Coated glass, method for manufacturing coated glass, and laminated glass

Abstract

The application provides a coated glass, a preparation method thereof and a laminated glass. The coated glass comprises a first substrate and a coating structure. The coating structure is arranged on at least one surface of the first substrate. The coating structure comprises at least one functional stack and at least one ZrOx layer. Each functional stack comprises a metal layer and two dielectric layers. The metal layer is arranged between the two dielectric layers. The ZrOx layer is arranged on the side of the dielectric layer away from the metal layer. X satisfies 1 < x < 2. The refractive index n of the ZrOx layer satisfies the range of 2.00 < n < 2.18. The technical scheme provided by the application can improve the hardness of the coating structure on the coated glass, thereby improving the scratch resistance and processing performance of the coated glass.

Description

Technical Field

[0001] The present application relates to the field of glass technology, and in particular to coated glass and a preparation method thereof, and laminated glass. Background Art

[0002] Coated glass refers to a coating or film layer with special functions formed on the surface of a glass substrate using vapor deposition technology. Vapor deposition technology is further divided into chemical vapor deposition (CVD) and physical vapor deposition (PVD). In actual products, physical vapor deposition technology can be used to manufacture coated glass containing 1-4 silver layers. Since the silver layer has the characteristics of reflecting infrared rays and good conductivity, coated glass containing silver layers can be used as insulating glass or electrically heated glass. When installed on a vehicle, insulating glass can prevent light other than visible light in sunlight, especially infrared rays, from entering the interior space, thereby significantly reducing air conditioning energy consumption and improving the thermal comfort of drivers and passengers. The temperature of electrically heated glass can increase as the current passes through it, thereby achieving functions such as preventing fogging or defogger, defrosting, and deicing, thereby improving driving safety.

[0003] When manufacturing coated glass for use as insulating glass or electrically heated glass in motor vehicles, it undergoes high-temperature heat treatment at temperatures of at least 500°C and bending processes, such as baking and press bending. This requires the coating or film on the coated glass to not only meet optical performance and appearance quality requirements, but also possess high mechanical properties, thermal stability, and chemical stability. Conventional coated glass containing silver layers has poor mechanical properties, especially those with three or four silver layers, whose film has low hardness. This makes it susceptible to scratching by hard objects during subsequent transportation, storage, handling, and processing, resulting in poor processing resistance. Summary of the Invention

[0004] The present application provides a coated glass and a preparation method thereof, and laminated glass, which can increase the hardness of the coating structure on the coated glass, thereby improving the scratch resistance and processing resistance of the coated glass.

[0005] In a first aspect, the present application provides a coated glass, the coated glass comprising:

[0006] a first substrate; and

[0007] A coating structure is provided on at least one surface of the first substrate, the coating structure comprising at least one functional stack and at least one ZrOx layer, each functional stack comprising a metal layer and two dielectric layers, the metal layer being located between the two dielectric layers, and the ZrOx layer being located on a side of the dielectric layer facing away from the metal layer, wherein x satisfies 1<x≤2, and a refractive index n of the ZrOx layer satisfies the range of 2.00≤n≤2.18.

[0008] It can be understood that the refractive index n of the ZrOx layer provided in the present application is in the range of 2.00≤n≤2.18. The ZrOx layer with a refractive index n in the range of 2.00≤n≤2.18 used in the present application can improve the hardness of the coating structure, thereby improving the scratch resistance and processing resistance of the coated glass, and preventing the coated glass from being easily scratched by hard objects during subsequent transportation, storage, handling, and processing.

[0009] In a possible implementation manner, the pencil hardness of the coating structure is greater than or equal to 9H.

[0010] In a possible implementation, the material of the metal layer is selected from any one metal or metal alloy of silver, gold, copper, aluminum, and platinum, and the physical thickness of the metal layer is 5 nm to 20 nm.

[0011] In one possible embodiment, the material of the dielectric layer is selected from oxides of at least one metal or metal alloy of Zn, Mg, Sn, Ti, Nb, Zr, Ni, In, Al, Ce, W, Mo, Sb, and Bi, and the physical thickness of the dielectric layer is 5 nm to 30 nm.

[0012] In a possible implementation, the coating structure includes an innermost adhesion layer, a first functional layer, and an outermost protective layer stacked in sequence, and at least one of the innermost adhesion layer and the outermost protective layer includes the ZrOx layer.

[0013] In one possible embodiment, the coating structure includes an innermost adhesion layer, a first functional stack, a first intermediate layer, a second functional stack, and an outermost protective layer stacked in sequence, and at least one of the innermost adhesion layer, the first intermediate layer, and the outermost protective layer includes the ZrOx layer.

[0014] In one possible embodiment, the coating structure includes an innermost adhesion layer, a first functional stack, a first intermediate layer, a second functional stack, a second intermediate layer, a third functional stack, and an outermost protective layer stacked in sequence, and at least one of the innermost adhesion layer, the first intermediate layer, the second intermediate layer, and the outermost protective layer includes the ZrOx layer.

[0015] In one possible embodiment, the coating structure includes an innermost adhesion layer, a first functional stack, a first intermediate layer, a second functional stack, a second intermediate layer, a third functional stack, a third intermediate layer, a fourth functional stack and an outermost protective layer stacked in sequence, and at least one of the innermost adhesion layer, the first intermediate layer, the second intermediate layer, the third intermediate layer and the outermost protective layer includes the ZrOx layer.

[0016] In a possible implementation manner, the innermost adhesion layer includes a ZrOx layer with a physical thickness of 10 nm to 40 nm.

[0017] In a possible implementation manner, the outermost protective layer includes a ZrOx layer with a physical thickness of 5 nm to 35 nm.

[0018] In a possible implementation manner, at least one of the first intermediate layer, the second intermediate layer, and the third intermediate layer includes a ZrOx layer having a physical thickness of 30 nm to 70 nm.

[0019] In a possible implementation manner, the specific structure of the outermost protective layer is: TiOx layer / ZnSnOx layer / the ZrOx layer.

[0020] In a possible implementation manner, the extinction coefficient k of the ZrOx layer is less than or equal to 0.0001.

[0021] In a second aspect, the present application provides a laminated glass comprising a second substrate, an adhesive layer and the coated glass described above, wherein the adhesive layer is connected between the second substrate and the coated glass, and the coating structure is located between the first substrate and the second substrate.

[0022] In one possible embodiment, the first substrate is transparent glass or extra-transparent glass, the total iron content of the transparent glass is less than or equal to 0.1%, and the visible light transmittance of the transparent glass is greater than or equal to 80%; the total iron content of the extra-transparent glass is less than or equal to 0.015%, and the visible light transmittance of the extra-transparent glass is greater than or equal to 90%.

[0023] In a third aspect, the present application provides a method for preparing coated glass:

[0024] Providing a first substrate:

[0025] forming a coating structure on at least one surface of the first substrate by a magnetron sputtering process;

[0026] The coating structure includes at least one functional stack and at least one ZrOx layer, each functional stack includes a metal layer and two dielectric layers, the metal layer is located between the two dielectric layers, and any ZrOx layer is formed on the side of the dielectric layer facing away from the metal layer, where x satisfies 1<x≤2, and the refractive index n of the ZrOx layer satisfies the range: 2.00≤n≤2.18.

[0027] In a possible implementation, a target power source for magnetron sputtering the ZrOx layer is a high-power pulsed magnetron sputtering power source, and a target material for magnetron sputtering the ZrOx layer is a ZrOy ceramic target, wherein y satisfies 1.4≤y<2. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solution of the present application, the following is a brief introduction to the drawings required for use in the implementation. Obviously, the drawings described below are only some implementation methods of the present application. For ordinary technicians in this field, other drawings can be obtained like these drawings without any creative work.

[0029] Figure 1 Schematic diagram of the structure of the laminated glass provided in the embodiment of the present application;

[0030] Figure 2 yes Figure 1 A schematic cross-sectional view of a first embodiment of coated glass is shown;

[0031] Figure 3 yes Figure 1 A schematic cross-sectional view of a second embodiment of the coated glass is shown;

[0032] Figure 4 yes Figure 1 A schematic cross-sectional view of a third embodiment of the coated glass is shown;

[0033] Figure 5 yes Figure 1 A schematic cross-sectional view of a fourth embodiment of the coated glass is shown;

[0034] Figure 6 It is a schematic flow chart of a method for preparing coated glass provided in an embodiment of the present application. DETAILED DESCRIPTION

[0035] For ease of understanding, the terms involved in the embodiments of the present application are first explained.

[0036] And / or: It is just a description of the association relationship of associated objects, indicating that three relationships can exist. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone.

[0037] Multiple: refers to two or more than two.

[0038] Connection: should be understood in a broad sense. For example, A and B are connected, which can be either directly connected or indirectly connected through an intermediary.

[0039] The values ​​of x and y in the chemical formula: If clearly defined, they shall be within the defined ranges. If not clearly defined, they may be determined based on the stoichiometric, substoichiometric, or superstoichiometric deposition methods used in the magnetron sputtering process.

[0040] High-temperature heat treatment: High-temperature heat treatment of at least 500°C, such as the self-weight bending process or press bending process in the production of automotive glass.

[0041] The specific implementation of the present application will be clearly described below with reference to the accompanying drawings.

[0042] See also Figure 1 , Figure 1 1 is a schematic structural diagram of a laminated glass 1000 provided in an embodiment of the present application. The laminated glass 1000 includes a coated glass 1001, an adhesive layer 1002, and a second substrate 1003. The adhesive layer 1002 is connected between the second substrate 1003 and the coated glass 1001. The coated glass 1001 includes a first substrate 100 and a coating structure 200. The coating structure 200 is provided on at least one surface of the first substrate 100. Exemplarily, the coating structure 200 is located between the first substrate 100 and the second substrate 1003, that is, the side of the first substrate 100 on which the coating structure 200 is provided is connected to the adhesive layer 1002. The pencil hardness of the coating structure 200 is greater than or equal to 9H, thereby improving the scratch resistance and processing resistance of the coated glass 1001.

[0043] It should be noted that Figure 1 The purpose is only to schematically describe the connection relationship between the coated glass 1001, the adhesive layer 1002 and the second substrate 1003, and is not to specifically limit the connection position, specific structure and quantity of each device. The structure shown in the embodiment of the present application does not constitute a specific limitation on the laminated glass 1000. In other embodiments of the present application, the laminated glass 1000 may include Figure 1 More or fewer components may be shown, or some components may be combined or separated, or the components may be arranged differently. Figure 1 The components shown can be implemented in hardware, software, or a combination of software and hardware.

[0044] In the present application, the laminated glass 1000 can be installed on a vehicle for use as a windshield, side window glass, rear windshield, or sunroof glass, etc. The coating structure 200 includes at least one functional stack and at least one ZrOx layer. Each functional stack includes a metal layer and two dielectric layers. The metal layer is located between the two dielectric layers. No ZrOx layer is in direct contact with any metal layer. That is, the ZrOx layer is located on the side of the dielectric layer facing away from the metal layer. At least one dielectric layer is provided between any ZrOx layer and its most adjacent metal layer. Where x satisfies 1<x≤2, and the refractive index n of the ZrOx layer satisfies the range: 2.00≤n≤2.18. The metal layer, dielectric layer, and ZrOx layer can be formed separately by magnetron sputtering processes.

[0045] The metal layer has the characteristics of infrared reflection and good conductivity. The coating structure 200 containing the metal layer provides thermal insulation to the coated glass 1001 and the laminated glass 1000, thereby significantly reducing air conditioning energy consumption and improving thermal comfort for the driver and passengers. Depending on the actual application requirements, the number of metal layers in the coating structure 200 can be, for example, one, two, three, four, five, or even more. In one possible embodiment, the coating structure 200 can also be used as a transparent conductive film. In this case, the laminated glass 1000 can be electrically heated when powered, thereby increasing the temperature of the laminated glass 1000, thereby preventing fogging or achieving defrosting, defrosting, and deicing functions, thereby improving driving safety. For example, the voltage applied to the laminated glass 1000 can be 12V to 380V. The material of the metal layer is selected from any metal or metal alloy selected from silver, gold, copper, aluminum, and platinum, specifically Ag, AgCu alloy, AgIn alloy, etc. The physical thickness of the metal layer is 5nm to 20nm. The dielectric layer is made of an oxide of at least one metal or metal alloy selected from the group consisting of Zn, Mg, Sn, Ti, Nb, Zr, Ni, In, Al, Ce, W, Mo, Sb, and Bi. Specific examples include AZO, NbOx, TiOx, ZnAlOx, ZnOx, SnOx, and ZnSnOx. The dielectric layer has a physical thickness of 5 nm to 30 nm. In some embodiments, a barrier layer (not shown) may be deposited between the metal layer and any of the dielectric layers. The barrier layer may be made of Ti, NiCr, Nb, and the like. The barrier layer has a physical thickness of less than or equal to 5 nm and is in direct contact with the metal layer. The barrier layer is primarily used to prevent the metal layer from contacting the oxidizing reaction gas during magnetron sputtering and to improve the optical properties of the coating structure 200.

[0046] Both the first substrate 100 and the second substrate 1003 may be transparent glass or ultra-clear glass (ultra-white glass). The total iron content of transparent glass is less than or equal to 0.1%, and the visible light transmittance of transparent glass is greater than or equal to 80%. The iron oxide (Fe2O3) content in ultra-clear glass is relatively low, and the visible light transmittance of ultra-clear glass is greater than or equal to 90%. Calculated by weight percentage, the first substrate 100 and the second substrate 1003 may contain 0-0.1% iron oxide (Fe2O3). For example, the iron oxide (Fe2O3) content in the first substrate 100 and the second substrate 1003 may be less than or equal to 0.09%, less than or equal to 0.08%, less than or equal to 0.07%, less than or equal to 0.05%, less than or equal to 0.04%, less than or equal to 0.03%, less than or equal to 0.02%, less than or equal to 0.015%, or less than or equal to 0.01%. The first substrate 100 and the second substrate 1003 may even contain substantially no iron oxide (Fe2O3). For example, the first substrate 100 and the second substrate 1003 may be soda-lime-silica ultra-transparent glass, borosilicate glass, or high-aluminum glass.

[0047] The adhesive layer 1002 is used to connect the first substrate 100 and the second substrate 1003 to improve the structural strength of the laminated glass 1000 so that it meets the safety standards and regulatory requirements of more scenarios. The material of the adhesive layer 1002 can be polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), thermoplastic polyurethane elastomer (TPU) or ionomeric polymer film (SGP), etc. Exemplarily, the adhesive layer 1002 can be a single-layer structure or a multi-layer structure. Examples of the multi-layer structure include a double-layer structure, a three-layer structure, a four-layer structure, a five-layer structure, etc. The adhesive layer 1002 can also have other functions, such as providing at least one colored area as a shadow band to reduce the interference of sunlight on the human eye, or adding an infrared absorber to provide sun protection or heat insulation, or adding an ultraviolet absorber to provide ultraviolet protection, or at least one layer of the multi-layer structure has a higher plasticizer content to provide sound insulation.

[0048] For the first possible implementation, see Figure 2 , Figure 2 yes Figure 1 The cross-sectional structure diagram of the first embodiment of coated glass 1001 is shown. The coating structure 200 has only one functional stack, specifically comprising an innermost adhesion layer 210, a first functional stack 220, and an outermost protective layer 290 stacked in sequence. At least one of the innermost adhesion layer 210 and the outermost protective layer 290 includes a ZrOx layer.

[0049] For the second possible implementation, see Figure 3 , Figure 3 yes Figure 1The cross-sectional structure of a second embodiment of coated glass 1001 is shown. Coating structure 200 comprises two functional stacks, specifically comprising an innermost adhesion layer 210, a first functional stack 220, a first intermediate layer 260, a second functional stack 230, and an outermost protective layer 290 stacked in sequence. At least one of innermost adhesion layer 210, first intermediate layer 260, and outermost protective layer 290 comprises a ZrOx layer.

[0050] For a third possible implementation, see Figure 4 , Figure 4 yes Figure 1 The cross-sectional structure of a third embodiment of coated glass 1001 is shown. Coating structure 200 comprises three functional stacks, specifically, an innermost adhesion layer 210, a first functional stack 220, a first intermediate layer 260, a second functional stack 230, a second intermediate layer 270, a third functional stack 240, and an outermost protective layer 290, stacked in sequence. At least one of innermost adhesion layer 210, first intermediate layer 260, second intermediate layer 270, and outermost protective layer 290 comprises a ZrOx layer.

[0051] For the fourth possible implementation, see Figure 5 , Figure 5 yes Figure 1 The cross-sectional structure of the fourth embodiment of coated glass 1001 is shown. The coating structure 200 has four functional stacks, specifically including an innermost adhesion layer 210, a first functional stack 220, a first intermediate layer 260, a second functional stack 230, a second intermediate layer 270, a third functional stack 240, a third intermediate layer 280, a fourth functional stack 250, and an outermost protective layer 290, stacked in sequence. At least one of the innermost adhesion layer 210, the first intermediate layer 260, the second intermediate layer 270, the third intermediate layer 280, and the outermost protective layer 290 includes a ZrOx layer.

[0052] exist Figure 2 、 Figure 3 、 Figure 4 and Figure 5In the embodiment, the innermost adhesion layer 210 is deposited directly on the surface of the first substrate 100 to reduce or prevent the diffusion of alkali metal ions from the glass into the coating structure 200. It can also increase the adhesion between the coating structure 200 and the surface of the first substrate 100, and help adjust the mechanical properties, optical properties, and high-temperature heat treatment performance of the coating structure 200. The innermost adhesion layer 210 is all the film layers between the surface of the first substrate 100 and the first functional stack 220. The innermost adhesion layer 210 can be a single film layer or composed of multiple sub-film layers. In some embodiments, the innermost adhesion layer 210 can include a ZrOx layer with a physical thickness of 10nm to 40nm. In other embodiments, the material of the innermost adhesion layer 210 can also be selected from oxides, nitrides or nitrogen oxides of at least one element among Si, Zn, Mg, Sn, Ti, Nb, Zr, Ni, In, Al, Ce, W, Mo, Sb, and Bi, and specific examples include SiAlZrNx, NbOx, SiNx, ZnSnOx, SiZrNx, etc.

[0053] The first functional stack 220 includes a first dielectric layer 221, a first metal layer 222, and a second dielectric layer 223, which are stacked in sequence. The first dielectric layer 221 is deposited on the innermost adhesion layer 210. The first and second dielectric layers 221 and 223 primarily protect the first metal layer 222 from damage by alkali metal ions, oxygen, and the like. The first dielectric layer 221 also serves as a crystallization seed layer for the first metal layer 222, thereby improving its deposition density. The second functional stack 230 includes a third dielectric layer 231, a second metal layer 232, and a fourth dielectric layer 233, which are stacked in sequence. The third and fourth dielectric layers 231 and 233 primarily protect the second metal layer 232 from damage by alkali metal ions, oxygen, and the like. The third dielectric layer 231 also serves as a crystallization seed layer for the second metal layer 232, thereby improving its deposition density. The third functional stack 240 includes a fifth dielectric layer 241, a third metal layer 242, and a sixth dielectric layer 243, which are stacked in sequence. The fifth and sixth dielectric layers 241 and 243 primarily protect the third metal layer 242 from damage by alkali metal ions, oxygen, and the like. The fifth dielectric layer 241 also serves as a crystallization seed layer for the third metal layer 242, thereby improving its deposition density. The fourth functional stack 250 includes a seventh dielectric layer 251, a fourth metal layer 252, and an eighth dielectric layer 253, which are stacked in sequence. The seventh and eighth dielectric layers 251 and 253 primarily protect the fourth metal layer 252 from damage by alkali metal ions, oxygen, and the like. The seventh dielectric layer 251 also serves as a crystallization seed layer for the fourth metal layer 252, thereby improving its deposition density.

[0054] exist Figure 3 、 Figure 4 and Figure 5In the embodiment, the coating structure 200 includes at least two functional stacks, with intermediate layers disposed between adjacent functional stacks, namely, a first intermediate layer 260, a second intermediate layer 270, and a third intermediate layer 280. The first intermediate layer 260 is located between the second dielectric layer 223 and the third dielectric layer 231, the second intermediate layer 270 is located between the fourth dielectric layer 233 and the fifth dielectric layer 241, and the third intermediate layer 280 is located between the sixth dielectric layer 243 and the seventh dielectric layer 251. These intermediate layers can improve the flatness and reflective color of the coating structure 200. These intermediate layers can be single layers or composed of multiple sub-layers. In some embodiments, at least one of the first intermediate layer 260, the second intermediate layer 270, and the third intermediate layer 280 includes a ZrOx layer with a physical thickness of 30 nm to 70 nm. The ZrOx layer has a high hardness, which can increase the hardness of the coating structure 200, thereby improving the scratch resistance and processing resistance of the coated glass. In other embodiments, the materials of the first intermediate layer 260, the second intermediate layer 270 and the third intermediate layer 280 can also be selected from oxides, nitrides or oxynitrides of at least one element among Si, Zn, Mg, Sn, Ti, Nb, Zr, Ni, In, Al, Ce, W, Mo, Sb, and Bi, and specific examples include ZrNx, SiOx, SiOxNy, SiAlZrNx, SiZrNx, SiNx, SiZrOx, SiAlZrOx, ZnSnOx, AZO, ITO, etc.

[0055] exist Figure 2 、 Figure 3 、 Figure 4 and Figure 5 In the embodiment, the outermost protective layer 290 is deposited on the outer side of the functional stack farthest from the first substrate 100. Figure 2 The outermost protective layer 290 is deposited on the side of the first functional stack 220 away from the first substrate 100, Figure 3 The outermost protective layer 290 is deposited on the side of the second functional stack 230 away from the first substrate 100, Figure 4 The outermost protective layer 290 is deposited on the side of the third functional stack 240 away from the first substrate 100, Figure 5 The outermost protective layer 290 is deposited on the side of the fourth functional stack 250 away from the first substrate 100. The outermost protective layer 290 is primarily used to protect the metal layers in the functional stack from corrosion and mechanical damage, and helps adjust the mechanical, optical, and high-temperature heat treatment properties of the coating structure 200. The outermost protective layer 290 is all the film layers on the outside of the functional stack in the coating structure 200 that are farthest from the first substrate 100. The outermost protective layer 290 can be a single film layer or composed of multiple sub-film layers. The thickness of the outermost protective layer 290 can be between 5nm and 70nm (including the endpoints of 5nm and 70nm).

[0056] In some embodiments, the outermost protective layer 290 may include a ZrOx layer with a physical thickness of 5 nm to 35 nm. In other embodiments, the material of the innermost adhesion layer 210 may also be selected from oxides, nitrides, or oxynitrides of at least one element selected from Si, Zn, Mg, Sn, Ti, Nb, Zr, Ni, In, Al, Ce, W, Mo, Sb, and Bi, and specific examples include ZrNx, SiOx, SiOxNy, SiAlZrNx, SiZrNx, SiNx, SiZrOx, and SiAlZrOx.

[0057] In some other embodiments, the outermost protective layer 290 includes three sub-film layers, and its specific structure can be: TiOx layer 291 / ZnSnOx layer 292 / ZrOx layer 293, the physical thickness of the TiOx layer 291 is less than or equal to 20 nm, and the physical thickness of the ZnSnOx layer 292 is less than or equal to 20 nm. The structure of TiOx layer 291 / ZnSnOx layer 292 / ZrOx layer 293 can make the coating structure 200 have better thermal ductility and can ensure that the coating structure 200 does not crack during high-temperature heat treatment.

[0058] In other embodiments, the outermost protective layer 290 includes two sub-layers, and its specific structure can be: TiOx layer 291 / ZnSnOx layer 292. The physical thickness of the TiOx layer 291 is less than or equal to 20 nm, and the physical thickness of the ZnSnOx layer 292 is less than or equal to 20 nm.

[0059] This application also provides a method for preparing coated glass 1001, please refer to Figure 6 , Figure 6 1 is a flow chart of a method for preparing coated glass 1001 provided in an embodiment of the present application. The preparation method includes:

[0060] S100: providing a first substrate 100.

[0061] S200: A coating structure 200 is formed on at least one surface of a first substrate 100 by a magnetron sputtering process; the coating structure 200 includes at least one functional stack and at least one ZrOx layer, each functional stack includes a metal layer and two dielectric layers, the metal layer is located between the two dielectric layers, and any ZrOx layer is formed on a side of the dielectric layer away from the metal layer, wherein x satisfies 1<x≤2, and the refractive index n of the ZrOx layer satisfies the range: 2.00≤n≤2.18 (including endpoint values ​​2.00 and 2.18).

[0062] In the present application, the target power source for magnetron sputtering the ZrOx layer is a high-power pulsed magnetron sputtering power source (HiPIMS), and the target material for magnetron sputtering the ZrOx layer is a ZrOy ceramic target, where y satisfies 1.4≤y<2. The refractive index n of the ZrOx layer obtained by magnetron sputtering using the HiPIMS power source is 2.00-2.18, so that the pencil hardness of the obtained coating structure 200 is greater than or equal to 9H. Specific examples of the refractive index n include 2.00, 2.01, 2.02, 2.03, 2.04, 2.05, 2.06, 2.07, 2.08, 2.09, 2.10, 2.11, 2.12, 2.13, 2.14, 2.15, 2.16, 2.17, 2.18, etc., and preferably the refractive index n of the ZrOx layer is 2.05-2.15.

[0063] Comparative Examples 1-6 and Examples 1-12

[0064] In the present application, a 2.1 mm thick transparent glass substrate was prepared, and the film layer structures of Comparative Examples 1-4 and Examples 1-12 were deposited on the surface of the transparent glass substrate by a magnetron sputtering process. The pencil hardness of the coated glass test samples of Comparative Examples 1-3 and Examples 1-12 before high-temperature heat treatment was measured, and the refractive index n and extinction coefficient k of the ZrOx layer of Comparative Examples 2-4 and Examples 1-12 after high-temperature heat treatment were measured. The measurement results are recorded in Table 1.

[0065] Comparative Example 1: transparent glass substrate / Ag layer.

[0066] Comparative Example 2: transparent glass substrate / Ag layer / DLC layer, the target material of the magnetron sputtering DLC ​​layer is a graphite target, the process gas is Ar, the target power supply is a high power pulsed magnetron sputtering power supply (HiPIMS), and the duty cycle is 5% to 17%.

[0067] Comparative Example 3: transparent glass substrate / Ag layer / AZO layer, the target material of the magnetron sputtering AZO layer is an AZO ceramic target, the process gases are Ar and O2, the target power supply is a medium frequency magnetron sputtering power supply (MF), and the duty cycle is 100%.

[0068] Comparative Examples 4-6: transparent glass substrate / Ag layer / ZrOx layer, the target material for magnetron sputtering ZrOx layer is ZrOy ceramic target (y=1.4), the process gas is Ar and O2, the target power supply is a medium frequency magnetron sputtering power supply (MF), and the duty cycle is 100%.

[0069] Example 1-12: transparent glass substrate / Ag layer / ZrOx layer, the target material for magnetron sputtering of the ZrOx layer is a ZrOy ceramic target (y=1.4), the process gases are Ar and O2, the target power supply is a high-power pulsed magnetron sputtering power supply (HiPIMS), and the duty cycle is 5% to 17%.

[0070] Among them, the target material of the Ag layer in magnetron sputtering comparative examples 1-4 and embodiments 1-12 is a silver metal target, the process gas is Ar, and the target power supply is a direct current power supply (DC).

[0071] Table 1: Measurement results of coated glass test samples of Comparative Examples 1-4 and Examples 1-12

[0072]

[0073] As can be seen from Table 1, the hardness of the Ag layer in Comparative Example 1 is poor, the hardness of the film layer in Comparative Example 2 can be significantly improved by depositing a DLC layer (HiPIMS) on the Ag layer, the hardness of the film layer in Comparative Example 3 is not significantly improved by depositing an AZO layer (MF) on the Ag layer, and the hardness of the film layer in Comparative Example 4 is not significantly improved by depositing a ZrOx layer (MF) on the Ag layer. Comparative Examples 5-6 can significantly improve the hardness of the film layer by depositing a ZrOx layer (MF) on the Ag layer, and can even increase it to 8H.

[0074] Compared with Comparative Examples 1-6, Example 1-12 can further increase the hardness of the film layer to greater than 9H by adopting a high-power pulsed magnetron sputtering power supply (HiPIMS) as a target power supply. Obviously, the ZrOx layer (HiPIMS) has a higher single-layer hardness than the DLC layer, the AZO layer and even the ZrOx layer (MF). The ZrOx layer (HiPIMS) is more conducive to use in the innermost adhesion layer, the first intermediate layer, the second intermediate layer, the third intermediate layer and the outermost protective layer of the coating structure 200.

[0075] Generally speaking, the duty cycle of a medium frequency magnetron sputtering power supply (MF) during operation is basically 100%, that is, the MF power supply acts on the target material uninterruptedly, while the duty cycle of a high power pulsed magnetron sputtering power supply (HiPIMS) during operation is 5% to 17%, that is, the HiPIMS power supply acts on the target material for a shorter time. When depositing the same material, under the same process conditions, the sputtering rate of the HiPIMS power supply is usually lower than the sputtering rate of the MF power supply. However, from the comparison of comparative examples 4-6 and embodiments 1-12, the opposite situation occurs on the ZrOx material. This is because the ZrOx material has poor conductivity and is difficult to ionize. It is difficult for the MF power supply to completely ionize the target material. During the sputtering process, problems such as unstable voltage, sparking of the target material, and severe arcing alarms often occur. Compared with comparative examples 4-6 in which the ZrOx layer was deposited using an MF power supply, the sputtering rate of the ZrOx layer deposited using a HiPIMS power supply in examples 1-12 was increased by 21.9% to 68%. The increase in sputtering rate is beneficial to the application of the material and greatly saves the costs of the cavity, cathode, power supply, etc. required for the application of the material.

[0076] Table 1 also shows that the ZrOx layer (MF) deposited using MF power has a refractive index n greater than 2.2 and an extinction coefficient k>0.001, while the ZrOx layer (HiPIMS) deposited using HiPIMS power has a lower refractive index n=2.00-2.18, more specifically n=2.06-2.12, and a lower extinction coefficient k≤0.0001, or even k≤0.00005. In other words, using HiPIMS power to deposit the ZrOx layer (HiPIMS) changes the compactness of the ZrOx layer (HiPIMS), and thus changes the refractive index n and extinction coefficient k of the ZrOx layer (HiPIMS), which is conducive to expanding the application range of the ZrOx layer (HiPIMS). It can be seen that the use of the ZrOx layer (HiPIMS) in the coating structure 200 can not only improve the film hardness of the coating structure 200 and enhance the scratch resistance and processing resistance of the coated glass, but also be more conducive to film system design and adjustment of the optical properties of the coating structure 200 such as transmittance, reflectivity, and absorptivity of light of different wavelengths.

[0077] Comparative Examples 7-10 and Examples 13-16

[0078] The present application prepares a 2.1 mm thick transparent glass substrate, and deposits the coating structure 200 of comparative examples 7-10 and embodiments 13-16 on the surface of the transparent glass substrate through a magnetron sputtering process. The coating structure 200 has three functional stacks, specifically including an innermost adhesion layer 210, a first functional stack 220, a first intermediate layer 260, a second functional stack 230, a second intermediate layer 270, a third functional stack 240 and an outermost protective layer 290 stacked in sequence. At least one of the innermost adhesion layer 210, the first intermediate layer 260, the second intermediate layer 270 and the outermost protective layer 290 includes a ZrOx layer (HiPIMS).

[0079] The sheet resistance R, pencil hardness, and alcohol wiping test results of the coating structures 200 of Comparative Examples 7-10 before and after the high-temperature heat treatment were measured, and the measurement results were recorded in Table 2.

[0080] Table 2: Measurement results of coated glass 1001 of comparative examples 7-10

[0081]

[0082]

[0083] The sheet resistance R, pencil hardness, and alcohol wiping test results of the coating structures 200 of Examples 13-16 before and after the high-temperature heat treatment were measured, and the measurement results were recorded in Table 3.

[0084] Table 3: Measurement results of coated glass 1001 of Examples 13-16

[0085]

[0086]

[0087] As can be seen from Table 2, the coating structures 200 in Comparative Examples 7-10 all have the same innermost adhesion layer 210, first functional stack 220, first intermediate layer 260, second functional stack 230, second intermediate layer 270, and third functional stack 240, with only the outermost protective layer 290 being different. Specifically, in Comparative Example 7, a ZrOx layer (n = 2.26) was deposited using a medium-frequency magnetron sputtering power source (MF) as the sub-film layer of the outermost protective layer 290 that is furthest from the first substrate 100. The pencil hardness of the coating structure 200 before and after the high-temperature heat treatment was 8H, respectively. In Comparative Example 8, a SiNx layer (n = 2.13) was deposited using a medium-frequency magnetron sputtering power source (MF) as the sub-film layer of the outermost protective layer 290 that is furthest from the first substrate 100. The pencil hardness of the coating structure 200 before and after the high-temperature heat treatment was 3H, respectively. Comparative Example 9 used a medium-frequency magnetron sputtering power source (MF) to deposit a SiZrNx layer (n = 2.17) as the sub-film layer in the outermost protective layer 290 that is farthest from the first substrate 100. The pencil hardness of the coating structure 200 before the high-temperature heat treatment was 5H, and the pencil hardness after the high-temperature heat treatment was 3H. Comparative Example 10 used a medium-frequency magnetron sputtering power source (MF) to deposit a SiZrOx layer (n = 1.59) as the sub-film layer in the outermost protective layer 290 that is farthest from the first substrate 100. The pencil hardness of the coating structure 200 before the high-temperature heat treatment was 7H, and the pencil hardness after the high-temperature heat treatment was 6H. It can be seen that the sheet resistance R of the coating structures 200 of Comparative Examples 1-4 can be reduced after the high-temperature heat treatment, and the alcohol wiping before and after the high-temperature heat treatment meets the requirements, indicating that the film system design of the coating structure 200 is reasonable. However, the pencil hardness of the coating structures 200 of Comparative Examples 3 and 4 decreased after high-temperature heat treatment, indicating that the outermost protective layers of Comparative Examples 3 and 4 cannot meet the requirements of weight bending or press bending processes used in the production of automotive glass. While the pencil hardness of the coating structure 200 of Comparative Example 2 can be increased to 4H after high-temperature heat treatment, this hardness is still relatively low, making it susceptible to scratches from hard objects during subsequent transportation, storage, handling, and processing, resulting in poor processing resistance.

[0088] As can be seen from Table 3, Example 13 uses a high-power pulsed magnetron sputtering power source (HiPIMS) to deposit a ZrOx layer (n=2.10) as the sub-film layer farthest from the first substrate 100 in the outermost protective layer 290, and the pencil hardness of the coating structure 200 before the high-temperature heat treatment is greater than 9H, and the pencil hardness after the high-temperature heat treatment is greater than 9H.

[0089] Compared to Comparative Examples 7-10, the pencil hardness of the coating structure 200 of Example 13 before high-temperature heat treatment was greater than that of the coating structures 200 of Comparative Examples 7-10 before high-temperature heat treatment, indicating that the coating structure 200 of Example 13 also had sufficient hardness before high-temperature heat treatment to meet the requirements of remote processing. Example 14 used a high-power pulsed magnetron sputtering source (HiPIMS) to deposit ZrOx layers (n=2.08) as the first and second intermediate layers. The pencil hardness of the coating structure 200 before and after high-temperature heat treatment was greater than 9H. In Example 15, a high-power pulsed magnetron sputtering power source (HiPIMS) is used to deposit a ZrOx layer (n=2.09) as the innermost adhesion layer 210 and a high-power pulsed magnetron sputtering power source (HiPIMS) is simultaneously used to deposit a ZrOx layer (n=2.10) as the sub-film layer farthest from the first substrate 100 in the outermost protective layer 290. The pencil hardness of the coating structure 200 before high-temperature heat treatment is greater than 9H, and the pencil hardness after high-temperature heat treatment is greater than 9H. In Example 16, a high-power pulsed magnetron sputtering power source (HiPIMS) is used to deposit a ZrOx layer (n=2.09) as the innermost adhesion layer 210, a high-power pulsed magnetron sputtering power source (HiPIMS) is used to deposit a ZrOx layer (n=2.08) as the first intermediate layer and the second intermediate layer, and a high-power pulsed magnetron sputtering power source (HiPIMS) is used to deposit a ZrOx layer (n=2.10) as the sub-film layer farthest from the first substrate 100 in the outermost protective layer 290. The pencil hardness of the coating structure 200 before high-temperature heat treatment is greater than 9H, and the pencil hardness after high-temperature heat treatment is greater than 9H.

[0090] In Table 3, the sheet resistance R of the coating structures 200 of Examples 13-16 after high-temperature heat treatment can be reduced to less than or equal to 1.1Ω / □, and the alcohol wiping requirements before and after the high-temperature heat treatment are met. The pencil hardness before and after the high-temperature heat treatment is greater than 9H, which proves that the use of a high-power pulsed magnetron sputtering power supply (HiPIMS) can not only promote the ionization of the ZrOy ceramic target to increase the sputtering rate, but also the prepared ZrOx layer has the advantages of a dense structure and a smooth surface, which can increase the hardness of the coating structure, improve the scratch resistance and processing resistance of the coated glass having the coating structures 200 of Examples 13-16, and can prevent the coating structure 200 from being scratched by hard objects during subsequent transportation, storage, handling, and processing, which is conducive to meeting the needs of remote processing.

[0091] Comparative Examples 11-12 and Examples 17-20

[0092] The present application prepares a 2.1 mm thick transparent glass substrate, and deposits the coating structure 200 of comparative examples 11-12 and embodiments 17-20 on the surface of the transparent glass substrate through a magnetron sputtering process. The coating structure 200 has four functional stacks, specifically including an innermost adhesion layer 210, a first functional stack 220, a first intermediate layer 260, a second functional stack 230, a second intermediate layer 270, a third functional stack 240, a third intermediate layer 280, a fourth functional stack 250 and an outermost protective layer 290 stacked in sequence. At least one of the innermost adhesion layer 210, the first intermediate layer 260, the second intermediate layer 270, the third intermediate layer 280 and the outermost protective layer 290 includes a ZrOx layer (HiPIMS).

[0093] The sheet resistance R, pencil hardness, and alcohol wiping test results of the coating structures 200 of Comparative Examples 11-12 and Example 17 before and after high-temperature heat treatment were measured, and the measurement results were recorded in Table 4.

[0094] Table 4: Measurement results of coated glass 1001 of Comparative Examples 11-12 and Example 17

[0095]

[0096]

[0097] The sheet resistance R, pencil hardness, and alcohol wiping test results of the coating structures 200 of Examples 18-20 before and after the high-temperature heat treatment were measured, and the measurement results were recorded in Table 5.

[0098] Table 5: Measurement results of coated glass 1001 of Examples 18-20

[0099]

[0100]

[0101] It can be seen from Table 4 and Table 5 that:

[0102] In comparative example 11, a medium-frequency magnetron sputtering power source (MF) is used to deposit a SiZrNx layer (n=2.17) as the sub-film layer in the outermost protective layer 290 that is farthest from the first substrate 100. The pencil hardness of the coating structure 200 before high-temperature heat treatment is 5H, and the pencil hardness after high-temperature heat treatment is 6H.

[0103] In comparative example 12, a medium-frequency magnetron sputtering power source (MF) is used to deposit a ZrOx layer (n=2.26) as the sub-film layer in the outermost protective layer 290 that is farthest from the first substrate 100. The pencil hardness of the coating structure 200 before high-temperature heat treatment is 8H, and the pencil hardness after high-temperature heat treatment is 8H.

[0104] Example 17 uses a high-power pulsed magnetron sputtering power source (HiPIMS) to deposit a ZrOx layer (n=2.10) as the sub-film layer farthest from the first substrate 100 in the outermost protective layer 290. The pencil hardness of the coating structure 200 before high-temperature heat treatment is greater than 9H, and the pencil hardness after high-temperature heat treatment is greater than 9H.

[0105] Example 18 uses a high-power pulsed magnetron sputtering power supply (HiPIMS) to deposit ZrOx layers (n=2.08) as the first intermediate layer, the second intermediate layer and the third intermediate layer. The pencil hardness of the coating structure 200 before high-temperature heat treatment is greater than 9H, and the pencil hardness after high-temperature heat treatment is greater than 9H.

[0106] In Example 19, a high-power pulsed magnetron sputtering power source (HiPIMS) is used to deposit a ZrOx layer (n=2.09) as the innermost adhesion layer 210 and a high-power pulsed magnetron sputtering power source (HiPIMS) is simultaneously used to deposit a ZrOx layer (n=2.10) as the sub-film layer farthest from the first substrate 100 in the outermost protective layer 290. The pencil hardness of the coating structure 200 before high-temperature heat treatment is greater than 9H, and the pencil hardness after high-temperature heat treatment is greater than 9H.

[0107] In Example 20, a high-power pulsed magnetron sputtering power source (HiPIMS) is used to deposit a ZrOx layer (n=2.09) as the innermost adhesion layer 210, a high-power pulsed magnetron sputtering power source (HiPIMS) is used to deposit a ZrOx layer (n=2.08) as the first intermediate layer, the second intermediate layer and the third intermediate layer, and a high-power pulsed magnetron sputtering power source (HiPIMS) is used to deposit a ZrOx layer (n=2.10) as the sub-film layer farthest from the first substrate 100 in the outermost protective layer 290. The pencil hardness of the coating structure 200 before high-temperature heat treatment is greater than 9H, and the pencil hardness after high-temperature heat treatment is greater than 9H.

[0108] Compared with Comparative Examples 11 and 12, the pencil hardness of the coating structure 200 of Examples 17-20 before high-temperature heat treatment is greater than the pencil hardness of the coating structure 200 of Comparative Examples 11-12 before high-temperature heat treatment, indicating that the coating structure 200 of Examples 17-20 also has sufficient hardness before high-temperature heat treatment to meet the requirements of remote processing.

[0109] In Tables 4 and 5, the sheet resistance R of the coating structures 200 of Examples 17-20 after high-temperature heat treatment can be reduced to less than or equal to 0.9Ω / □, and the alcohol wiping requirements before and after the high-temperature heat treatment are met, and the pencil hardness before and after the high-temperature heat treatment is greater than 9H, which proves that the use of a high-power pulsed magnetron sputtering power supply (HiPIMS) can not only promote the ionization of the ZrOy ceramic target to increase the sputtering rate, but also the prepared ZrOx layer has the advantages of dense structure and smooth surface, which can improve the hardness of the coating structure, enhance the scratch resistance and processing resistance of the coated glass having the coating structure 200 of Examples 17-20, and can prevent the coating structure 200 from being scratched by hard objects during subsequent transportation, storage, handling, and processing, which is conducive to meeting the needs of off-site processing.

[0110] The above is a detailed introduction to the embodiments of the present application. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method and core idea of ​​the present application. At the same time, for those skilled in the art, according to the idea of ​​the present application, there may be changes in the specific implementation methods and application scope. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. A coated glass, characterized in that: The coated glass comprises: a first substrate; and A coating structure is provided on at least one surface of the first substrate, comprising an innermost adhesion layer, at least one functional stack, and an outermost protective layer stacked in sequence, wherein the innermost adhesion layer comprises a ZrOx layer, and the material of the outermost protective layer is selected from oxides, nitrides, or oxynitrides of at least one element selected from Si, Zn, Mg, Sn, Ti, Nb, Zr, Ni, In, Al, Ce, W, Mo, Sb, and Bi. Each of the functional stacks comprises a metal layer and two dielectric layers, wherein the metal layer is located between the two dielectric layers, and the ZrOx layer is located on a side of the dielectric layer facing away from the metal layer, wherein x satisfies 1<x≤2, and the refractive index n of the ZrOx layer satisfies the range of 2.00≤n≤2.

18. The ZrOx layer is deposited by magnetron sputtering using a high-power pulsed magnetron sputtering power supply.

2. The coated glass according to claim 1, characterized in that: The pencil hardness of the coating structure is greater than or equal to 9H.

3. The coated glass according to claim 1, wherein: The material of the metal layer is selected from any one metal or metal alloy of silver, gold, copper, aluminum, and platinum, and the physical thickness of the metal layer is 5nm to 20nm.

4. The coated glass according to claim 1, wherein: The material of the dielectric layer is selected from oxides of at least one metal or metal alloy of Zn, Mg, Sn, Ti, Nb, Zr, Ni, In, Al, Ce, W, Mo, Sb, and Bi, and the physical thickness of the dielectric layer is 5 nm to 30 nm.

5. The coated glass according to claim 1, characterized in that: The coating structure includes an innermost adhesion layer, a first functional stack, and an outermost protective layer stacked in sequence, and the outermost protective layer includes the ZrOx layer.

6. The coated glass according to claim 1, characterized in that: The coating structure includes the innermost adhesion layer, the first functional stack, the first intermediate layer, the second functional stack and the outermost protective layer stacked in sequence, and at least one of the first intermediate layer and the outermost protective layer includes the ZrOx layer.

7. The coated glass according to claim 1, characterized in that: The coating structure includes the innermost adhesion layer, the first functional stack, the first intermediate layer, the second functional stack, the second intermediate layer, the third functional stack and the outermost protective layer stacked in sequence, and at least one of the first intermediate layer, the second intermediate layer and the outermost protective layer includes the ZrOx layer.

8. The coated glass according to claim 1, characterized in that: The coating structure includes the innermost adhesion layer, the first functional stack, the first intermediate layer, the second functional stack, the second intermediate layer, the third functional stack, the third intermediate layer, the fourth functional stack and the outermost protective layer stacked in sequence, and at least one of the first intermediate layer, the second intermediate layer, the third intermediate layer and the outermost protective layer includes the ZrOx layer.

9. The coated glass according to any one of claims 5 to 8, characterized in that: The innermost adhesion layer includes a ZrOx layer with a physical thickness of 10nm to 40nm.

10. The coated glass according to any one of claims 5 to 8, characterized in that: The outermost protective layer includes a ZrOx layer with a physical thickness of 5nm to 35nm.

11. The coated glass according to any one of claims 6 to 8, characterized in that: At least one of the first intermediate layer, the second intermediate layer, and the third intermediate layer includes a ZrOx layer having a physical thickness of 30 nm to 70 nm.

12. The coated glass according to any one of claims 5 to 8, characterized in that: The specific structure of the outermost protective layer is: TiOx layer / ZnSnOx layer / the ZrOx layer.

13. The coated glass according to claim 1, characterized in that: The extinction coefficient k of the ZrOx layer is less than or equal to 0.0001.

14. A laminated glass, characterized in that: The method comprises a second substrate, an adhesive layer and the coated glass according to any one of claims 1 to 13, wherein the adhesive layer is connected between the second substrate and the coated glass, and the coating structure is located between the first substrate and the second substrate.

15. The laminated glass according to claim 14, characterized in that: The first substrate is transparent glass or extra-transparent glass, the total iron content of the transparent glass is less than or equal to 0.1%, and the visible light transmittance of the transparent glass is greater than or equal to 80%; the total iron content of the extra-transparent glass is less than or equal to 0.015%, and the visible light transmittance of the extra-transparent glass is greater than or equal to 90%.

16. A method for preparing coated glass, characterized in that: Providing a first substrate: forming a coating structure on at least one surface of the first substrate by a magnetron sputtering process; The coating structure includes an innermost adhesion layer, at least one functional stack, and an outermost protective layer stacked in sequence, wherein the innermost adhesion layer includes a ZrOx layer, and the material of the outermost protective layer is selected from oxides, nitrides, or oxynitrides of at least one element selected from Si, Zn, Mg, Sn, Ti, Nb, Zr, Ni, In, Al, Ce, W, Mo, Sb, and Bi. Each of the functional stacks includes a metal layer and two dielectric layers, wherein the metal layer is located between the two dielectric layers, and any ZrOx layer is formed on a side of the dielectric layer facing away from the metal layer, wherein x satisfies 1<x≤2, and the refractive index n of the ZrOx layer satisfies the range of 2.00≤n≤2.

18. The target power supply for magnetron sputtering the ZrOx layer is a high-power pulsed magnetron sputtering power supply.

17. The method for preparing coated glass according to claim 16, wherein: The target material for magnetron sputtering the ZrOx layer is a ZrOy ceramic target, wherein y satisfies 1.4≤y<2.

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