cathodeSecond DC single- protective planar Ti Ar Ti 4.30E-03 1.3 layer cathodeSecond AC dualtransition rotating ZnAI Ar: 02=1:1.5 ZnAIOx 4.80E-03 8 layer cathodeThird AC dualdielectric rotating Zn51Sn4 Ar: 02=1:1.7 Zn51Sn49O 4.30E-03 76.2 layer cathode 9 5 XThird seed AC duallayer rotating AZO Ar: 02=20:1 ZnAIOx 3.80E-03 8 cathodeThird DC single- functional planar Ag Ar Ag 3.40E-03 12 layer cathodeThird DC single- protective planar Ti Ar Ti 4.30E-03 1.2 layer cathodeThird AC dualtransition rotating ZnAI Ar: 02=1:1.5 ZnAIOx 4.40E-03 8 layer cathodeFourth AC dualdielectric rotating Zn51Sn4 Ar: 02=1:1.7 Zn51Sn49O 4.70E-03 74.6 layer cathode 9 5 XFourth seed AC duallayer rotating AZO Ar: 02=20:1 ZnAIOx 3.80E-03 8 cathodeFourth DC single- functional planar Ag Ar Ag 3.50E-03 14 layer cathodeFourth DC single- protective planar Ti Ar Ti 3.70E-03 2 layer cathodeFourth AC dualtransition rotating ZnAI Ar: 02=1:1.5 ZnAIOx 4.90E-03 8 layer cathodeOutermost AC dualSiliconprotective rotating aluminum Ar:N2=1:1 SiNx 3.90E-03 30layer cathode targetComparative Example Example State ItemExample 4 8 9 Alcohol wipe3 1 1 resistance testBeforeSheet resistance 1.6 1.55 1.52 heatVisible lighttreatment 67.5 67.3 67.3 transmittance T (%)Pencil hardness test 3B B B Alcohol wipe3 1 1 resistance testSheet resistance 1.2 1.05 1 After heat Visible light74.7 76.9 76.9 treatment transmittance T (%)Pencil hardness test 2B 9H 9H Appearance 3 1 1Haze (%) 0.7 0.37 0.3

[0067] From the comparison of the conventional film stack Comparative Example 4 with Examples 8 and 9 above, it can be seen that at similar film layer thicknesses, Examples 8 and 9 have superior thermal performance and better mechanical properties and thermal stability, and have greater error tolerance in production. From the comparison between Example 8 and Example 9, it can be seen that in the quadruple-silver film stack, using silverindium alloy as the material source for all four functional layers provides higher stability during heat treatment and more product advantages.

[0068] Therefore, from all the above examples, if superior product thermal performance is preferred, then Example 7 and Example 9 have more advantages. If lower cost is preferred while still having certain excellent properties, then Example 6 and Example 8 are better.

[0069] The outermost protective layer of the low-emissivity film of the present invention can improve the surface mechanical properties and thermal stability of the film layers, giving the entire film layers higher hardness, improving product processability, reducing requirements for downstream processing equipment, and saving production costs. Furthermore, the design of each transition layer can further improve the thermal stability of the film layers. Compared to conventional film stacks, it exhibits lower haze change after treatment at 600-700°C. The silver layers in the prepared low-emissivity film have lower sheet resistance compared to film stacks prepared by conventional methods at the same thickness.

[0070] Moreover, silver-indium alloy is selected as the material source for the first and fourth functional layers. With this alloy material in combination with the argon-krypton mixed atmosphere and by deposition method utilizing direct current magnetron sputtering, the corrosion resistance of the silver layers can be effectively enhanced. It can also, to some extent, improve the film formation mode in which elemental silver material accumulates in an island-like manner,thereby resulting in a flatter surface of the functional layers and resulting in lower sheet resistance compared to silver layers of existing film stacks of the same thickness.

[0071] In another aspect, the present application further provides a coated laminated glass, including a first glass layer, an intermediate layer, and a second glass layer. The intermediate layer is disposed between the first glass layer and the second glass layer. The low-emissivity film described above is coated on the surface of the first glass layer close to the intermediate layer and / or on the surface of the second glass layer close to the intermediate layer.

[0072] The intermediate layer in the coated laminated glass can be a glass interlayer that bonds the first and second glass layers. The coated laminated glass of the present application is a product where the low-emissivity film from any of the above examples is coated, using magnetron sputtering, onto the inner surfaces (on the side close to the intermediate layer) of the two glass layers of an existing laminated glass after being cleaned with deionized water.

[0073] The coated laminated glass provided by the present application can be assembled in vehicles. When the coated laminated glass is assembled in a vehicle, the first glass layer faces the interior of the vehicle, and the second glass layer faces the exterior. The low-emissivity film can be coated on the inner surface of the first glass layer, or on the inner surface of the second glass layer.

[0074] In another aspect, the present application further provides a coated hollow glass, including a first glass layer, a connecting frame, and a second glass layer. The connecting frame is a frame body with two opposing open faces, and the first glass layer and the second glass layer are connected via the connecting frame, so that the connected first glass layer, second glass layer, and connecting frame constitute an internally hollow structure. The forgoing low-emissivity film is coated on the surface of the first glass layer closeto the second glass layer and / or the surface of the second glass layer away from the first glass layer.

[0075] The first glass layer, the connecting frame (which may be an aluminum frame), and the second glass layer in the coated hollow glass may be selected from the structure of the existing hollow glass. The coated hollow glass of the present application is a product where the low-emissivity film from any of the above examples is coated, using magnetron sputtering, onto the indoor surfaces (on the side of the hollow glass close to the indoor side after installation) of the two glass layers of an existing hollow glass after being cleaned with deionized water.

[0076] The coated hollow glass provided by the present application can be assembled on a window of a house, with the glass layer coated with the low-emissivity film in the coated hollow glass facing an outdoor side of the house.

[0077] In addition, it should be noted that the low-emissivity film of the present application may be not only coated onto glass products, but also used on other substrates, such as oily films, plastic parts, and the like.

[0078] The above description is only the specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or replacements that can be easily conceived by those skilled in the art within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

AMENDED CLAIMSreceived by the International Bureau on 17 July 2026 (1707.2026)1. A coated glass comprising a low-emissivity film, characterized by comprising a first composite layer, a second composite layer, a third composite layer, a fourth composite layer, and an outermost protective layer which are sequentially stacked;whereinthe first composite layer comprises a first dielectric layer, a first functional layer, and a first transition layer which are sequentially stacked;the second composite layer comprises a second dielectric layer, a second functional layer, and a second transition layer which are sequentially stacked;the third composite layer comprises a third dielectric layer, a third functional layer, and a third transition layer which are sequentially stacked;the fourth composite layer comprises a fourth dielectric layer, a fourth functional layer, and a fourth transition layer which are sequentially stacked;the first dielectric layer is configured to block diffusion of destructive atoms into the first functional layer during heat treatment, and the second dielectric layer, the third dielectric layer, and the fourth dielectric layer are configured to increase an optical path of visible light;the first functional layer, the second functional layer, the third functional layer, and the fourth functional layer are configured to reflect infrared rays, the first functional layer and the fourth functional layer are made of a silver-indium alloy material, and the second functional layer and the third functional layer are made of a silver material;the first transition layer, the second transition layer, the third transition layer, and the fourth transition layer are configured to improve thermal stability of the low-emissivity film and a mutual bonding force among the first composite layer, the second composite layer, the third composite layer, the fourth composite layer, and the outermost protective layer; the first transition layer, the second transition layer, the third transition layer, and the fourth transition layer are made of a mixturematerial of a zinc-aluminum alloy and a zinc-tin alloy, and the first transition layer, the second transition layer, the third transition layer, and the fourth transition layer are prepared according to a dual-rotating medium-frequency alternating current magnetron sputtering cathode;the outermost protective layer comprises a first sub-layer, a second sub- layer, and a third sub-layer, the first sub-layer is made of an oxide material of a zinc-tin alloy, the second sub-layer is made of a silicon nitride material, the third sub-layer is made of a mixture material of zirconium oxide and titanium oxide, and the third sublayer is prepared according to a single-rotating magnetron sputtering cathode equipped with a Hipims power supply; the outermost protective layer is configured to provide chemical stability and mechanical durability during transportation and storage, and to improve the thermal stability of the low-emissivity film.

2. The coated glass according to claim 1 , wherein a first seed layer is disposed between the first dielectric layer and the first functional layer;a second seed layer is disposed between the second dielectric layer and the second functional layer;a third seed layer is disposed between the third dielectric layer and the third functional layer;a fourth seed layer is disposed between the fourth dielectric layer and the fourth functional layer;the first seed layer, the second seed layer, the third seed layer, and the fourth seed layer are respectively bedding layers for the first functional layer, the second functional layer, the third functional layer, and the fourth functional layer;the first seed layer, the second seed layer, the third seed layer, and the fourth seed layer are made of a zinc oxide film layer or a zinc oxide film layer doped with a target element, wherein the target element is one of aluminum, gallium, indium, tin, molybdenum, yttrium, boron, silicon, germanium, titanium, hafnium, zirconium, fluorine, and scandium.

3. The coated glass according to claim 2, wherein a first protective layer is disposed between the first functional layer and the first transition layer;a second protective layer is disposed between the second functional layer and the second transition layer;a third protective layer is disposed between the third functional layer and the third transition layer;a fourth protective layer is disposed between the fourth functional layer and the fourth transition layer;the first protective layer, the second protective layer, the third protective layer, and the fourth protective layer are respectively configured to protect the first functional layer, the second functional layer, the third functional layer, and the fourth functional layer from damage during processing.

4. The coated glass according to claim 3, wherein the optical thickness of the first protective layer, the second protective layer, the third protective layer, and the fourth protective layer is 0.3-3 nm;the material of the first protective layer, the second protective layer, the third protective layer, and the fourth protective layer is a single metal or an alloy of multiple metals selected from zinc, titanium, nickel, chromium, zirconium, molybdenum, tantalum, germanium, and tin, or at least one of oxides, nitrides, oxynitrides, incomplete oxides, incomplete nitrides, and incomplete oxynitrides of the above metals and alloys thereof.

5. The coated glass according to claim 4, wherein the optical thickness of the first functional layer, the second functional layer, the third functional layer, and the fourth functional layer is 8-20 nm;the mass fraction ratio of silver to indium in the silver-indium alloy material used for the first functional layer and the fourth functional layer is 98 to 2.

6. The coated glass according to claim 5, wherein the first functional layer, the second functional layer, the third functional layer, and the fourth functional layer are prepared by deposition via direct current magnetron sputtering technology at a background vacuum degree lower than 6x1 O’6mbar and in a mixed atmosphere with an argon to krypton gas flow ratio ranging from 10:1 to 5:1.

7. The coated glass according to claim 6, wherein the first dielectric layer, the second dielectric layer, the third dielectric layer, and the fourth dielectric layer are made of a material having an extinction coefficient, as an optical constant, ranging from 0 to 0.05 in a visible light region.

8. The coated glass according to claim 7, wherein the optical thickness of the first sub-layer is 5-20 nm, the optical thickness of the second sub-layer is 10-30 nm, and the optical thickness of the third sub-layer is 3-11 nm;the mass fraction ratio of zirconium oxide to titanium oxide in the mixture material used for the third sub-layer is 9 to 1.

9. A coated laminated glass, comprising the coated glass according to any one of claims 1-8,characterized by comprising a first glass layer, an intermediate layer, and a second glass layer; whereinthe intermediate layer is disposed between the first glass layer and the second glass layer;the low-emissivity film is coated on the surface of the first glass layer close to the intermediate layer and / or on the surface of the second glass layer close to the intermediate layer.

10. A coated hollow glass, comprising the coated glass according to any one of claims 1-8,characterized by comprising a first glass layer, a connecting frame, and a second glass layer; whereinthe connecting frame is a frame body with two opposing open faces, and the first glass layer and the second glass layer are connected via the connecting frame, so that the connected first glass layer, second glass layer, and connecting frame constitute an internally hollow structure;the low-emissivity film is coated on the surface of the first glass layer close to the second glass layer and / or on the surface of the second glass layer away from the first glass layer.

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