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

Abstract

The invention provides a low-emissivity film, coated laminated glass and coated hollow glass, and the low-emissivity film comprises a first combination layer, a second combination layer, a third combination layer, a fourth combination layer and an outermost protection layer; the first combined layer, the second combined layer, the third combined layer and the fourth combined layer respectively comprise a dielectric layer, a functional layer and a transition layer; the first dielectric layer is used for preventing destructive atoms from diffusing to the first functional layer in the heat treatment process, and the second dielectric layer, the third dielectric layer and the fourth dielectric layer are used for increasing the optical path of visible light; the first functional layer and the fourth functional layer are made of silver-indium alloy materials, and the second functional layer and the third functional layer are made of silver materials; the transition layer is made of a mixture material of a zinc-aluminum alloy and a zinc-tin alloy; and the third sub-layer included in the outermost protection layer is prepared according to a single-rotation magnetron sputtering cathode matched with a Hipims power supply, so that the surface mechanical property and the thermal stability of the film layer can be improved.

Description

Technical Field

[0001] The present invention relates to the field of glass coating, and particularly to a low-emissivity thin film, a coated laminated glass, and a coated insulating glass. Background Art

[0002] Currently, in traditional low-emissivity film systems, the functional layer uses a single silver layer, and the process gas uses traditional argon gas, resulting in poor performance of the prepared film layer, weak processability. The transition layer is composed of two materials stacked together, resulting in an insecure bonding force of the overall film layer. The protective layer is prepared by medium-frequency sputtering technology, with low film hardness and film layer density, and insufficient protection performance. Therefore, the film system prepared therefrom is not conducive to the use of coated products. Summary of the Invention

[0003] In view of the above technical problems, the technical solution adopted by the present invention is as follows:

[0004] According to one aspect of the present application, there is provided a low-emissivity thin film, including a first composite layer, a second composite layer, a third composite layer, a fourth composite layer, and an outermost protective layer that are sequentially stacked.

[0005] The first composite layer includes a first dielectric layer, a first functional layer, and a first transition layer that are sequentially stacked.

[0006] The second composite layer includes a second dielectric layer, a second functional layer, and a second transition layer that are sequentially stacked.

[0007] The third composite layer includes a third dielectric layer, a third functional layer, and a third transition layer that are sequentially stacked.

[0008] The fourth composite layer includes a fourth dielectric layer, a fourth functional layer, and a fourth transition layer that are sequentially stacked.

[0009] The first dielectric layer is used to block the diffusion of destructive atoms to the first functional layer during the heat treatment process, and the second dielectric layer, the third dielectric layer, and the fourth dielectric layer are used to increase the optical path of visible light.

[0010] The first functional layer, the second functional layer, the third functional layer, and the fourth functional layer are used 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.

[0011] The first transition layer, the second transition layer, the third transition layer, and the fourth transition layer are used to improve the thermal stability of the low-emissivity film and the adhesion between 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 of zinc-aluminum alloy and 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 AC magnetron sputtering cathode;

[0012] The outermost protective layer includes a first sub-layer, a second sub-layer, and a third sub-layer. The first sub-layer is made of an oxide material of zinc-tin alloy, the second sub-layer is made of silicon nitride material, and the third sub-layer is made of a mixture of zirconium oxide and titanium oxide. Moreover, 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 used to provide chemical stability and mechanical durability during transportation and storage, as well as to improve the thermal stability of the low-emissivity film.

[0013] In an exemplary embodiment of the present application, a first seed layer is provided between the first dielectric layer and the first functional layer;

[0014] A second seed layer is provided between the second dielectric layer and the second functional layer;

[0015] A third seed layer is provided between the third dielectric layer and the third functional layer;

[0016] A fourth seed layer is provided between the fourth dielectric layer and the fourth functional layer;

[0017] The first seed layer, the second seed layer, the third seed layer, and the fourth seed layer are respectively the implantation layers for the first functional layer, the second functional layer, the third functional layer, and the fourth functional layer;

[0018] The first seed layer, the second seed layer, the third seed layer, and the fourth seed layer are made of zinc oxide film layers or zinc oxide film layers doped with target elements, where the target elements are one of aluminum, gallium, indium, tin, molybdenum, yttrium, boron, silicon, germanium, titanium, hafnium, zirconium, fluorine, and scandium.

[0019] In an exemplary embodiment of the present application, a first protective layer is provided between the first functional layer and the first transition layer;

[0020] A second protective layer is provided between the second functional layer and the second transition layer;

[0021] A third protective layer is provided between the third functional layer and the third transition layer;

[0022] A fourth protective layer is provided between the fourth functional layer and the fourth transition layer;

[0023] The first protective layer, the second protective layer, the third protective layer, and the fourth protective layer are respectively used to protect the first functional layer, the second functional layer, the third functional layer, and the fourth functional layer from being damaged during the processing.

[0024] 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 nanometers;

[0025] The materials of the first protective layer, the second protective layer, the third protective layer, and the fourth protective layer are 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 their alloys.

[0026] 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 nanometers;

[0027] The mass fraction ratio of silver compounds and indium compounds in the silver - indium alloy material used for the first functional layer and the fourth functional layer is 98 to 2.

[0028] In an exemplary embodiment of the present application, the first functional layer, the second functional layer, the third functional layer, and the fourth functional layer are deposited and prepared by DC magnetron sputtering technology under a background vacuum of less than 6×10 -6 mbar and in a mixed atmosphere with an argon - to - krypton flow rate ratio of 10:1 to 5:1.

[0029] 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 materials with an extinction coefficient of 0 - 0.05 for the optical constants in the visible light region.

[0030] In an exemplary embodiment of the present application, the optical thickness of the first sub - layer is 5 - 20 nanometers, the optical thickness of the second sub - layer is 10 - 30 nanometers, and the optical thickness of the third sub - layer is 3 - 11 nanometers;

[0031] The mass fraction ratio of zirconium oxide and titanium oxide in the mixture material used for the third sub - layer is 9 to 1.

[0032] According to one aspect of the present application, there is also provided a coated insulating glass, including a first glass layer, an intermediate layer, and a second glass layer;

[0033] The intermediate layer is disposed between the first glass layer and the second glass layer;

[0034] The above - mentioned low - emissivity thin 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.

[0035] According to one aspect of the present application, there is also provided a coated insulating glass, including a first glass layer, a connecting frame, and a second glass layer;

[0036] The connecting frame is a frame body with two opposite surfaces penetrating. Through the connecting frame, the first glass layer and the second glass layer are connected, so that the connected first glass layer, second glass layer, and connecting frame form an internal hollow structure;

[0037] The above-mentioned low-emissivity thin 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 far from the first glass layer.

[0038] The present invention has at least the following beneficial effects:

[0039] In the low-emissivity thin film of the present invention, the outermost protective layer prepared according to the single-rotating magnetron sputtering cathode equipped with a Hipims power supply can improve the surface mechanical properties and thermal stability of the film layer, making the entire film layer have higher hardness, improving the processability of the product, reducing the requirements for downstream processing equipment, saving production costs, and the design of each transition layer can further improve the thermal stability of the film layer. Compared with the traditional film system, after being treated at 600 - 700 degrees Celsius, it has a lower haze change. The silver layer of the prepared low-emissivity thin film has a lower sheet resistance at the same thickness compared with the film system prepared by the traditional method. Moreover, the first functional layer and the fourth functional layer select an alloy of silver and indium as the material source. This alloy material, combined with a mixed atmosphere of argon and krypton, can effectively enhance the corrosion resistance of the silver layer through the deposition preparation method of DC magnetron sputtering, and can also improve the film formation method of the elemental silver material source with island-like accumulation, making the surface of the functional layer flatter and having a lower sheet resistance compared with the silver layer of the existing film system at the same thickness. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0041] Figure 1 It is a schematic structural diagram of the film layer of the low-emissivity thin film provided by the embodiment of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0042] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative efforts belong to the protection scope of the present invention.

[0043] On the one hand, a first embodiment of a low-emissivity film is proposed in the present application. The low-emissivity film includes a first composite layer and an outermost protective layer stacked in sequence.

[0044] Among them, 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 stacked in sequence.

[0045] The first dielectric layer is used to block the diffusion of destructive atoms (such as sodium ions, oxygen atoms, sulfur ions, etc. from the film deposition surface of the glass substrate) to the first functional layer during the heat treatment process, which can avoid the contamination and damage of the first functional layer, and can also reduce the reflection of visible light by the low-emissivity film. The first dielectric layer is made of a material with an extinction coefficient of 0-0.05 in the visible light region, so as not to reduce the transmittance in the visible light region. The geometric thickness of the first dielectric layer is 20-45 nanometers.

[0046] The first seed layer is the implantation layer of 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 self-characteristics of the zinc oxide film layer, doping other elements in the zinc oxide film layer is beneficial to improving the sputtering stability of the zinc oxide film layer and reducing film layer defects, and has a good bonding force with the first functional layer. The geometric thickness of the first seed layer is 8-15 nanometers.

[0047] The first functional layer is used to reflect infrared rays and reduce the transmission of infrared rays from the low-emissivity film. Therefore, the first functional layer can select materials that can reflect infrared energy, such as silver, gold, copper, aluminum, etc. The present application preferably uses silver or a silver-containing alloy. Among them, the silver-containing alloy in the present invention is preferably an alloy of silver and at least one of gold, aluminum, copper, and indium. The first functional layer in the present application preferably uses a silver-indium alloy material, and the mass fraction ratio of silver compounds and indium compounds in the silver-indium alloy material used in the first functional layer is 98:2, which can effectively reduce the emissivity and improve the heat insulation performance. Moreover, by using a silver-indium alloy with a mass fraction of 98:2, the anti-pollution property of silver can also be effectively improved. The optical thickness of the first functional layer is 8-20 nanometers, the geometric thickness of the first functional layer is 8-15 nanometers, and the first functional layer is under a background vacuum degree lower than 6×10 -6It is prepared by DC magnetron sputtering deposition in a mixed atmosphere of millibar, with the flow ratio of argon to krypton being 10:1 to 5:1.

[0048] The first protective layer is used to protect the first functional layer from being damaged 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, tin, or at least one of the oxides, nitrides, oxynitrides, suboxides, subnitrides, and suboxynitrides of the above metals and their alloys. The optical thickness of the first protective layer is 0.3 - 3 nm, and the geometric thickness is 0.3 - 2 nm.

[0049] The first transition layer is used to improve the thermal stability of the low - emissivity film and the interfacial bonding force between the first composite layer and the outermost protective layer. The first transition layer is made of a mixture of zinc - aluminum alloy and zinc - tin alloy. The first transition layer is prepared according to a dual - rotation medium - frequency AC magnetron sputtering cathode. Its main feature lies in that the two material sources of the dual - rotation use different materials for mixed sputtering doping (for example, when using metal oxides such as zinc, aluminum, and tin as the first transition layer, the zinc - based target is first doped with a small amount of aluminum and tin, and finally when connecting to the next film layer, it is the oxides of zinc and tin), so that the film layer material forms a progressive change, increasing the thermal stability and the bonding force of the film layer. The geometric thickness of the first transition layer is 10 - 15 nm.

[0050] Among them, the outermost protective layer, as the outermost layer of the low - emissivity film described in this application, is set above the outermost transition layer, and is used to provide additional chemical stability and mechanical durability during transportation and storage, as well as improve the thermal stability of the low - emissivity film to enhance 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 stacked in sequence.

[0051] The present invention does not limit the types of film layer materials selected for the outermost protective layer. For example, titanium dioxide (TiO 2 ), silicon nitride (Si 3 N 4 ), zirconium dioxide (ZrO 2 ), titanium (Ti), silicon dioxide (SiO 2 ), carbon (C), etc., which are well - known to those skilled in the art. The thickness of the outermost protective layer should be within the range that can provide sufficient protection.

[0052] Preferably, the first sub - layer is made of an oxide material of zinc - tin alloy, and the optical thickness of the first sub - layer is 5 - 20 nm.

[0053] Preferably, the second sub - layer is made of silicon nitride material, and the optical thickness of the second sub - layer is 10 - 30 nm.

[0054] Preferably, the third sub-layer is made of a mixture material of zirconium oxide (ZrO x ) and titanium oxide (TiO x ). The mass fraction ratio of zirconium oxide to titanium oxide in the mixture material used for the third sub-layer is 9:1. The optical thickness of the third sub-layer is 3 - 11 nanometers, and the third sub-layer is prepared according to a single-rotating magnetron sputtering cathode equipped with a Hipims power supply.

[0055] When the first embodiment of the low-emissivity thin film described in this application is deposited on a glass substrate by a coating process (an existing vacuum coating method can be used), the first dielectric layer is close to the glass substrate, that is, the first dielectric layer, the first seed layer, the first functional layer, the first protective layer, the first transition layer, the first sub-layer, the second sub-layer, and the third sub-layer are sequentially arranged on the coating surface of the glass substrate.

[0056] On the other hand, a second embodiment of the low-emissivity thin film is proposed in this application. The low-emissivity thin film includes a first composite layer, a second composite layer, and an outermost protective layer that are sequentially stacked. Among them, the functions, composition structures, material selections, optical thicknesses, and preparation methods of the first composite layer and the outermost protective layer are the same as those of the first composite layer and the outermost protective layer in the first embodiment of the low-emissivity thin film, so they will not be elaborated in this embodiment.

[0057] Among them, 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 that are sequentially stacked.

[0058] The second dielectric layer is used to increase the optical path of visible light, enhance the interference of visible light, and reduce the reflection in the visible light region. The second dielectric layer is made of a material with an extinction coefficient of 0 - 0.05 for the optical constant in the visible light region to avoid reducing the transmittance in the visible light region. The second dielectric layer is made of an oxide of zinc tin alloy, and the geometric thickness of the second dielectric layer is 50 - 80 nanometers.

[0059] The second seed layer is the implantation 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 self-characteristics of the zinc oxide film layer, doping other elements in the zinc oxide film layer is beneficial to improving the sputtering stability of the zinc oxide film layer and reducing film layer defects, and has a good bonding force with the second functional layer. The geometric thickness of the second seed layer is 8 - 15 nanometers.

[0060] The second functional layer is used to reflect infrared rays and reduce the transmission of infrared rays through the low-emissivity film. Therefore, the second functional layer can select materials that can reflect infrared energy, such as silver, gold, copper, aluminum, etc. In this application, silver or silver-containing alloys are preferably used. Among them, the silver-containing alloy in the present invention is preferably an alloy of silver and at least one of gold, aluminum, copper, and indium. The second functional layer of the present invention preferably uses a silver-based material. The optical thickness of the second functional layer is 8-20 nanometers, and the geometric thickness of the second functional layer is 12-18 nanometers. The second functional layer is deposited and prepared by DC magnetron sputtering technology under a background vacuum of less than 6×10 -6 mbar and a mixed atmosphere with an argon-to-krypton flow ratio of 10:1 to 5:1.

[0061] The second protective layer is used to protect the second functional layer from being damaged during the 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 their alloys. The optical thickness of the second protective layer is 0.3-3 nanometers, and the geometric thickness of the second protective layer is 0.3-2 nanometers.

[0062] 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 uses a mixture of zinc-aluminum alloy and zinc-tin alloy. The second transition layer is prepared according to a dual-rotating medium-frequency AC magnetron sputtering cathode. Its main feature is that the two material sources of the dual rotation use different materials for mixed sputtering doping (for example, when using metal oxides such as zinc, aluminum, and tin as the second transition layer, the zinc-based target is first doped with a small amount of aluminum and tin, and finally when connecting to the next film layer, it is the oxides of zinc and tin), so that the film layer material forms a progressive change, increasing the thermal stability and film layer bonding force of the film layer. The geometric thickness of the second transition layer is 10-15 nanometers.

[0063] When the second embodiment of the low-emissivity film described in this application is laid on a glass substrate by a coating process, the first dielectric layer is close to the glass substrate, that is, the first dielectric layer, the first seed layer, the first functional layer, the first protective layer, the first transition layer, the second dielectric layer, the second seed layer, the second functional layer, the second protective layer, the second transition layer, the first sub-layer, the second sub-layer, and the third sub-layer are sequentially arranged on the coating surface of the glass substrate.

[0064] On the other hand, a third embodiment of the low-emissivity film is proposed in the present application. The low-emissivity film includes a first composite layer, a second composite layer, a third composite layer, and an outermost protective layer that are sequentially stacked. Among them, the functions, compositional structures, material selections, optical thicknesses, and preparation methods of the first composite layer, the second composite layer, and the outermost protective layer are the same as those of the first composite layer, the second composite layer, and the outermost protective layer in the second embodiment of the low-emissivity film, so they will not be elaborated herein.

[0065] Among them, 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 that are sequentially stacked.

[0066] The third dielectric layer is used to increase the optical path of visible light, enhance the interference of visible light, and reduce the reflection in the visible light region. The third dielectric layer uses a material with an extinction coefficient of 0-0.05 in the visible light region in terms of optical constants, so as not to reduce the transmittance in the visible light region. The third dielectric layer uses an oxide of zinc tin alloy, and the geometric thickness of the third dielectric layer is 50-80 nanometers.

[0067] The third seed layer is a landing layer for the third functional layer. The third seed layer uses 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 self-characteristics of the zinc oxide film layer, doping other elements in the zinc oxide film layer is beneficial to improving the sputtering stability of the zinc oxide film layer and reducing film layer defects, and has a good bonding force with the third functional layer. The geometric thickness of the third seed layer is 8-15 nanometers.

[0068] The third functional layer is used to reflect infrared rays and reduce the transmission of infrared rays from the low-emissivity film. Therefore, the third functional layer can select materials that can reflect infrared energy, such as silver, gold, copper, aluminum, etc. The present application preferably uses silver or a silver-containing alloy. Among them, the silver-containing alloy in the present invention is preferably an alloy of silver and at least one of gold, aluminum, copper, and indium. The third functional layer of the present invention uses a silver-based material. The optical thickness of the third functional layer is 8-20 nanometers, and the geometric thickness of the third functional layer is 12-20 nanometers. The third functional layer is deposited and prepared by direct current magnetron sputtering technology under a background vacuum of less than 6×10 -6 mbar and a mixed atmosphere with an argon and krypton flow ratio of 10:1 to 5:1.

[0069] The third protective layer is used to protect the third functional layer from being damaged during the 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 the oxides, nitrides, oxynitrides, incomplete oxides, incomplete nitrides, and incomplete oxynitrides of the above metals and their alloys. The optical thickness of the third protective layer is 0.3 - 3 nanometers, and the geometric thickness of the third protective layer is 0.3 - 2 nanometers.

[0070] The third transition layer is used to improve the thermal stability of the low-emissivity thin film and the interfacial bonding force between the third composite layer and the outermost protective layer. The third transition layer is made of a mixture of zinc-aluminum alloy and zinc-tin alloy. The third transition layer is prepared according to a dual-rotating medium-frequency alternating magnetron sputtering cathode. Its main feature is that the two material sources of the dual-rotation use different materials for mixed sputtering doping (for example, when using metal oxides such as zinc, aluminum, and tin as the third transition layer, the zinc-based target is first doped with a small amount of aluminum and tin, and finally, when connecting to the next film layer, it is the oxides of zinc and tin), so that the film layer material forms a progressive change, increasing the thermal stability of the film layer and the film layer bonding force. The geometric thickness of the third transition layer is 10 - 15 nanometers.

[0071] When the third embodiment of the low-emissivity thin film described in the present application is deposited on a glass substrate by a coating process, the first dielectric layer is adjacent to the glass substrate, that is, the first dielectric layer, the first seed layer, the first functional layer, the first protective layer, the first transition layer, the second dielectric layer, the second seed layer, the second functional layer, the second protective layer, the second transition layer, the third dielectric layer, the third seed layer, the third functional layer, the third protective layer, the third transition layer, the first sub-layer, the second sub-layer, and the third sub-layer are sequentially arranged on the coating surface of the glass substrate.

[0072] On the other hand, the present application proposes a fourth embodiment of the low-emissivity thin film, as Figure 1 shown, the low-emissivity thin 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. Among them, the functions, compositional structures, material selections, 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 of the first composite layer, the second composite layer, the third composite layer, and the outermost protective layer in the third embodiment of the low-emissivity thin film, so they will not be elaborated in this embodiment.

[0073] Among them, 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.

[0074] The fourth dielectric layer is used to increase the optical path of visible light, enhance the interference of visible light, and reduce the reflection in the visible light region. The fourth dielectric layer is made of a material with an extinction coefficient of 0 - 0.05 in the visible light region to avoid reducing the transmittance in the visible light region. The fourth dielectric layer is made of an oxide of zinc tin alloy. Therefore, the first dielectric layer, the second dielectric layer, the third dielectric layer, and the fourth dielectric layer can be a single material film layer or a stacked film layer composed of sub-layers deposited with multiple different materials. The geometric thickness of the fourth dielectric layer is 50 - 80 nanometers.

[0075] The fourth sub-layer is the implantation layer of the fourth functional layer. The fourth sub-layer uses 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 self-characteristics of the zinc oxide film layer, doping other elements in the zinc oxide film layer is beneficial to improving the sputtering stability of the zinc oxide film layer and reducing film layer defects, and has a good bonding force with the fourth functional layer. The geometric thickness of the fourth sub-layer is 8 - 15 nanometers.

[0076] The fourth functional layer is used to reflect infrared rays and reduce the transmission of infrared rays from the low-emissivity thin film. Therefore, the fourth functional layer can select a material capable of reflecting infrared energy, such as silver, gold, copper, aluminum, etc. In this application, silver or a silver-containing alloy is preferably used. Among them, the silver-containing alloy in the present invention is preferably an alloy of silver and at least one of gold, aluminum, copper, and indium. The fourth functional layer of the present invention uses a silver indium alloy material, and the mass fraction ratio of silver compounds and indium compounds in the silver indium alloy material used in the fourth functional layer is 98 to 2, which can effectively reduce the emissivity and improve the heat insulation performance. Moreover, by using a silver indium alloy with a mass fraction of 98 to 2, the anti-pollution property of silver can also be effectively improved. The optical thickness of the fourth functional layer is 8 - 20 nanometers, the geometric thickness of the fourth functional layer is 15 - 22 nanometers, and the fourth functional layer is deposited and prepared by direct current magnetron sputtering technology under a background vacuum of less than 6×10 -6 mbar and a mixed atmosphere with an argon and krypton gas flow ratio of 10 to 1 to 5 to 1. Among them, when the gas volume of krypton accounts for 10% to 20% of the total gas volume, the film formation quality of sputtered silver atoms is the best.

[0077] The fourth protective layer is used to protect the fourth functional layer from being damaged during the processing. The material of the fourth protective layer uses a single metal or an alloy of multiple metals among 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 their alloys. The optical thickness of the fourth protective layer is 0.3 - 3 nanometers, and the geometric thickness of the fourth protective layer is 0.3 - 2 nanometers.

[0078] The fourth transition layer is used to improve the thermal stability of the low-emissivity thin film and the interfacial adhesion between the fourth composite layer and the outermost protective layer. The fourth transition layer is made of a mixture of zinc-aluminum alloy and zinc-tin alloy. The fourth transition layer is prepared according to a dual-rotating medium-frequency AC magnetron sputtering cathode. Its main feature lies in that the two material sources of the dual rotation use different materials for mixed sputtering doping (for example, when using metal oxides such as zinc, aluminum, and tin as the fourth transition layer, the zinc-based target is first doped with a small amount of aluminum and tin, and finally when connecting to the next film layer, it is the oxides of zinc and tin), so that the film layer material forms a progressive change, increasing the thermal stability and film layer adhesion of the film layer. The geometric thickness of the fourth transition layer is 10-15 nanometers.

[0079] When the fourth embodiment of the low-emissivity thin film described in the present application is deposited on a glass substrate by a coating process, the first dielectric layer is adjacent to the glass substrate, that is, the first dielectric layer, the first seed layer, the first functional layer, the first protective layer, the first transition layer, the second dielectric layer, the second seed layer, the second functional layer, the second protective layer, the second transition layer, the third dielectric layer, the third seed layer, the third functional layer, the third protective layer, the third transition layer, the fourth dielectric layer, the fourth seed layer, the fourth functional layer, the fourth protective layer, the fourth transition layer, the first sub-layer, the second sub-layer, and the third sub-layer are sequentially arranged on the coating surface of the glass substrate.

[0080] In addition, in order to further enhance the mechanical properties and thermal stability of the low-emissivity thin film described in the present application, a protective layer (this protective layer is different from the first protective layer, the second protective layer, the third protective layer, and the fourth protective layer) 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 selected from a single metal or an alloy of multiple metals among 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 their alloys. It can be understood that the present invention only provides a protective layer above the first functional layer, the second functional layer, the third functional layer, and the fourth functional layer. The present invention is not limited thereto. The number of protective layers is set according to specific circumstances. Therefore, the present invention also protects any situation that meets the requirements, such as one protective layer, two protective layers, three protective layers, four protective layers, five protective layers, six protective layers, seven protective layers, and eight protective layers.

[0081] Further, in any of the above embodiments of the low-emissivity film, the optional materials for the first dielectric layer, the second dielectric layer, the third dielectric layer, and the fourth dielectric layer are at least one of metal oxides such as zinc, tin, magnesium, titanium, niobium, bismuth, zirconium, silicon, aluminum and their alloy oxides, or at least one of metal nitrides, oxynitrides such as silicon, aluminum, titanium, thallium, zirconium, niobium and their alloy nitrides, oxynitrides.

[0082] The optional materials for the first functional layer, the second functional layer, the third functional layer, and the fourth functional layer are at least one of silver, copper, gold, aluminum, silver indium alloy, copper indium alloy, and silver copper alloy.

[0083] The optional materials for the first protective layer, the second protective layer, the third protective layer, and the fourth protective layer are at least one of metals such as nickel, titanium, zinc, aluminum, chromium, zirconium, germanium, tungsten, molybdenum and their alloys or at least one of their incomplete oxides.

[0084] The optional materials for the first transition layer, the second transition layer, the third transition layer, and the fourth transition layer are at least one of metal oxides such as zinc, aluminum, tin, titanium, niobium, thallium, zirconium, magnesium, bismuth and their alloy oxides.

[0085] The optional materials for the outermost protective layer are at least one of metal oxides such as titanium, zinc, tin, aluminum, silicon, zirconium and their alloy oxides or nitrides.

[0086] Next, in order to more specifically illustrate and more convincingly support the inventive points of the present invention, some specific embodiments are listed below for auxiliary proof:

[0087] In terms of mechanical properties, the ability of the film layer of the low-emissivity film to withstand frictional loss and the adhesion between the film layers are mainly examined. Among them, for the manual friction evaluation, a clean cotton cloth dipped in alcohol is used, and the finger is pressed on the film surface and rubbed repeatedly. One round trip of rubbing is recorded as 1 time, and continuous rubbing is carried out 30 times. The following scoring is carried out according to the damage condition of the film surface: Grade 5 means the film peels off with light rubbing, Grade 4 means the film peels off with forceful rubbing, Grade 3 means slight peeling, Grade 2 means no peeling, only slight scratches, and Grade 1 means the film surface looks good and there is no visible damage to the naked eye. The pencil hardness test mainly examines the hardness of the outermost layer of the film layer. A 500-gram weight is pressed on the selected standard hardness pencil and slowly dragged. The pencil hardness is experimentally tested in order from soft to hard until the film layer surface has no scratches for the first time, and the film layer hardness is determined. From soft to hard, they are: 6B, 5B, 4B, 3B, 2B, HB, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H.

[0088] In terms of thermal stability, the appearance of the film layer mainly observes whether the silver layer of the low-emissivity film is contaminated and damaged after heat treatment. According to the situation, it is divided into the following 5 levels: Level 5 has high-density white dots all over the plate under strong light, Level 4 has medium-density white dots all over the plate, Level 3 has low-density white dots all over the plate, Level 2 has individual slight white dots, and Level 1 has no white dots. Then look at the haze value. The smaller the haze value, the less the silver layer is affected during the heat treatment process, and the more stable the entire film layer is.

[0089] Example 1

[0090]

[0091]

[0092] Comparative Example 1

[0093]

[0094] Example 2

[0095]

[0096] Example 3

[0097]

[0098]

[0099]

[0100] From the comparison of the experimental results of Comparative Example 1 and Example 1 above, it can be seen that the contribution of the outermost protective layer to the mechanical properties and thermal stability of the entire film layer of the low-emissivity film is significant. From the comparison of Example 1 with Example 2 and Example 3, it can be seen that the preparation methods of the functional layers used in Example 2 and Example 3 significantly improve the sheet resistance of the film layer.

[0101] Example 4

[0102]

[0103] Comparative Example 2

[0104]

[0105]

[0106] Example 5

[0107]

[0108]

[0109] From the comparison between Comparative Example 2 and Examples 4 and 5 of the above traditional film systems, it can be seen that when the film layer thicknesses are similar, the thermal performance of Examples 4 and 5 is more excellent, the mechanical properties and thermal stability are better, and the production has a higher error tolerance. From the comparison between Example 4 and Example 5, it can be seen that in the double-silver film system, using an alloy of silver and indium as the material source for both functional layers is more stable and has more product advantages during heat treatment.

[0110] Example 6

[0111]

[0112]

[0113] Example 7

[0114]

[0115] Comparative Example 3

[0116]

[0117]

[0118]

[0119] From the comparison between Comparative Example 3 and Examples 6 and 7 above, it can be seen that when the film layer thicknesses are similar, the thermal performance of Examples 6 and 7 is more excellent, the mechanical properties and thermal stability are better, and the production has a higher error tolerance. From the comparison between Example 6 and Example 7, it can be seen that in the triple-silver film system, using an alloy of silver and indium as the material source for all three functional layers is more stable and has more product advantages during heat treatment.

[0120] Example 8

[0121]

[0122]

[0123] Example 9

[0124]

[0125] Comparative Example 4

[0126]

[0127]

[0128] From the comparison between the traditional film system Comparative Example 4 and Examples 8 and 9 above, it can be seen that when the film layer thicknesses are similar, the thermal performance of Examples 8 and 9 is more excellent, the mechanical properties and thermal stability are better, and there is a higher error tolerance in production. From the comparison between Example 8 and Example 9, it can be seen that in the four-silver film system, when all four functional layers use an alloy of silver and indium as the material source, it is more stable and has product advantages during heat treatment.

[0129] Therefore, from all the above examples, it can be known that if the thermal performance of the product is preferred, Examples 7 and 9 are more advantageous; if a lower cost is preferred and certain excellent properties are also possessed, Examples 6 and 8 are better.

[0130] 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 layer, make the entire film layer have higher hardness, improve the processability of the product, reduce the requirements for downstream processing equipment, save production costs, and the design of each transition layer can further improve the thermal stability of the film layer. Compared with the traditional film system, after being treated at 600-700 degrees Celsius, there is a lower haze change, and the silver layer of the prepared low-emissivity film has a lower sheet resistance at the same thickness compared with the film system prepared by the traditional method.

[0131] Moreover, the first functional layer and the fourth functional layer select an alloy of silver and indium as the material source. This alloy material, combined with a mixed atmosphere of argon and krypton, can effectively enhance the corrosion resistance of the silver layer through the deposition preparation method of DC magnetron sputtering, and can also improve to a certain extent the film formation method of elemental silver material source in island-like accumulation, making the surface of the functional layer flatter, and having a lower sheet resistance compared with the silver layer of the existing film system with the same thickness.

[0132] On the other hand, the present application also proposes a coated interlayer glass, which includes a first glass layer, an intermediate layer, and a second glass layer. The intermediate layer is arranged between the first glass layer and the second glass layer, and the above-mentioned low-emissivity film is coated on the surface of the first glass layer close to the intermediate layer and / or the surface of the second glass layer close to the intermediate layer.

[0133] Among them, the intermediate layer in the coated interlayer glass can be a glass film that bonds the first glass layer and the second glass layer. The coated interlayer glass of the present application is a product in which the low-emissivity film in any of the above embodiments is coated on the inner surfaces (the side close to the intermediate layer) of the two glasses of the existing interlayer glass that has been cleaned with deionized water by the magnetron sputtering method.

[0134] The coated interlayer glass proposed by the present application can be assembled on an automobile. When the coated interlayer glass is assembled on the automobile, the first glass layer faces the inside of the vehicle, the second glass layer faces the outside of the vehicle, and the low-emissivity film can be coated on the inner surface of the first glass layer or the inner surface of the second glass layer.

[0135] On the other hand, the present application also provides a coated insulating glass, which includes a first glass layer, a connecting frame, and a second glass layer. The connecting frame is a frame body with two opposite surfaces penetrating therethrough. The first glass layer and the second glass layer are connected through the connecting frame, so that the connected first glass layer, second glass layer, and connecting frame form an internal hollow structure, and the above-mentioned low-emissivity thin 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 far from the first glass layer.

[0136] Among them, the first glass layer, the connecting frame (which can be an aluminum frame), and the second glass layer in the coated insulating glass can adopt the structure of the existing insulating glass. The coated insulating glass of the present application is a product in which the low-emissivity thin film in any of the above embodiments is coated on the indoor surfaces (the side close to the indoor side after the insulating glass is installed) of the two glass layers of the existing insulating glass that have been cleaned with deionized water by magnetron sputtering method.

[0137] The coated insulating glass proposed by the present application can be assembled on the windows of a house, with the glass layer coated with the low-emissivity thin film facing the outdoor side of the house.

[0138] In addition, it should be noted that the low-emissivity thin film of the present application can not only be coated on glass products, but also be used on other substrates, such as oily films, plastic parts, etc.

[0139] As described above, the above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention should be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. A low-emissivity film, characterized in that: It includes a first combined layer, a second combined layer, a third combined layer, a fourth combined layer, and an outermost protective layer which are stacked in sequence; The first combined layer includes a first dielectric layer, a first functional layer, and a first transition layer which are stacked in sequence; The second combined layer includes a second dielectric layer, a second functional layer, and a second transition layer which are stacked in sequence; The third composite layer comprises a third dielectric layer, a third functional layer, and a third transition layer which are stacked in sequence; The fourth composite layer comprises a fourth dielectric layer, a fourth functional layer, and a fourth transition layer which are stacked in sequence; The first dielectric layer is used to block the diffusion of destructive atoms into the first functional layer during the heat treatment process, and the second dielectric layer, the third dielectric layer, and the fourth dielectric layer are used to increase the optical path of visible light; The first functional layer, the second functional layer, the third functional layer and the fourth functional layer are used to reflect infrared rays, the first functional layer and the fourth functional layer are made of silver-indium alloy, and the second functional layer and the third functional layer are made of silver; The first transition layer, the second transition layer, the third transition layer, and the fourth transition layer are used to improve the thermal stability of the low-emissivity film and the mutual bonding force between the first combination layer, the second combination layer, the third combination layer, the fourth combination 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 of zinc-aluminum alloy and 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 double-rotating medium-frequency AC magnetron sputtering cathode; The outermost protective layer includes a first sublayer, a second sublayer, and a third sublayer. The first sublayer is made of an oxide material of zinc-tin alloy, the second sublayer is made of silicon nitride material, and the third sublayer is made of a mixture material of zirconium oxide and titanium oxide. The third sublayer is prepared based on a single-rotation magnetron sputtering cathode with a Hipims power supply. The outermost protective layer is used to provide chemical stability and mechanical durability during transportation and storage, and to improve the thermal stability of the low-emissivity film.

2. The low-emissivity film according to claim 1, characterized in that: 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 implantation layers of the first functional layer, the second functional layer, the third functional layer, and the fourth functional layer respectively; The first seed layer, the second seed layer, the third seed layer, and the fourth seed layer are made of zinc oxide film layers or zinc oxide film layers doped with target elements, wherein the target element is one of aluminum, gallium, indium, tin, molybdenum, yttrium, boron, silicon, germanium, titanium, hafnium, zirconium, fluorine, and scandium.

3. The low-emissivity film according to claim 2, characterized in that: A first protective layer is provided between the first functional layer and the first transition layer; A second protective layer is provided between the second functional layer and the second transition layer; A third protective layer is provided between the third functional layer and the third transition layer; A fourth protective layer is provided 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 used to protect the first functional layer, the second functional layer, the third functional layer, and the fourth functional layer from being damaged during processing, respectively.

4. The low-emissivity film according to claim 3, characterized in that: 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 nanometers; The materials of the first protective layer, the second protective layer, the third protective layer, and the fourth protective layer are 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 their alloys.

5. The low-emissivity film according to claim 4, characterized in that: The optical thickness of the first functional layer, the second functional layer, the third functional layer and the fourth functional layer is 8-20 nanometers; The mass fraction ratio of silver compound and indium compound in the silver-indium alloy material used in the first functional layer and the fourth functional layer is 98:

2.

6. The low-emissivity film according to claim 5, characterized in that: The first functional layer, the second functional layer, the third functional layer, and the fourth functional layer have a background vacuum degree lower than 6×10 -6 The nanostructured carbon nanotubes were prepared by deposition using a DC magnetron sputtering technique in a mixed atmosphere of argon and krypton with a flow rate ratio of 10:1 to 5:1 at mbar.

7. The low-emissivity film according to claim 6, characterized in that: The first dielectric layer, the second dielectric layer, the third dielectric layer, and the fourth dielectric layer are made of materials with an extinction coefficient of 0-0.05 in the visible light region.

8. The low-emissivity film according to claim 7, characterized in that: The optical thickness of the first sublayer is 5-20 nanometers, the optical thickness of the second sublayer is 10-30 nanometers, and the optical thickness of the third sublayer is 3-11 nanometers; The mass fraction ratio of zirconium oxide to titanium oxide in the mixture material used for the third sub-layer is 9:

1.

9. A coated laminated glass, characterized in that: It includes 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 surface of the first glass layer close to the intermediate layer and / or the surface of the second glass layer close to the intermediate layer is coated with the low-emissivity film according to any one of claims 1 to 8.

10. A coated insulating glass, characterized in that: It includes a first glass layer, a connection frame, and a second glass layer; The connection frame is a frame body with two opposite surfaces penetrating therethrough, and the first glass layer and the second glass layer are connected through the connection frame, so that the first glass layer, the second glass layer and the connection frame after being connected form an internal hollow structure; The low-emissivity film according to any one of claims 1 to 8 is coated on a surface of the first glass layer close to the second glass layer and / or on a surface of the second glass layer away from the first glass layer.

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