CN114409273A

CN114409273A - Three-silver low-emissivity glass and preparation method thereof

Info

Publication number: CN114409273A
Application number: CN202210016601.6A
Authority: CN
Inventors: 曹晖; 张洁林; 杨斌; 黄凤珠; 福原康太
Original assignee: Fuyao Glass Industry Group Co Ltd
Current assignee: Fuyao Glass Industry Group Co Ltd
Priority date: 2022-01-04
Filing date: 2022-01-04
Publication date: 2022-04-29
Anticipated expiration: 2042-01-04
Also published as: CN114409273B

Abstract

The invention relates to three-silver low-emissivity glass and a preparation method thereof. The three-silver low-emissivity glass comprises a glass substrate, a first functional layer, a first barrier layer, a second functional layer, a second barrier layer, a third functional layer, a protective layer and a sacrificial layer which are sequentially stacked; the protective layer comprises SiAlZrN_xLayer of said SiAlZrN_xIn layer N⁺Is 10 to 35 percent; the sacrificial layer comprises a first sacrificial sublayer, and the first sacrificial sublayer is a graphite-like amorphous carbon film. The three-silver low-emissivity glass adopts a HiPIMS power supply to deposit a graphite-like amorphous carbon film (GLC) and contains SiAlZrN_xA protective layer of a layer for providing protection to the tri-silver low emissivity glass. And the graphite-like amorphous carbon film can react to generate CO in a high-temperature environment₂And removing the silver layer without affecting the optical performance of the three-silver low-radiation film layer.

Description

Three-silver low-emissivity glass and preparation method thereof

Technical Field

The application relates to the field of coated glass for buildings and vehicles, in particular to three-silver low-emissivity glass and a preparation method thereof, and also provides laminated glass comprising the three-silver low-emissivity glass.

Background

The three-silver low-emissivity glass is a film system product formed by depositing a plurality of layers of metal or other compounds including three silver layers on the surface of the glass. The metal layers such as silver layer have high reflectivity to infrared rays, so that the metal layers have good heat insulation performance. Meanwhile, based on the good conductivity of the silver layer, the three-silver low-emissivity glass can be matched with a bus bar and a power supply to perform electric heating so as to realize defrosting and demisting performances. However, the film system of the three-silver low-emissivity glass has a complex and thick structure, which easily results in low mechanical strength, poor abrasion resistance and poor oxidation resistance of the film layer, so that the three-silver low-emissivity glass is easily scratched and oxidized in the processes of transportation, storage, transportation and processing after being prepared, and needs to be immediately subjected to subsequent processing such as heat treatment in a short time, thus the requirement of remote processing cannot be met, and unnecessary loss and cost increase of products are caused.

Disclosure of Invention

The application provides three-silver low-emissivity glass and a preparation method thereof, wherein the three-silver low-emissivity glass adopts a HiPIMS power supply to deposit a graphite-like amorphous carbon film (GLC) and contains SiAlZrN_xA protective layer of a layer for providing protection to the tri-silver low emissivity glass. The graphite-like amorphous carbon film comprises SiAlZrN_xThe protective layer of the layer can prevent the three-silver low-emissivity glass from being scratched, scratched and oxidized in the transportation and processing processes, can meet the requirements of different places for processing, and the graphite-like amorphous carbon film can react to generate CO in a high-temperature environment₂And removing the silver layer without affecting the optical performance of the three-silver low-radiation film layer.

The three-silver low-emissivity glass is characterized by comprising a glass substrate, and a first functional layer, a first barrier layer, a second functional layer, a second barrier layer, a third functional layer, a protective layer and a sacrificial layer which are sequentially stacked on at least one surface of the glass substrate; the first functional layer, the second functional layer and the third functional layer can reflect infrared rays; the protective layer comprises SiAlZrN_xLayer of said SiAlZrN_xIn layer N⁺Is 10 to 35 percent; the sacrificial layer comprises a first sacrificial sublayer, and the first sacrificial sublayer isA graphite-like amorphous carbon film.

The protective layer is obtained by deposition of a HiPIMS power supply, the HiPIMS power supply deposition process is a process for supplying megawatt instantaneous high power to a target material in a short pulse, the plasma density of a film layer can be greatly improved, and the HiPIMS power supply can enable SiAlZrN of the protective layer_xIn layer N⁺The mass fraction of the protective layer reaches 10-35%, the ionization rate of the protective layer is increased, the adhesive force of the protective layer is stronger, and the film structure of the three-silver low-emissivity glass is stable; and the high energy and the high ionization rate of the HiPIMS power deposition process can ensure that the compactness of the protective layer is high, so that the friction coefficient of the protective layer is reduced, the hardness is improved, and the corrosion resistance is enhanced. The method also adopts a graphite-like amorphous carbon film as a first sacrificial sublayer, wherein the graphite-like amorphous carbon film is obtained by deposition of a HiPIMS power supply; the graphite-like amorphous carbon film has the properties of high hardness and low friction coefficient, and can avoid scratching and scuffing of glass chips and small particles in the processes of transportation, cutting, edging and heat treatment; the high-compactness graphite-like amorphous carbon film is obtained by the HiPIMS power deposition process, water molecules can be effectively prevented from invading the interior of the film system structure of the three-silver low-radiation glass in a water environment, the oxidation resistance of the three-silver low-radiation glass is improved, and the adaptability to a humid environment and a marine environment is enhanced; the wear rate of the graphite-like amorphous carbon film in water environment is lower than that in atmospheric environment; under the oil environment, the graphite-like amorphous carbon film can form a continuous and effective oil lubricating film, so that the wear rate of the graphite-like amorphous carbon film under the oil environment is lower than that under the atmosphere and the water environment, and the graphite-like amorphous carbon film has low wear rate under the water environment and the oil environment, so that the film layer of the three-silver low-radiation film is less damaged in the cutting, edge grinding and heat treatment processes, the integrity of the film layer structure is higher, the quality problems of scratching, wiping, oxidation and the like in the processing process are improved, and the requirements of different-place processing are met; the graphite-like amorphous carbon film can react to generate CO in a high-temperature environment₂Removing, when in practical use, the three-silver low radiation is not influencedOptical properties of the irradiated layer.

Wherein the Vickers hardness of the graphite-like amorphous carbon film is 10.2 to 15.2Gpa, and the friction coefficient is 0.05 to 0.07.

Wherein the first sacrificial sublayer has a thickness of 20nm to 70 nm.

The sacrificial layer further comprises a second sacrificial sublayer, the second sacrificial sublayer is arranged on the surface, far away from the third functional layer, of the first sacrificial sublayer, and the second sacrificial sublayer comprises at least one of a water-soluble polyvinyl alcohol film, a hot-melt protective film and a polyethylene film.

The first functional layer, the second functional layer and the third functional layer respectively comprise a first dielectric layer, a metal layer and a second dielectric layer which are sequentially stacked, and the metal layer comprises at least one of Ag, Au, Cu, Al and alloys thereof.

Wherein the first dielectric layer comprises AZO, Ti alloy and NbO_x、TiO_x、NiCr、NiCrO_x、ZnAlO_x、ZnO_x、SnO_xAt least one of; the second dielectric layer comprises AZO, Ti alloy and NbO_x、TiO_x、NiCr、NiCrO_x、ZnAlO_x、ZnO_x、SnO_xAt least one of (1).

Wherein the first barrier layer comprises ZnSnO_x、SiAlZrN_x、SiAlN_x、SiN_x、SiZrN_x、ZnO_x、AZO、ZnAlO_xAt least one of ITO; the second barrier layer comprises ZnSnO_x、SiAlZrN_x、SiAlN_x、SiN_x、SiZrN_x、ZnO_x、AZO、ZnAlO_xAnd ITO.

Wherein the first barrier layer comprises SiAlZrN_xSiAlZrN of the first barrier layer_xIn N⁺Is less than SiAlZrN of the protective layer_xIn layer N⁺Mass fraction of (a); the second barrier layer comprises SiAlZrN_xSiAlZrN of said second barrier layer_xIn N⁺Is less than Si of the protective layerAlZrN_xIn layer N⁺Mass fraction of (c).

Wherein the protective layer further comprises ZnSnO_xLayer of said ZnSnO_xThe layer is deposited by a medium frequency power supply, the ZnSnO_xA layer disposed on the SiAlZrN_xA layer and said third functional layer.

Wherein an adhesion layer is arranged between the glass substrate and the first functional layer, and the adhesion layer comprises SiAlZrN_x、ZrO_x、NbO_x、SiN_x、ZnSnO_x、SiZrN_xAt least one of (1).

Wherein the adhesion layer comprises SiAlZrN_xSiAlZrN of said adhesion layer_xIn N⁺Is less than SiAlZrN of the protective layer_xIn layer N⁺Mass fraction of (c).

The application also provides a preparation method of the three-silver low-emissivity glass, which is characterized by comprising the following steps:

providing a glass substrate; and

depositing an adhesion layer, a first functional layer, a first barrier layer, a second functional layer, a second barrier layer, a third functional layer, a protective layer and a first sacrificial sublayer on the surface of the glass substrate in sequence in a magnetron sputtering mode; wherein the first sacrificial sublayer is a graphite-like amorphous carbon film having a Vickers hardness of 10.2 to 15.2Gpa and a coefficient of friction of 0.05 to 0.07.

The preparation method of the three-silver low-emissivity glass is simple to operate, low in requirements on process equipment, low in cost and suitable for industrial mass production.

Wherein the method further comprises:

and arranging a water-soluble polyvinyl alcohol film, a hot-melt protective film or a polyethylene film on the surface of the first sacrificial sublayer, which is away from the glass substrate, so as to obtain the three-silver low-emissivity glass.

Wherein depositing the first sacrificial sublayer comprises:

the target material is configured into graphite, a HiPIMS power supply is used as the target material power supply, 1 to 3 double rotating cathodes are adopted, and the air pressure is 1.0 multiplied by 10^-3mbar to 6.0 x 10^-3And carrying out magnetron sputtering in an argon atmosphere of mbar, and depositing the first sacrificial sublayer.

Wherein the protective layer comprises SiAlZrN_xLayer of said SiAlZrN deposited_xThe layers include:

the target material is SiAlZr, a HiPIMS power supply is used as the target material power supply, 1 to 3 double rotating cathodes are adopted, and the air pressure is 1.0 multiplied by 10^-3mbar to 6.0 x 10^-3mbar argon and nitrogen mixed gas is subjected to magnetron sputtering to deposit the SiAlZrN_xAnd (3) a layer.

Wherein the protective layer further comprises ZnSnO_xLayer of said ZnSnO_xA layer disposed on the SiAlZrN_xBetween the layer and the third functional layer, depositing the ZnSnO_xThe layers include:

the target material is ZnSn, the intermediate frequency power supply is used as the target material power supply, 1 to 6 double rotating cathodes are adopted, and the air pressure is 1.0 multiplied by 10^-3mbar to 6.0 x 10^-3Carrying out magnetron sputtering in a mixed gas of mbar argon and nitrogen to deposit the ZnSnO_xAnd (3) a layer.

The present application also provides a laminated glass, which is characterized by comprising:

a glass plate;

an adhesive layer; and

the three-silver low-emissivity glass;

the bonding layer is arranged between the glass plate and the three-silver low-emissivity glass, and the protective layer is arranged close to the bonding layer compared with the glass substrate.

The laminated glass is formed by laminating and bonding a glass plate, a bonding layer and the three-silver low-emissivity glass, wherein a sacrificial layer on the three-silver low-emissivity glass is removed; the sacrificial layer prevents the three-silver low-emissivity glass from being scratched by glass chips and small particles in the processes of cutting, edging and heat treatment, and also prevents the three-silver low-emissivity glass from being oxidized in a humid environment, so that the loss rate of the three-silver low-emissivity glass in the processes of transportation and processing is reduced, and the preparation cost of the laminated glass is further reduced; the sacrificial layer can be completely removed by methods such as water washing, heating and the like, and the optical performance of the film layer of the three-silver low-radiation glass is not influenced; when the three-silver low-emissivity glass is prepared into laminated glass, the yield is high, and the optical effect is good.

The present application further provides a vehicle, comprising:

a vehicle body; and

the door window, the door window set up in the vehicle body, the door window includes this application laminated glass.

The Vehicle includes the laminated glass described herein, which may be, but is not limited to, a sedan, a multi-Purpose Vehicle (MPV), a Sport Utility Vehicle (SUV), an Off-Road Vehicle (ORV), a pickup truck, a minibus, a van, and the like.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

FIG. 1 is a schematic structural diagram of a three-silver low-emissivity glass provided by an embodiment of the invention;

fig. 2 is a schematic structural diagram of a first functional layer according to an embodiment of the present invention;

FIG. 3 is a schematic flow chart of a method for preparing a three-silver low-emissivity glass provided by an embodiment of the invention;

fig. 4 is a schematic structural diagram of a laminated glass according to an embodiment of the present invention;

fig. 5 is a schematic structural diagram of a vehicle according to an embodiment of the present invention.

Description of reference numerals:

100-three silver low emissivity glass; 110-a glass substrate; 111-an adhesion layer; 120-a first functional layer; 121-a first dielectric layer; 122-a metal layer; 123-a second dielectric layer; 130-a first barrier layer; 140-a second functional layer; 150-a second barrier layer; 160-a third functional layer; 170-a protective layer; 180-a sacrificial layer; 181-a first sacrificial sublayer; 182-a second sacrificial sublayer; 200-laminated glass; 210-a glass plate; 220-an adhesive layer; 300-a vehicle; 310-a vehicle body; 320-vehicle window.

Detailed Description

The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without inventive step, are within the scope of the present disclosure.

The terms "first," "second," and the like in the description and claims of the present application and in the above-described drawings are used for distinguishing between different objects and not for describing a particular order. Furthermore, the terms "include" and "have," as well as any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those steps or elements listed, but may alternatively include other steps or elements not listed, or inherent to such process, method, article, or apparatus.

Reference herein to "an embodiment" or "an implementation" means that a particular feature, structure, or characteristic described in connection with the embodiment or implementation can be included in at least one embodiment of the application. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. It is explicitly and implicitly understood by one skilled in the art that the embodiments described herein can be combined with other embodiments.

In the embodiments of the present application, when referring to the numerical ranges a to b, if not specifically indicated, the end value a is included, and the end value b is included.

As shown in fig. 1 and 2The third-silver low-emissivity glass 100 comprises a glass substrate 110, and a first functional layer 120, a first barrier layer 130, a second functional layer 140, a second barrier layer 150, a third functional layer 160, a protective layer 170 and a sacrificial layer 180 which are sequentially stacked on at least one surface of the glass substrate 110; the first functional layer 120, the second functional layer 140, and the third functional layer 160 can reflect infrared rays; the protective layer 170 comprises SiAlZrN_xLayer of said SiAlZrN_xIn layer N⁺Is 10 to 35 percent; the sacrificial layer 180 includes a first sacrificial sublayer 181, and the first sacrificial sublayer 181 is a graphite-like amorphous carbon film.

SiAlZrN of the protective layer 170_xIn layer N⁺Is 10 to 35 percent, in particular the SiAlZrN_xIn layer N⁺May be, but is not limited to, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 35%.

The vickers hardness of the graphite-like amorphous carbon film is 10.2Gpa to 15.2Gpa, and specifically, the vickers hardness of the graphite-like amorphous carbon film may be, but is not limited to, 10.2Gpa, 10.7Gpa, 11.2Gpa, 11.7Gpa, 12.2Gpa, 12.7Gpa, 13.2Gpa, 13.7Gpa, 14.2Gpa, 14.7Gpa, 15.2 Gpa.

The coefficient of friction of the graphite-like amorphous carbon film is 0.05 to 0.07, and particularly, the coefficient of friction of the graphite-like amorphous carbon film may be, but is not limited to, 0.05, 0.052, 0.054, 0.056, 0.058, 0.06, 0.062, 0.064, 0.066, 0.068, 0.07.

The protective layer 170 described herein is deposited using a HiPIMS power supply, which is a process that supplies megawatts of instantaneous high power to the target in short pulses, greatly increasing the plasma density of the film, in which the HiPIMS power supply can cause the SiAlZrN of the protective layer 170 to be deposited_xIn layer N⁺Reaches 10 to 35% by mass, and the ionization rate of the protective layer 170 is increasedThe protective layer 170 has high adhesive force, so that the film structure of the tri-silver low-emissivity glass 100 is stable, and the high energy and high ionization rate of the HiPIMS power deposition process can ensure that the compactness of the protective layer 170 is high, so that the friction coefficient of the protective layer 170 is reduced, the hardness is improved, and the corrosion resistance is enhanced. The graphite-like amorphous carbon film is used as the first sacrificial sublayer 181 and is obtained by HiPIMS power deposition; the graphite-like amorphous carbon film has the properties of high hardness and low friction coefficient, and can avoid scratching and scratching of glass chips and small particles in the processes of transportation, cutting, edge grinding and heat treatment (such as toughening and bending); the high-compactness graphite-like amorphous carbon film is obtained by the HiPIMS power deposition process, water molecules can be effectively prevented from invading the interior of the film system structure of the three-silver low-emissivity glass 100 in a water environment, the oxidation resistance of the three-silver low-emissivity glass 100 is improved, and the adaptability to a humid environment and a marine environment is enhanced; the wear rate of the graphite-like amorphous carbon film in water environment is lower than that in atmospheric environment; in an oil environment, the graphite-like amorphous carbon film can form a continuous and effective oil lubricating film, so that the wear rate of the graphite-like amorphous carbon film in the oil environment is lower than that in the atmosphere and the water environment, and the graphite-like amorphous carbon film has low wear rate in the water environment and the oil environment, so that the three-silver low-radiation glass 100 has the advantages that the damage to a film layer is less, the integrity of the structure of the film layer is higher, the quality problems of scratching, wiping, oxidation and the like in the processing process are improved in the cutting, edging and heat treatment processes, and the processing requirements in different places can be met; the graphite-like amorphous carbon film can react to generate CO in a high-temperature environment₂The removal does not affect the optical properties of the three-silver low emissivity glass 100 when in actual use.

In some embodiments, the thickness of the first sacrificial sublayer 181 is 20nm to 70 nm. In particular, the thickness of the first sacrificial sublayer 181 may be, but is not limited to, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70 nm. When the thickness of the first sacrificial sub-layer 181 is 20nm to 70nm, the properties of high hardness, low friction coefficient and high compactness can provide good protection for the three-silver low-emissivity glass 100, and when the thickness of the first sacrificial sub-layer 181 is less than 20nm, the first sacrificial sub-layer 181 is too thin to effectively protect the glass chips and small particles of the three-silver low-emissivity glass 100 from scratching and scratching during transportation, cutting, edging and heat treatment; when the thickness of the first sacrificial sublayer 181 is higher than 70nm, although the protective effect provided to the three-silver low emissivity glass 100 is enhanced, the equipment cost and the manufacturing cost are greatly increased.

In some embodiments, the sacrificial layer 180 further includes a second sacrificial sublayer 182, the second sacrificial sublayer 182 is disposed on a surface of the first sacrificial sublayer 181 away from the third functional layer 160, and the second sacrificial sublayer 182 includes at least one of a water-soluble polyvinyl alcohol film, a hot-melt protective film, and a polyethylene film. The second sacrificial sublayer 182 can reduce scratches and scratches on the film layer caused by large particles and large glass chips in the transportation and cutting processes, and can further enhance the oxidation resistance of the film layer of the three-silver low-emissivity glass 100. Alternatively, the second sacrificial sublayer 182 is a water-soluble polyvinyl alcohol film, which is soluble in water, cheap, suitable for use in large quantities in actual production, and capable of being washed with water without residue.

In some embodiments, an adhesion layer 111 is provided between the glass substrate 110 and the first functional layer 120, the adhesion layer 111 comprising SiAlZrN_x、ZrO_x、NbO_x、SiN_x、ZnSnO_x、SiZrN_xAt least one of (1). The adhesion layer 111 serves to increase the adhesion between the film layer of the three-silver low emissivity glass 100 and the glass substrate 110. Optionally, the adhesion layer 111 is SiAlZrN_xSiAlZrN of the adhesion layer_xIn N⁺Is less than SiAlZrN of the protective layer_xIn layer N⁺Can further reduce the cost on the basis of improving the product quality, such as SiAlZrN of the adhesion layer_xIn N⁺The mass fraction of (b) may be exemplified by 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, etc，SiAlZrN_xThe material can improve the hardness of the film layer of the three-silver low-emissivity glass 100, and prevent Na ions in the glass substrate 110 from diffusing into the film system to damage the Ag layer during high-temperature toughening or bending, so that the whole film system of the three-silver low-emissivity glass 100 has better heat resistance and better machining performance under a high-temperature condition, and the phenomenon that the film layer of the three-silver low-emissivity glass 100 is softer is improved from the bottom layer.

In some embodiments, the first functional layer 120, the second functional layer 140, and the third functional layer 160 each include a first dielectric layer 121, a metal layer 122, and a second dielectric layer 123, which are sequentially stacked, the metal layer 122 includes at least one of Ag, Au, Cu, Al, and an alloy thereof, and the metal layer 122 is capable of reflecting infrared rays. Optionally, the metal layer 122 is made of Ag, and the Ag is used as the metal layer 122, so that the infrared reflectivity of the three-silver low-emissivity glass 100 can be improved, the heat insulation effect is good, and the three-silver low-emissivity glass can be electrically heated by matching with a power supply and a bus bar to achieve defrosting and defogging performances. Optionally, the first functional layer 120, the second functional layer 140, and the third functional layer 160 described herein have the same structure, and are stacked by the first dielectric layer 121, the metal layer 122, and the second dielectric layer 123, so that the metal layer 122 is protected by the first dielectric layer 121 and the second dielectric layer 123, and the inter-film adhesion of the three-silver low-emissivity glass 100 is enhanced.

In some embodiments, the first dielectric layer 121 comprises AZO, Ti alloy, NbO_x、TiO_x、NiCr、NiCrO_x、ZnAlO_x、ZnO_x、SnO_xAt least one of; the second dielectric layer 123 comprises AZO, Ti alloy and NbO_x、TiO_x、NiCr、NiCrO_x、ZnAlO_x、ZnO_x、SnO_xAt least one of (1). The first dielectric layer 121 and the second dielectric layer 123 are oxygen-deficient film layers, have a good oxygen isolation effect, can well protect the functional layer Ag, and increase the adhesive force between the film layers; wherein, the AZO adopts ZnAlO_xSputtering deposited of ceramic target material, ZnAlO_xIs sputtered and deposited by ZnAl alloy target material and ZnAlO_xCompared with the AZO layer, the film layer of the AZO layer is compact. Optionally, a first mediumThe layer 121 is an AZO layer, which can well pave the deposition of an Ag layer, and the adhesive force between film layers is increased; optionally, the second dielectric layer 123 is also an AZO layer, which has high hardness and machinability and is beneficial to improving the mechanical strength of the three-silver low-emissivity glass 100.

In some embodiments, the first barrier layer 130 includes ZnSnO_x、SiAlZrN_x、SiAlN_x、SiN_x、SiZrN_x、ZnO_x、AZO、ZnAlO_xAt least one of ITO; wherein N in SiAlZrNx of the first barrier layer 130⁺Is less than N in the SiAlZrNx layer of the protective layer⁺The mass fraction of (b) can further reduce the cost on the basis of improving the product quality, such as N in SiAlZrNx of the first barrier layer 130⁺The mass fraction of (b) may be exemplified by 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, etc.; the second barrier layer 150 includes ZnSnO_x、SiAlZrN_x、SiAlN_x、SiN_x、SiZrN_x、ZnO_x、AZO、ZnAlO_xAt least one of ITO; wherein N in SiAlZrNx of the second barrier layer 130⁺Is less than N in the SiAlZrNx layer of the protective layer⁺The mass fraction of (b) can further reduce the cost on the basis of improving the product quality, such as N in SiAlZrNx of the first barrier layer 130⁺The mass fraction of (b) may be exemplified by 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, etc.; the first barrier layer 130 and the second barrier layer 150 are oxygen-deficient film layers, have a good oxygen isolation effect, have a strong bonding force with other film layers, improve the overall adhesion of the film layers, and can further protect the first functional layer 120 and the second functional layer 140, and the first barrier layer 130 and the second barrier layer 150 have good corrosion resistance, mechanical resistance and high temperature resistance, and improve the overall machinability of the film layers.

Optionally, the first barrier layer 130 is ZnSnO_x，ZnSnO_xHas good ductility, prevents the film layers from cracking due to different thermal ductility coefficients in the baking and bending process, and simultaneously ZnSnO_xThe conductive film is made of a semiconductor material, and can reduce the sheet resistance of an automobile electric heating film layer and the radiance of infrared rays; ZnSnO when AZO is used as at least one of the first dielectric layer 121 and the second dielectric layer 123_xAnd ZnAlO_xThe film has strong binding force, and is beneficial to improving the integral adhesive force of the film.

Optionally, the first barrier layer 130 is SiAlZrN_x，SiAlZrN_xThe material has superior physical properties and chemical corrosion resistance. The plated film has strong corrosion resistance, mechanical scratch resistance and high temperature resistance, and the integral machinability of the film is improved.

In some embodiments, the protective layer 170 further comprises ZnSnO_xLayer of said ZnSnO_xThe layer is deposited by a medium frequency power supply, the ZnSnO_xA layer disposed on the SiAlZrN_xLayer and said third functional layer 160. The ZnSnO_xIn the layer of ZnSnO_xHas good ductility, and prevents the film layers from cracking due to different thermal ductility coefficients in the baking bending process.

Referring to fig. 3, the present application further provides a method for manufacturing a three-silver low-emissivity glass 100, which includes:

s101, providing a glass substrate 110; and

optionally, the glass substrate 110 is cleaned and dried, and then placed in a magnetron sputtering coater. Through the cleaning and drying of the glass substrate 110, the influence of impurities on the surface of the glass substrate 110 on the subsequent magnetron sputtering deposition is avoided.

S102, sequentially depositing an adhesion layer 111, a first functional layer 120, a first barrier layer 130, a second functional layer 140, a second barrier layer 150, a third functional layer 160, a protective layer 170 and a first sacrificial sublayer 180 on the surface of the glass substrate 110 in a magnetron sputtering mode; wherein the first sacrificial sublayer 181 is a graphite-like amorphous carbon film having a vickers hardness of 10.2 to 15.2Gpa and a friction coefficient of 0.05 to 0.07.

Specifically, the vickers hardness of the graphite-like amorphous carbon film may be, but is not limited to, 10.2Gpa, 10.7Gpa, 11.2Gpa, 11.7Gpa, 12.2Gpa, 12.7Gpa, 13.2Gpa, 13.7Gpa, 14.2Gpa, 14.7Gpa, 15.2 Gpa; the coefficient of friction of the graphite-like amorphous carbon film may be, but is not limited to, 0.05, 0.052, 0.054, 0.056, 0.058, 0.06, 0.062, 0.064, 0.066, 0.068, 0.07.

In some embodiments, depositing the adhesion layer 111 comprises:

the target material is configured as SiAlZr, and MF (intermediate frequency power supply) is used as a target material power supply; using 1-3 double rotating cathodes as target material, and making the air pressure be 1.0X 10^-3mbar to 6.0 x 10^-3Carrying out magnetron sputtering in a mixed gas of mbar argon and nitrogen, wherein the thickness of the film layer is 15nm to 30 nm.

In some embodiments, depositing the first functional layer 120 includes sequentially depositing a first dielectric layer 121, a metal layer 122, and a second dielectric layer 123. Alternatively,

depositing first dielectric layer 121 includes: the target material is configured to AZO, and MF (intermediate frequency power supply) is used as a target material power supply; using 1-3 double rotating cathodes as target material, and making the air pressure be 1.0X 10^-3mbar to 6.0 x 10^-3And carrying out magnetron sputtering in an argon atmosphere of mbar, wherein the thickness of the film layer is 10nm to 15 nm.

Depositing the metal layer 122 includes: the target material is configured to be Ag; DC (direct current power supply) is used as a target power supply; 1 single-plane cathode is used as a target material, and the air pressure is 2.0 multiplied by 10^-3mbar to 3.0 x 10^-3And carrying out magnetron sputtering in an argon atmosphere of mbar, wherein the thickness of the film layer is 5nm to 15 nm.

Depositing the second dielectric layer 123 includes: the target material is configured to AZO, and MF (intermediate frequency power supply) is used as a target material power supply; using 1-3 double rotating cathodes as target material, and making the air pressure be 1.0X 10^-3mbar to 6.0 x 10^-3And carrying out magnetron sputtering in an argon atmosphere of mbar, wherein the thickness of the film layer is 10nm to 15 nm.

In some embodiments, depositing the first barrier layer 130 includes:

the target material is configured as ZnSn, and MF (intermediate frequency power supply) is used as a target material power supply; 4 to 6 double rotating cathodes are adopted as target materials, and the air pressure is 1.0 multiplied by 10^-3mbar to 6.0 x 10^-3mbar of argon and oxygenAnd in gas, carrying out magnetron sputtering, wherein the volume ratio of argon to oxygen is 1: 2. the thickness of the film layer is 45nm to 60 nm.

In some embodiments, depositing the first barrier layer 130 includes:

the target material is configured as SiAlZr, and MF (intermediate frequency power supply) is used as a target material power supply; 4 to 6 double rotating cathodes are adopted as target materials, and the air pressure is 1.0 multiplied by 10^-3mbar to 6.0 x 10^-3Carrying out magnetron sputtering in a mixed gas of mbar argon and nitrogen, wherein the thickness of the film layer is 40nm to 55 nm.

The second functional layer 140, the second barrier layer 150 and the third functional layer 160 are deposited in sequence as described above. Alternatively, the method of depositing the second functional layer 140 is the same as the method of depositing the first functional layer 120. Optionally, the method of depositing the second barrier layer 150 is the same as the method of depositing the first barrier layer 130. Optionally, the method of depositing the third functional layer 160 is the same as the method of depositing the first functional layer 120.

In some embodiments, the protective layer 170 comprises SiAlZrN_xLayer of said SiAlZrN deposited_xThe layers include:

the target material is SiAlZr, a HiPIMS power supply is used as the target material power supply, 1 to 3 double rotating cathodes are adopted, and the air pressure is 1.0 multiplied by 10^-3mbar to 6.0 x 10^-3mbar argon and nitrogen mixed gas is subjected to magnetron sputtering to deposit the SiAlZrN_xThe thickness of the film layer is 15nm to 30 nm.

In some embodiments, the protective layer 170 further comprises ZnSnO_xLayer of said ZnSnO_xA layer disposed on the SiAlZrN_xBetween the layer and the third functional layer 160, the ZnSnO is deposited_xThe layers include:

the target material is ZnSn, the intermediate frequency power supply is used as the target material power supply, 1 to 3 double rotating cathodes are adopted, and the air pressure is 1.0 multiplied by 10^-3mbar to 6.0 x 10^-3Carrying out magnetron sputtering in a mixed gas of mbar argon and oxygen, wherein the thickness of the film layer is 10nm to 15 nm.

In some embodiments, depositing the first sacrificial sublayer 180 comprises:

the target material is configured into graphite, a HiPIMS power supply is used as a target material power supply, and 1-3 double rotating cathodes are used as target materials; at an air pressure of 1.0X 10^-3mbar to 6.0 x 10^-3Performing magnetron sputtering in an argon atmosphere of mbar, and depositing the first sacrificial sublayer 180, wherein the coating thickness of the first sacrificial sublayer 180 is 20nm to 70 nm.

Referring to fig. 3, the preparation method of the three-silver low-emissivity glass 100 provided by the present application is simple to operate, low in requirements for process equipment, and low in cost, and is suitable for industrial mass production.

In some embodiments, the method comprises:

s101, providing a glass substrate 110;

s102, sequentially depositing an adhesion layer 111, a first functional layer 120, a first barrier layer 130, a second functional layer 140, a second barrier layer 150, a third functional layer 160, a protective layer 170 and a first sacrificial sublayer 180 on the surface of the glass substrate 110 in a magnetron sputtering mode; wherein the first sacrificial sublayer 181 is a graphite-like amorphous carbon film having a Vickers hardness of 10.2 to 15.2Gpa, a friction coefficient of 0.05 to 0.07 and

for detailed descriptions of step S101 and step S102, refer to the detailed descriptions of the above embodiments, which are not repeated herein.

And S103, arranging a water-soluble polyvinyl alcohol film, a hot-melt protective film or a polyethylene film on the surface of the first sacrificial sublayer 181, which is far away from the glass substrate 110, so as to obtain the three-silver low-emissivity glass.

Optionally, a water-soluble polyvinyl alcohol film is coated on the surface of the first sacrificial sublayer 181, which faces away from the glass substrate, and after drying treatment, the three-silver low-emissivity glass 100 is obtained.

Referring to fig. 4, the present application further provides a laminated glass 200, which includes:

a glass plate 210;

an adhesive layer 220; and

a tri-silver low emissivity glass 100 as described herein;

the adhesive layer 220 is disposed between the glass plate 210 and the three-silver low emissivity glass 100, and the protective layer 170 is disposed closer to the adhesive layer 220 than the glass substrate 110.

Wherein the sacrificial layer 180 of the three-silver low-emissivity glass 100 has been removed.

Referring to fig. 5, the present application further provides a vehicle 300, comprising:

a vehicle body 310; and

a window 320, said window 320 being disposed on said vehicle body 310, said window 320 comprising a laminated glass 200 as described herein.

The vehicle window 320 may be a front windshield, a side window, a rear windshield or a skylight of a vehicle, and the laminated glass 200 has excellent heat insulation performance. When the vehicle window 320 is a front windshield, the visible light transmittance of the laminated glass 200 is greater than or equal to 70%. The laminated glass 200 is further provided with at least two bus bars, and the bus bars are electrically connected with the metal layer of the three-silver low-emissivity glass 100, so that the current of a power supply can be introduced into the film layer of the three-silver low-emissivity glass 100, and the laminated glass is electrically heated to realize defrosting and demisting performances. The vehicle further includes a head-up display projection system capable of generating P-polarized light, and the metal layer of the three-silver low emissivity glass 100 is used to reflect the P-polarized light, thereby implementing a head-up display function.

The technical solution of the present application is further described below by referring to a plurality of examples.

Example 1

The preparation method of example 1 is as follows, and the material of the film layer is shown in table 1.

Taking a 2.1mm automobile plate glass original sheet as a glass substrate 110, cleaning and drying the glass substrate by a cleaning machine, and then feeding the glass substrate into a magnetron sputtering coating machine;

magnetron sputtering adhesion layer 111: SiAlZrN_x(ii) a The number of the targets is as follows: 2 double rotating cathodes are arranged; a target power supply: MF (medium frequency power supply); the target material is configured as SiAlZr, and the process gas is N₂And Ar, sputtering pressure 3.0X 10^-3mbar, and the thickness of the film layer is 17.6 nm;

magnetron sputtering a first dielectric layer of the first functional layer 120121: AZO; the number of the targets is as follows: 1 double rotating cathode; a target power supply: MF (medium frequency power supply); the target material is configured as ZnAlO_xCeramic target, process gas Ar, sputtering pressure 3.0X 10^-3mbar, and the thickness of the film layer is 12.8 nm;

magnetron sputtering the metal layer 122 of the first functional layer 120: ag; the number of the targets is as follows: 1 single plane cathode; a target power supply: DC (direct current power supply); the target material is configured to be Ag, the process gas is Ar, and the sputtering pressure is 2.0 multiplied by 10^-3mbar, and the thickness of the film layer is 11.3 nm;

magnetron sputtering the second dielectric layer 123 of the first functional layer 120: AZO; the number of the targets is as follows: 1 double rotating cathode; a target power supply: MF (medium frequency power supply); the target material is configured as ZnAlO_xCeramic target, process gas Ar, sputtering pressure 3.0X 10^-3mbar, and the thickness of the film layer is 12.8 nm;

magnetron sputtering the first barrier layer 130: ZnSnOx; the number of the targets is as follows: 4 double rotating cathodes are arranged; a target power supply: MF (medium frequency power supply); the target material is ZnSn, and the process gas is Ar and O₂Sputtering pressure 3.0X 10^-3mbar, and the thickness of the film layer is 52.7 nm;

magnetron sputtering the first dielectric layer 121 of the second functional layer 140: AZO; the number of the targets is as follows: 1 double rotating cathode; a target power supply: MF (medium frequency power supply); the target material is configured as ZnAlO_xCeramic target, process gas Ar, sputtering pressure 3.0X 10^-3mbar, and the thickness of the film layer is 12.8 nm;

magnetron sputtering the metal layer 122 of the second functional layer 140: ag; the number of the targets is as follows: 1 single plane cathode; a target power supply: DC (direct current power supply); the target material is configured to be Ag, the process gas is Ar, and the sputtering pressure is 2.0 multiplied by 10^-3mbar, and the thickness of the film layer is 13.7 nm;

magnetron sputtering the second dielectric layer 123 of the second functional layer 140: AZO; the number of the targets is as follows: 1 double rotating cathode; a target power supply: MF (medium frequency power supply); the target material is configured as ZnAlO_xCeramic target, process gas Ar, sputtering pressure 3.0X 10^-3mbar, and the thickness of the film layer is 12.8 nm;

magnetron sputtering of the second barrier layer 150: ZnSnO_x(ii) a The number of the targets is as follows: 4 double rotating cathodes are arranged; a target power supply: MF (medium frequency power supply);the target material is ZnSn, and the process gas is Ar and O₂Sputtering pressure 3.0X 10^-3mbar, and the thickness of the film layer is 54.2 nm;

magnetron sputtering the first dielectric layer 121 of the third functional layer 160: AZO; the number of the targets is as follows: 1 double rotating cathode; a target power supply: MF (medium frequency power supply); the target material is configured as ZnAlO_xCeramic target, process gas Ar, sputtering pressure 3.0X 10^-3mbar, and the thickness of the film layer is 12.8 nm;

magnetron sputtering the metal layer 122 of the third functional layer 160: ag; the number of the targets is as follows: 1 single plane cathode; a target power supply: DC (direct current power supply); the target material is configured to be Ag, the process gas is Ar, and the sputtering pressure is 2.0 multiplied by 10^-3mbar, and the thickness of the film layer is 14.5 nm;

magnetron sputtering the second dielectric layer 123 of the third functional layer 160: AZO; the number of the targets is as follows: 1 double rotating cathode; a target power supply: MF (medium frequency power supply); the target material is configured as ZnAlO_xCeramic target, process gas Ar, sputtering pressure 3.0X 10^-3mbar, and the thickness of the film layer is 12.8 nm;

magnetron sputtering protective layer 170: ZnSnO_x+SiAlZrN_x(ZnSnO was deposited first)_xPost-deposition SiAlZrN_x)；

ZnSnO_xLayer (b): the number of the targets is as follows: 1 double rotating cathode; a target power supply: MF (medium frequency power supply); the target material is ZnSn, and the process gas is Ar and O₂Sputtering pressure 3.0X 10^-3mbar, and the thickness of the film layer is 14.8 nm;

SiAlZrN_xlayer (b): the number of the targets is as follows: 1 double rotating cathode; a target power supply: HiPIMS (high power pulsed magnetron sputtering power supply); the target material is configured as SiAlZr, and the process gas proportion is N₂And Ar, sputtering pressure 3.0X 10^-3mbar, and the thickness of the film layer is 16.2 nm;

magnetron sputtering of the first sacrificial sublayer 181: GLC; the number of the targets is as follows: 1 double rotating cathode; a target power supply: HiPIMS (high power pulsed magnetron sputtering power supply); the target material is configured as graphite; the process gas is Ar, the sputtering pressure is 3.0 multiplied by 10^-3mbar, and the thickness of the film layer is 50 nm;

coating the second sacrificial sublayer 182: after the film coating is finished, conveying the film to a film coating chamber, and after the optical detection is finished, entering a water-soluble PVA spraying area; after spraying, the mixture enters a drying area for drying treatment; wherein the thickness of the water-soluble PVA film layer is 7 um.

Example 2

The preparation method of the example 2 is substantially the same as that of the example 1, except that the second sacrificial sublayer 182 is not provided in the example 2, and the material of the film layer of the example 2 is shown in table 1.

Example 3

The preparation method of the embodiment 3 is as follows, and the material of the film layer is shown in Table 2

Cleaning and drying a 6mm plate glass sheet by a cleaning machine, and then feeding the cleaned and dried plate glass sheet into a magnetron sputtering coating machine;

magnetron sputtering adhesion layer 111: SiAlZrN_x(ii) a The number of the targets is as follows: 2 double rotating cathodes are arranged; a target power supply: MF (medium frequency power supply); the target material is configured as SiAlZr, and the process gas is N₂And Ar, sputtering pressure 3.0X 10^-3mbar, and the thickness of the film layer is 26.2 nm;

magnetron sputtering the first dielectric layer 121 of the first functional layer 120: AZO; the number of the targets is as follows: 1 double rotating cathode; a target power supply: MF (medium frequency power supply); the target material is configured as ZnAlO_xCeramic target, process gas Ar, sputtering pressure 3.0X 10^-3mbar, and the thickness of the film layer is 13.9 nm;

magnetron sputtering the metal layer 122 of the first functional layer 120: ag; the number of the targets is as follows: 1 single plane cathode; a target power supply: DC (direct current power supply); the target material is configured to be Ag, the process gas is Ar, and the sputtering pressure is 2.0 multiplied by 10^-3mbar, and the thickness of the film layer is 7.9 nm;

magnetron sputtering the second dielectric layer 123 of the first functional layer 120: AZO; the number of the targets is as follows: 1 double rotating cathode; a target power supply: MF (medium frequency power supply); the target material is configured as ZnAlO_xCeramic target, process gas Ar, sputtering pressure 3.0X 10^-3mbar, and the thickness of the film layer is 15 nm;

magnetron sputtering the first barrier layer 130: SiAlZrN_x(ii) a The number of the targets is as follows: 4 double rotating cathodes are arranged; a target power supply: MF (medium frequency power supply); the target material is configured as SiAlZr, and the process gas is N₂And Ar, sputteringAir pressure of 3.0 x 10^-3mbar, and the thickness of the film layer is 44.9 nm;

magnetron sputtering the first dielectric layer 121 of the second functional layer 140: AZO; the number of the targets is as follows: 1 double rotating cathode; a target power supply: MF (medium frequency power supply); the target material is configured as ZnAlO_xCeramic target, process gas Ar, sputtering pressure 3.0X 10^-3mbar, and the thickness of the film layer is 14.5 nm;

magnetron sputtering the second dielectric layer 123 of the second functional layer 140: AZO; the number of the targets is as follows: 1 double rotating cathode; a target power supply: MF (medium frequency power supply); the target material is configured as ZnAlO_xCeramic target, process gas Ar, sputtering pressure 3.0X 10^-3mbar, and the thickness of the film layer is 17.6 nm;

magnetron sputtering of the second barrier layer 150: SiAlZrN_x(ii) a The number of the targets is as follows: 4 double rotating cathodes are arranged; a target power supply: MF (medium frequency power supply); the target material is configured as SiAlZr, and the process gas is N₂And Ar, sputtering pressure 3.0X 10^-3mbar, and the thickness of the film layer is 45.5 nm;

magnetron sputtering the metal layer 122 of the third functional layer 160: ag; the number of the targets is as follows: 1 single plane cathode; a target power supply: DC (direct current power supply); the target material is configured to be Ag, the process gas is Ar, and the sputtering pressure is 2.0 multiplied by 10^-3mbar, and the thickness of the film layer is 14.7 nm;

magnetron sputtering the second dielectric layer 123 of the third functional layer 160: AZO; the number of the targets is as follows: 1 double rotating cathode; a target power supply: MF (medium frequency power supply); the target material is configured as ZnAlO_xCeramic target, process gas Ar, sputtering pressure 3.0X 10^-3mbar, and the thickness of the film layer is 12.9 nm;

magnetron sputtering protective layer 170: SiAlZrN_x(ii) a The number of the targets is as follows: 1 double rotating cathode; a target power supply: HiPIMS (high power pulsed magnetron sputtering power supply); the target material is configured as SiAlZr, and the process gas proportion is N₂And Ar, sputtering pressure 3.0X 10^- ³mbar, and the thickness of the film layer is 21.7 nm;

magnetron sputtering of the first sacrificial sublayer 181: GLC; the number of the targets is as follows: 1 double rotating cathode; a target power supply: HiPIMS (high power pulsed magnetron sputtering power supply); the target material is configured as graphite; the process gas is Ar, the sputtering pressure is 3.0 multiplied by 10^-3mbar, and the thickness of the film layer is 40 nm;

coating the second sacrificial sublayer 182: after the film coating is finished, conveying the film to a film coating chamber, and after the optical detection is finished, entering a water-soluble PVA spraying area; after spraying, the mixture enters a drying area for drying treatment; wherein the thickness of the water-soluble PVA film layer is 9 um.

Example 4

The preparation method of the example 4 is substantially the same as that of the example 2, except that the second sacrificial sublayer 182 is not provided in the example 4, and the material of the film layer of the example 4 is shown in table 2.

Comparative example 1

The preparation method of the comparative example 1 is substantially the same as that of the example 1, except that the second sacrificial sublayer 182 and the first sacrificial sublayer 181 are not provided in the comparative example 1, and the material of the film layer of the comparative example 1 is shown in table 1.

Comparative example 2

The comparative example 2 was prepared substantially in the same manner as in example 1, except that the comparative example 2 was not provided with the second sacrificial sublayer 182, and the first sacrificial sublayer 181, and the SiAlZrN in the protective layer 170 of the comparative example 2 was_xThe layers were deposited using medium frequency power (MF) and the material of the film of comparative example 2 is shown in table 1.

Comparative example 3

The preparation method of the comparative example 3 is substantially the same as that of the example 2, except that the comparative example 3 is not provided with the second sacrificial sublayer 182 and the first sacrificial sublayer 181, and the material of the film layer of the comparative example 3 is shown in table 2.

Comparative example 4

The preparation method of the comparative example 4 is substantially the same as that of the example 2, except that the comparative example 4 is not provided with the second sacrificial sublayer 182 and the first sacrificial sublayer 181, and the protective layer 170 of the comparative example 4 is deposited by using a medium frequency power supply (MF), and the material of the film layer of the comparative example 4 is shown in table 2.

The film layer materials and experimental results of the examples 1, 2, 1 and 2 are shown in the table 1;

the three-silver low-emissivity glass obtained in example 1, example 2, comparative example 1 and comparative example 2 was subjected to an oxidation resistance test, a pencil hardness test, an alcohol wiping test and a water washing test before being subjected to a heat treatment (e.g., tempering, bending, etc.) at 550 ℃ to 650 ℃, and the three-silver low-emissivity glass obtained in example 1, example 2, comparative example 1 and comparative example 2 was subjected to a heat treatment (e.g., tempering, bending, etc.) at 550 ℃ to 650 ℃ and then to a pencil hardness test, an alcohol wiping test and a water washing test, and the results of the above tests are shown in table 1.

TABLE 1

The film layer materials and the experimental results of the examples 3, 4, 3 and 4 are shown in the table 2;

the three-silver low-emissivity glass obtained in example 3, example 4, comparative example 3 and comparative example 4 was subjected to an oxidation resistance test, a pencil hardness test, an alcohol wiping test and a water washing test before being subjected to a heat treatment (e.g., tempering, bending, etc.) at 550 ℃ to 650 ℃, and the three-silver low-emissivity glass obtained in example 3, example 4, comparative example 3 and comparative example 4 was subjected to a heat treatment (e.g., tempering, bending, etc.) at 550 ℃ to 650 ℃ and then to a pencil hardness test, an alcohol wiping test and a water washing test, and the results of the above tests are shown in table 2.

TABLE 2

As can be seen from tables 1 and 2, in comparison with comparative examples 1 to 4, examples 1 to 4 all used HiPIMS power deposition of SiAlZrN_xThe layer and the graphite-like amorphous carbon film (GLC) improve various performances of a film layer of the three-silver low-radiation glass 100, the oxidation resistance duration of the three-silver low-radiation glass is longer than 180 hours before heat treatment, and a water-soluble polyvinyl alcohol film (PVA) is additionally arranged as a second sacrificial sublayer 182 in the examples 1 and 3, compared with the examples 2 and 4, the oxidation resistance duration of the three-silver low-radiation glass 100 is improved to be longer than 200 hours before heat treatment, so that the surface hardness, alcohol wiping resistance and oxidation resistance of the three-silver low-radiation glass 100 are greatly improved, and the requirements of different-place processing are met.

Among them, the protective layers of comparative examples 2 and 4 include SiAlZrN as compared with comparative examples 1 and 3_xHowever, it was deposited using a medium frequency power supply (MF), and the results of the pencil hardness test and the alcohol rub test of the three-silver low emissivity glass 100 of comparative examples 2 and 4 before heat treatment were the worst, as compared to SiAlZrN deposited using a medium frequency power supply (MF)_xLayer comparison, SiAlZrN deposited by HiPIMS power supply_xThe layer is more compact, the surface hardness is higher, and the film adhesion is stronger.

In the product transportation, storage and processing experiments, the storage period of the three-silver low-emissivity glass 100 is obviously prolonged, and meanwhile, the quality problems caused in the storage and transportation processes are greatly improved. The film layer is hardly damaged in the deep processing cutting and edging processes, the PVA water film is cleaned in the cleaning process after edging, no residue is left, the GLC film can be cleaned in the heat treatment process (such as tempering, bending and the like), and no residue is left, so that various performances of the heat-treated three-silver low-radiation film layer can be sufficient for subsequent processing.

Although embodiments of the present application have been shown and described, it is understood that the above embodiments are illustrative and not restrictive, and that those skilled in the art may make changes, modifications, substitutions and alterations to the above embodiments without departing from the scope of the present application, and that such changes and modifications are also to be considered as within the scope of the present application.

Claims

1. The three-silver low-emissivity glass is characterized by comprising a glass substrate, and a first functional layer, a first barrier layer, a second functional layer, a second barrier layer, a third functional layer, a protective layer and a sacrificial layer which are sequentially stacked on at least one surface of the glass substrate; the first functional layer, the second functional layer and the third functional layer can reflect infrared rays; the protective layer comprises SiAlZrN_xLayer of said SiAlZrN_xIn layer N⁺Is 10 to 35 percent; the sacrificial layer comprises a first sacrificial sublayer, and the first sacrificial sublayer is a graphite-like amorphous carbon film.

2. The tri-silver low emissivity glass of claim 1, wherein the graphite-like amorphous carbon film has a vickers hardness of 10.2Gpa to 15.2Gpa and a coefficient of friction of 0.05 to 0.07.

3. The tri-silver low emissivity glass of claim 1, wherein the first sacrificial sublayer has a thickness of 20nm to 70 nm.

4. The tri-silver low emissivity glass of claim 1, wherein the sacrificial layer further comprises a second sacrificial sublayer disposed on a surface of the first sacrificial sublayer distal from the third functional layer, the second sacrificial sublayer comprising at least one of a water soluble polyvinyl alcohol film, a hot melt type protective film, a polyethylene film.

5. The tri-silver low emissivity glass of claim 1, wherein the first functional layer, the second functional layer, and the third functional layer each comprise a first dielectric layer, a metal layer, and a second dielectric layer in a stacked arrangement, the metal layer comprising at least one of Ag, Au, Cu, Al, and alloys thereof.

6. The tri-silver low emissivity glass of claim 5, wherein said first dielectric layer comprises AZO, Ti alloy, NbO_x、TiO_x、NiCr、NiCrO_x、ZnAlO_x、ZnO_x、SnO_xAt least one of; the second dielectric layer comprises AZO, Ti alloy and NbO_x、TiO_x、NiCr、NiCrO_x、ZnAlO_x、ZnO_x、SnO_xAt least one of (1).

7. The tri-silver low emissivity glass of claim 1, wherein the first barrier layer comprises ZnSnO_x、SiAlZrN_x、SiAlN_x、SiN_x、SiZrN_x、ZnO_x、AZO、ZnAlO_xAt least one of ITO; the second barrier layer comprises ZnSnO_x、SiAlZrN_x、SiAlN_x、SiN_x、SiZrN_x、ZnO_x、AZO、ZnAlO_xAnd ITO.

8. The tri-silver low emissivity glass of claim 7, wherein the first barrier layer comprises SiAlZrN_xSiAlZrN of the first barrier layer_xIn N⁺Is less than SiAlZrN of the protective layer_xIn layer N⁺Mass fraction of (a); the second barrier layer comprises SiAlZrN_xSiAlZrN of said second barrier layer_xIn N⁺Is less than SiAlZrN of the protective layer_xIn layer N⁺Mass fraction of (c).

9. The tri-silver low emissivity glass of claim 1, wherein said protection is from radiationThe layer further comprises ZnSnO_xLayer of said ZnSnO_xThe layer is deposited by a medium frequency power supply, the ZnSnO_xA layer disposed on the SiAlZrN_xA layer and said third functional layer.

10. The tri-silver low emissivity glass of claim 1, wherein an adhesion layer comprising at least one of SiAlZrNx, ZrOx, NbOx, SiNx, ZnSnOx, SiZrNx is disposed between the glass substrate and the first functional layer.

11. The tri-silver low emissivity glass of claim 10, wherein the adhesion layer comprises SiAlZrN_xSiAlZrN of said adhesion layer_xIn N⁺Is less than SiAlZrN of the protective layer_xIn layer N⁺Mass fraction of (c).

12. A preparation method of three-silver low-emissivity glass is characterized by comprising the following steps:

providing a glass substrate; and

13. The method of making a tri-silver low emissivity glass according to claim 12, wherein said method further comprises:

14. The method of making a tri-silver low emissivity glass of claim 12, wherein depositing said first sacrificial sub-layer comprises:

15. The method of making a tri-silver low emissivity glass of claim 12, wherein said protective layer comprises a layer of SiAlZrNx, said SiAlZrN being deposited_xThe layers include:

16. The method of making a tri-silver low emissivity glass of claim 15, wherein said protective layer further comprises ZnSnO_xLayer of said ZnSnO_xA layer disposed on the SiAlZrN_xBetween the layer and the third functional layer, depositing the ZnSnO_xThe layers include:

the target material is ZnSn, the intermediate frequency power supply is used as the target material power supply, 1 to 6 double rotating cathodes are adopted, and the air pressure is 1.0 multiplied by 10^- ³mbar to 6.0 x 10^-3Carrying out magnetron sputtering in a mixed gas of mbar argon and nitrogen to deposit the ZnSnO_xAnd (3) a layer.

17. A laminated glass, comprising:

a glass plate;

an adhesive layer; and

the tri-silver low emissivity glass of any one of claims 1 to 11;