Coated glass and preparation method therefor, and laminated glass

Abstract

Provided in the present application are coated glass and a preparation method therefor, and laminated glass. The coated glass comprises a first substrate and a coating structure, which is arranged on at least one surface of the first substrate. The coating structure comprises at least one functional laminated layer, each of which comprises a lower dielectric layer, a metal layer and an upper dielectric layer, which are sequentially stacked, wherein at least one of the lower dielectric layer and the upper dielectric layer comprises a ZrOx layer, x satisfying 1<x≤2, and the extinction coefficient k of the ZrOx layer being less than or equal to 0.0001. The technical solution in the present application enables the coating structure to have better levels of heat treatment stability and overall mechanical stability.

Description

Coated glass and preparation method thereof, laminated glass

[0001] This application claims priority to the Chinese patent application filed with the China Patent Office on August 11, 2023, with application number 202311013182.1 and application name “Coated glass and its preparation method, laminated glass”, the entire contents of which are incorporated by reference into this application. Technical Field

[0002] 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

[0003] 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.

[0004] When manufacturing coated glass for use as insulating glass or electrically heated glass in motor vehicles, it also needs to undergo high-temperature heat treatment at at least 500°C and bending forming, such as the baking and press bending processes for automotive glass. Since the silver layer is easily corroded and oxidized, dielectric layers need to be provided above and below each silver layer. These dielectric layers are used to protect the silver layer from being damaged during subsequent processing such as the baking and press bending processes. Although the dielectric layer in traditional coated glass can improve the mechanical and thermal stability of the film layer, its oxygen barrier capacity is poor, causing the coated glass to fog after heat treatment. In particular, coated glass including 3-4 silver layers also has defects such as poor film adhesion and redness of the film edge.

[0005] Summary of the Invention

[0006] The embodiments of the present application provide a coated glass and a preparation method thereof, and laminated glass, which can enable the coating structure to have better thermal treatment stability and overall mechanical stability.

[0007] In a first aspect, the present application provides a coated glass, comprising:

[0008] a first substrate; and

[0009] A coating structure is provided on at least one surface of the first substrate, the coating structure comprising at least one functional stack, each functional stack comprising a lower dielectric layer, a metal layer, and an upper dielectric layer stacked in sequence, at least one of the lower dielectric layer and the upper dielectric layer comprising a ZrOx layer, wherein x satisfies 1<x≤2, and an extinction coefficient k of the ZrOx layer is less than or equal to 0.0001.

[0010] It can be understood that a ZrOx layer with an extinction coefficient k less than or equal to 0.0001 is more stable during high-temperature heat treatment, effectively isolating the external high-temperature heat from being transferred to the metal layer, allowing the coated glass to withstand higher-temperature heat treatments. Furthermore, a ZrOx layer with an extinction coefficient k less than or equal to 0.0001 can better isolate oxygen ions from diffusing into the metal layer, resulting in minimal fogging and no edge reddening of the coated structure after heat treatment. Furthermore, a ZrOx layer with an extinction coefficient k less than or equal to 0.0001 exhibits stronger film-to-substrate bonding, preventing separation from the glass during processing due to weak interlayer bonding, thereby improving the overall mechanical stability of the coated structure.

[0011] In a possible implementation, the haze of the coated glass is less than or equal to 0.25%.

[0012] In a possible implementation manner, the refractive index n of the ZrOx layer satisfies the range: 2.00≤n≤2.18.

[0013] 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-20 nm.

[0014] In a possible implementation manner, the upper dielectric layer includes two ZrOx layers, wherein the refractive index of one ZrOx layer is greater than the refractive index of the other ZrOx layer.

[0015] In one possible embodiment, the number of the functional stack is one, the coating structure includes an innermost adhesion layer, the lower dielectric layer, the metal layer, the upper dielectric layer and an outermost protective layer stacked in sequence, and the upper dielectric layer includes 1-3 ZrOx layers.

[0016] In one possible embodiment, the number of the functional stacks is two, the two functional stacks are respectively a first stack and a second stack, the coating structure includes an innermost adhesion layer, the first stack, an intermediate layer, the second stack and an outermost protective layer stacked in sequence, and at least one of the upper dielectric layer of the first stack and the upper dielectric layer of the second stack includes 1-3 ZrOx layers.

[0017] In one possible embodiment, the number of the functional stacks is three, and the three functional stacks are respectively a first stack, a second stack, and a third stack. The coating structure also includes two intermediate layers, and the two intermediate layers are respectively a first intermediate layer and a second intermediate layer. The coating structure includes an innermost adhesion layer, the first stack, the first intermediate layer, the second stack, the second intermediate layer, the third stack, and an outermost protective layer stacked in sequence. At least one of the upper dielectric layer of the first stack, the upper dielectric layer of the second stack, and the upper dielectric layer of the third stack includes 1-3 ZrOx layers.

[0018] In one possible embodiment, the number of the functional stacks is four, and the four functional stacks are respectively a first stack, a second stack, a third stack, and a fourth stack. The coating structure also includes three intermediate layers, and the three intermediate layers are respectively a first intermediate layer, a second intermediate layer, and a third intermediate layer. The coating structure includes an innermost adhesion layer, the first stack, the first intermediate layer, the second stack, the second intermediate layer, the third stack, the third intermediate layer, the fourth stack, and an outermost protective layer stacked in sequence. At least one of the upper dielectric layer of the first stack, the upper dielectric layer of the second stack, the upper dielectric layer of the third stack, and the upper dielectric layer of the fourth stack includes 1-3 ZrOx layers.

[0019] In one possible embodiment, the ZrOx layer in the upper dielectric layer is in direct contact with the metal layer, or a barrier layer is provided between the ZrOx layer and the metal layer, the barrier layer is in direct contact with the metal layer, the physical thickness of the barrier layer is less than or equal to 5 nm, and the material of the barrier layer is selected from at least one metal or metal alloy of Ti, Ni, Cr, Nb, and W.

[0020] In one possible embodiment, the upper dielectric layer further includes an upper dielectric sublayer, which is located on the side of the ZrOx layer facing away from the metal layer, and the material of the upper dielectric sublayer includes an oxide of at least one metal or metal alloy selected from the group consisting of Zr, Zn, Mg, Sn, Ti, Nb, Ni, In, Al, Ce, W, Mo, Sb, and Bi.

[0021] In one possible embodiment, the lower dielectric layer includes a first sublayer in direct contact with the metal layer, and the material of the first sublayer includes an oxide of at least one metal or metal alloy selected from the group consisting of Zn, Mg, Sn, Ti, Nb, Ni, In, Al, Ce, W, Mo, Sb, and Bi.

[0022] In a possible implementation manner, the lower dielectric layer further includes a second sublayer, the second sublayer is located on a side of the first sublayer away from the metal layer, and the second sublayer is the ZrOx layer.

[0023] In one possible embodiment, the physical thickness of the innermost adhesion layer is 10nm-40nm, the physical thickness of the upper dielectric layer or the lower dielectric layer is 5nm-30nm, the physical thickness of the middle layer is 30nm-70nm, and the physical thickness of the outermost protective layer is 5nm-70nm.

[0024] In one possible embodiment, the specific structure of the outermost protective layer is: TiOx layer / ZnSnOx layer / outermost sublayer, the physical thickness of the outermost sublayer is 5nm-50nm, and the material of the outermost sublayer includes at least one of SiAlZrNx, SiZrNx, SiNx, SiZrOx and SiAlZrOx.

[0025] In a second aspect, the present application provides a laminated glass comprising a second substrate, an adhesive layer and the coated glass, 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.

[0026] 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%.

[0027] In a third aspect, the present application further provides a method for preparing coated glass, comprising:

[0028] Providing a first substrate:

[0029] forming a coating structure on at least one surface of the first substrate by a magnetron sputtering process;

[0030] The coating structure includes at least one functional stack, each of which includes a lower dielectric layer, a metal layer, and an upper dielectric layer stacked in sequence, at least one of the lower dielectric layer and the upper dielectric layer includes a ZrOx layer, where x satisfies 1<x≤2, and the extinction coefficient k of the ZrOx layer is less than or equal to 0.0001.

[0031] 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

[0032] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments of the present application will be described below.

[0033] FIG1 is a schematic structural diagram of a laminated glass provided in an embodiment of the present application;

[0034] FIG2 is a schematic cross-sectional view of a first embodiment of the coated glass shown in FIG1 ;

[0035] FIG3 is a schematic cross-sectional view of a second embodiment of the coated glass shown in FIG1 ;

[0036] FIG4 is a schematic cross-sectional view of a third embodiment of the coated glass shown in FIG1 ;

[0037] FIG5 is a schematic cross-sectional view of a fourth embodiment of the coated glass shown in FIG1 ;

[0038] FIG6 is a schematic flow chart of a method for preparing coated glass provided in an embodiment of the present application. DETAILED DESCRIPTION

[0039] For ease of understanding, the terms involved in the embodiments of the present application are first explained.

[0040] 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.

[0041] Multiple: refers to two or more than two.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] The specific implementation of the present application will be clearly described below with reference to the accompanying drawings.

[0046] Please refer to Figure 1, which is a schematic diagram of the structure of a laminated glass 1000 provided in an embodiment of the present application. Laminated glass 1000 includes 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 disposed 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, i.e., the side of the first substrate 100 provided with the coating structure 200 is connected to the adhesive layer 1002. The coating structure 200 includes at least one functional stack. Each functional stack includes a lower dielectric layer, a metal layer, and an upper dielectric layer stacked in sequence. At least one of the lower dielectric layer and the upper dielectric layer includes a ZrOx layer, where x satisfies 1<x≤2, and the extinction coefficient k of the ZrOx layer is less than or equal to 0.0001. A ZrOx layer with an extinction coefficient k less than or equal to 0.0001 performs more stably during high-temperature heat treatment, effectively isolating the external high-temperature heat from being conducted to the metal layer, allowing the coated glass to withstand higher-temperature heat treatment. Furthermore, a ZrOx layer with an extinction coefficient k less than or equal to 0.0001 can better isolate oxygen ions from diffusing into the metal layer, resulting in extremely slight fogging of the coating structure after heat treatment and no edge reddening, allowing the haze of the coated glass 1001 to be less than or equal to 0.25%, or even less than or equal to 0.20%.

[0047] It should be noted that FIG1 is intended only to schematically illustrate the connection relationship between the coated glass 1001, the adhesive layer 1002, and the second substrate 1003, and does not specifically limit the connection position, specific structure, or quantity of each device. The structure illustrated in the embodiment of this application does not constitute a specific limitation on the laminated glass 1000. In other embodiments of this application, the laminated glass 1000 may include more or fewer components than shown in FIG1, or may combine or separate certain components, or arrange the components differently. The components shown in FIG1 may be implemented in hardware, software, or a combination of software and hardware.

[0048] 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, among others. The lower dielectric layer, metal layer, and upper dielectric layer in each functional stack can be formed separately by a magnetron sputtering process. In the direction away from the first substrate 100, the lower dielectric layer in the functional stack is located below the metal layer in the functional stack, i.e., the lower dielectric layer is closer to the first substrate 100 than the metal layer; and the upper dielectric layer in the functional stack is located above the metal layer in the functional stack, i.e., the upper dielectric layer in the functional stack is further away from the first substrate 100 than the metal layer in the functional stack.

[0049] 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.

[0050] Both the first substrate 100 and the second substrate 1003 may be transparent glass or ultra-clear glass (ultra-white glass). 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%. 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%. Calculated by weight percentage, the first substrate 100 and the second substrate 1003 may include 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.

[0051] 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.

[0052] In a first possible embodiment, please refer to FIG2 , which is a schematic cross-sectional view of the first embodiment of the coated glass 1001 shown in FIG1 . The number of functional stacks in the coating structure 200 is one. The coating structure 200 includes an innermost adhesion layer 210, a first lower dielectric layer 221, a first metal layer 222, a first upper dielectric layer 223, and an outermost protective layer 290, which are stacked in sequence. The first lower dielectric layer 221, the first metal layer 222, and the first upper dielectric layer 223 constitute a functional stack. The first upper dielectric layer 223 includes one to three ZrOx layers.

[0053] In a second possible embodiment, please refer to FIG3 , which is a schematic cross-sectional view of the second embodiment of the coated glass 1001 shown in FIG1 . The coating structure 200 includes two functional stacks: a first stack 220 and a second stack 230. The first stack 220 includes a first lower dielectric layer 221, a first metal layer 222, and a first upper dielectric layer 223. The second stack 230 includes a second lower dielectric layer 231, a second metal layer 232, and a second upper dielectric layer 233. The coating structure 200 specifically includes an innermost adhesion layer 210, a first lower dielectric layer 221, a first metal layer 222, a first upper dielectric layer 223, an intermediate layer 260, a second lower dielectric layer 231, a second metal layer 232, a second upper dielectric layer 233, and an outermost protective layer 290, stacked in sequence. At least one of the first upper dielectric layer 223 and the second upper dielectric layer 233 includes one to three ZrOx layers.

[0054] In a third possible embodiment, please refer to FIG4 , which is a schematic cross-sectional view of the third embodiment of the coated glass 1001 shown in FIG1 . The coating structure 200 includes three functional stacks: a first stack 220, a second stack 230, and a third stack 240. The first stack 220 includes a first lower dielectric layer 221, a first metal layer 222, and a first upper dielectric layer 223. The second stack 230 includes a second lower dielectric layer 231, a second metal layer 232, and a second upper dielectric layer 233. The third stack 240 includes a third lower dielectric layer 241, a third metal layer 242, and a third upper dielectric layer 243. The coating structure also includes two intermediate layers: a first intermediate layer 260 and a second intermediate layer 270. The coating structure 200 specifically includes an innermost adhesion layer 210, a first lower dielectric layer 221, a first metal layer 222, a first upper dielectric layer 223, a first intermediate layer 260, a second lower dielectric layer 231, a second metal layer 232, a second upper dielectric layer 233, a second intermediate layer 270, a third lower dielectric layer 241, a third metal layer 242, a third upper dielectric layer 243 and an outermost protective layer 290, which are stacked in sequence. At least one of the first upper dielectric layer 223, the second upper dielectric layer 233 and the third upper dielectric layer 243 includes 1-3 ZrOx layers.

[0055] In a fourth possible embodiment, please refer to FIG5 , which is a schematic cross-sectional view of the fourth embodiment of the coated glass 1001 shown in FIG1 . The coating structure 200 includes four functional stacks, namely a first stack 220, a second stack 230, a third stack 240, and a fourth stack 250. The first stack 220 includes a first lower dielectric layer 221, a first metal layer 222, and a first upper dielectric layer 223. The second stack 230 includes a second lower dielectric layer 231, a second metal layer 232, and a second upper dielectric layer 233. The third stack 240 includes a third lower dielectric layer 241, a third metal layer 242, and a third upper dielectric layer 243. The fourth stack 250 includes a fourth lower dielectric layer 251, a fourth metal layer 252, and a fourth upper dielectric layer 253. The coating structure also includes three intermediate layers, namely a first intermediate layer 260, a second intermediate layer 270, and a third intermediate layer 280. The coating structure 200 specifically includes an innermost adhesion layer 210, a first lower dielectric layer 221, a first metal layer 222, a first upper dielectric layer 223, a first intermediate layer 260, a second lower dielectric layer 231, a second metal layer 232, a second upper dielectric layer 233, a second intermediate layer 270, a third lower dielectric layer 241, a third metal layer 242, a third upper dielectric layer 243, a third intermediate layer 280, a fourth lower dielectric layer 251, a fourth metal layer 252, a fourth upper dielectric layer 253 and an outermost protective layer 290, which are stacked in sequence. At least one of the first upper dielectric layer 223, the second upper dielectric layer 233, the third upper dielectric layer 243 and the fourth upper dielectric layer includes 1-3 ZrOx layers.

[0056] In Figures 2, 3, 4, and 5, 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 also increases the adhesion between the coating structure 200 and the surface of the first substrate 100 and helps adjust the mechanical, optical, and high-temperature heat-treatment properties of the coating structure 200. The innermost adhesion layer 210 comprises all film layers between the surface of the first substrate 100 and the first stack 220. The innermost adhesion layer 210 can be a single film layer or comprised of multiple sub-film layers. In some embodiments, the physical thickness of the innermost adhesion layer 210 is 10 nm to 40 nm, and the material of the innermost adhesion layer 210 can 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.

[0057] In each functional stack, the upper dielectric layer primarily protects the metal layer from oxygen ion damage. The physical thickness of the upper dielectric layer ranges from 5nm to 30nm. The upper dielectric layer can be a single layer or composed of multiple sub-layers. Preferably, the upper dielectric layer includes one to three ZrOx layers with an extinction coefficient k less than or equal to 0.0001. The ZrOx layers exhibit greater stability during high-temperature heat treatment, effectively isolating the metal layer from external heat transfer, enabling the coated glass to withstand higher-temperature heat treatments. Furthermore, the ZrOx layers with an extinction coefficient k less than or equal to 0.0001 can better isolate oxygen ions from diffusing into the metal layer, resulting in minimal fogging of the coated structure after heat treatment and no edge reddening. This results in a haze of less than or equal to 0.25%, or even less than or equal to 0.20%, for the coated glass 1001. Preferably, the extinction coefficient of the ZrOx layer is k≤0.00009, or k≤0.00008, k≤0.00007, k≤0.00006, k≤0.00005, etc.

[0058] Among them, the ZrOx layer in the upper dielectric layer is in direct contact with the metal layer, or a barrier layer is provided between the ZrOx layer and the metal layer, the barrier layer is in direct contact with the metal layer, the physical thickness of the barrier layer is less than or equal to 5 nm, and the material of the barrier layer is selected from at least one metal or metal alloy of Ti, Ni, Cr, Nb, and W. The barrier layer is mainly used to prevent the metal layer from contacting the oxidizing reaction gas during the magnetron sputtering process and to improve the optical properties of the coating structure 200.

[0059] In some embodiments, the upper dielectric layer may be a single film layer. When the single film layer is a ZrOx layer, the ZrOx layer is in direct contact with the metal layer or in direct contact with the barrier layer. In other embodiments, the upper dielectric layer may also be composed of multiple sub-film layers, and one, two, or three of the multiple sub-film layers are ZrOx layers. When one of the multiple sub-film layers is a ZrOx layer, the ZrOx layer is in direct contact with the metal layer or in direct contact with the barrier layer. When two of the multiple sub-film layers are ZrOx layers, the refractive index of one of the ZrOx layers is greater than the refractive index of the other ZrOx layer, and the ZrOx layer with the larger refractive index is in direct contact with the metal layer or in direct contact with the barrier layer. When three of the multiple sub-film layers are ZrOx layers, the refractive index of one of the ZrOx layers is greater than the refractive index of the other two ZrOx layers, and the ZrOx layer with the larger refractive index is in direct contact with the metal layer or in direct contact with the barrier layer. In some other embodiments, the multiple sub-film layers also include an upper dielectric sub-layer, which is located on the side of the ZrOx layer facing away from the metal layer. The material of the upper dielectric sub-layer includes an oxide of at least one metal or metal alloy selected from the group consisting of Zr, Zn, Mg, Sn, Ti, Nb, Ni, In, Al, Ce, W, Mo, Sb, and Bi, such as ZnO, AZO, and ZnSnOx.

[0060] In each functional stack, the lower dielectric layer is primarily used to protect the metal layer from damage by alkali metal ions and to serve as a crystallization seed layer for the metal layer to improve its deposition density. The physical thickness of the lower dielectric layer is 5nm-30nm. The lower dielectric layer can be a single film layer or composed of multiple sub-film layers. In some embodiments, the lower dielectric layer includes a first sub-layer in direct contact with the metal layer. The material of the first sub-layer includes an oxide of at least one metal or metal alloy selected from Zn, Mg, Sn, Ti, Nb, Ni, In, Al, Ce, W, Mo, Sb, and Bi, such as ZnO, AZO, or ZnSnOx. In other embodiments, the lower dielectric layer further includes a second sub-layer, located on the side of the first sub-layer facing away from the metal layer. The second sub-layer is a ZrOx layer.

[0061] In Figures 3, 4, and 5, 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 physical thickness of the intermediate layers ranges from 30 nm to 70 nm. Specifically, the first intermediate layer 260 is located between the first upper dielectric layer 223 and the second lower dielectric layer 231, the second intermediate layer 270 is located between the second upper dielectric layer 233 and the third lower dielectric layer 241, and the third intermediate layer 280 is located between the third upper dielectric layer 243 and the fourth lower 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, the materials of the first intermediate layer 260, the second intermediate layer 270 and the third intermediate layer 280 can 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.

[0062] In Figures 2, 3, 4, and 5, an outermost protective layer 290 is deposited on the outside of the functional stack farthest from the first substrate 100. The outermost protective layer 290 in Figure 2 is deposited on the side of the functional stack farthest from the first substrate 100. The outermost protective layer 290 in Figure 3 is deposited on the side of the second stack 230 farthest from the first substrate 100. The outermost protective layer 290 in Figure 4 is deposited on the side of the third stack 240 farthest from the first substrate 100. The outermost protective layer 290 in Figure 5 is deposited on the side of the fourth stack 250 farthest 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 properties, optical properties, and high-temperature heat treatment performance of the coating structure 200. The outermost protective layer 290 comprises all film layers on the outside of the functional stack farthest from the first substrate 100 in the coating structure 200. The outermost protective layer 290 can be a single film layer or composed of multiple sub-film layers. The physical thickness of the outermost protection layer 290 may be between 5 nm and 70 nm (including endpoints of 5 nm and 70 nm).

[0063] In some embodiments, the material of the outermost protective layer 290 can also be selected from the oxide, nitride or nitrogen oxide 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, etc.

[0064] 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 / outermost sub-layer 293, the physical thickness of the outermost sub-layer 293 is 5nm-50nm, the material of the outermost sub-layer 293 includes at least one of SiAlZrNx, SiZrNx, SiNx, SiZrOx and SiAlZrOx, the physical thickness of the TiOx layer 291 is less than or equal to 20nm, and the physical thickness of the ZnSnOx layer 292 is less than or equal to 20nm. The structure of TiOx layer 291 / ZnSnOx layer 292 / outermost sub-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.

[0065] 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.

[0066] The present application also provides a method for preparing coated glass 1001. Please refer to FIG6 , which is a flow chart of a method for preparing coated glass 1001 provided in an embodiment of the present application. The preparation method includes:

[0067] S100: providing a first substrate 100.

[0068] S200: forming a coating structure 200 on at least one surface of the first substrate 100 by a magnetron sputtering process;

[0069] The coating structure 200 includes at least one functional stack, each functional stack includes a lower dielectric layer, a metal layer and an upper dielectric layer stacked in sequence, at least one of the lower dielectric layer and the upper dielectric layer includes a ZrOx layer, where x satisfies 1<x≤2, and the extinction coefficient k of the ZrOx layer is less than or equal to 0.0001.

[0070] 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.

[0071] The use of HiPIMS power supply to deposit the ZrOx layer (HiPIMS) changes the density of the ZrOx layer (HiPIMS), and thus changes the refractive index n and extinction coefficient k of the ZrOx layer (HiPIMS). The refractive index n of the ZrOx layer obtained by magnetron sputtering using HiPIMS power supply is 2.00~2.18, and the extinction coefficient k≤0.0001, which is conducive to expanding the application range of the ZrOx layer (HiPIMS).

[0072] The extinction coefficient k can be exemplified by 0.0001, 0.00009, 0.00008, 0.00007, 0.00006, 0.00005, 0.00004, 0.00003, 0.00002, 0.00001, or even less than 0.00001. Preferably, the extinction coefficient k of the ZrOx layer is ≤ 0.00005. The refractive index n can be exemplified by 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 to 2.15.

[0073] Comparative Examples 1-6 and Examples 1-12

[0074] In the present application, a 2.1 mm thick transparent glass substrate was prepared, and the film structures of Comparative Examples 1-6 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 1-6 and Examples 1-12 before high-temperature heat treatment was measured, and the refractive index n and extinction coefficient k of Comparative Examples 2-6 and Examples 1-12 after high-temperature heat treatment were measured. The measurement results are recorded in Table 1.

[0075] Comparative Example 1: transparent glass substrate / Ag layer.

[0076] 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%.

[0077] 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%.

[0078] 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%.

[0079] 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%.

[0080] Among them, the target material of the Ag layer in the magnetron sputtering comparative examples 1-6 and embodiments 1-12 is a silver metal target, the process gas is Ar, and the target power supply is a direct current (DC) power supply.

[0081] Table 1: Measurement results of coated glass test samples of Comparative Examples 1-6 and Examples 1-12

[0082] As can be seen from Table 1, the hardness of the Ag layer in Comparative Example 1 is poor, the extinction coefficient k of the DLC layer (HiPIMS) deposited on the Ag layer in Comparative Example 2 is much greater than 0.0001, the extinction coefficient k of the AZO layer (MF) deposited on the Ag layer in Comparative Example 3 is greater than 0.0001, and the extinction coefficient k of the ZrOx layer (MF) deposited on the Ag layer in Comparative Examples 4-6 are all greater than 0.001. Compared with Comparative Examples 1-6, Example 1-12 adopts a high-power pulsed magnetron sputtering power supply (HiPIMS) as a target power supply, which can reduce the extinction coefficient k of the ZrOx layer (HiPIMS) to less than 0.0001, or even less than or equal to 0.00005, and even less than or equal to 0.00001. Obviously, the ZrOx layer (HiPIMS) has a lower extinction coefficient than the DLC layer, the AZO layer and even the ZrOx layer (MF). The ZrOx layer (HiPIMS) is more conducive to use in the lower dielectric layer and the upper dielectric layer of the functional stack, and is particularly suitable for use in the upper dielectric layer of the functional stack, so as to better isolate the external high-temperature heat from being conducted to the metal layer and better isolate the oxygen ions from diffusing into the metal layer.

[0083] 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.

[0084] 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.

[0085] Comparative Examples 7-9 and Examples 13-17

[0086] The present application prepares a 2.1 mm thick transparent glass substrate, and deposits the coating structure 200 of comparative examples 7-9 and embodiments 13-17 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 lower dielectric layer 221, a first metal layer 222, a first upper dielectric layer 223, a first intermediate layer 260, a second lower dielectric layer 231, a second metal layer 232, a second upper dielectric layer 233, a second intermediate layer 270, a third lower dielectric layer 241, a third metal layer 242, a third upper dielectric layer 243 and an outermost protective layer 290 stacked in sequence. At least one of the first upper dielectric layer 223, the second upper dielectric layer 233 and the third upper dielectric layer 243 includes 1-3 ZrOx layers (HiPIMS).

[0087] The sheet resistance R, pencil hardness, and alcohol wiping test results of the coating structures 200 of Comparative Examples 7-9 and Example 13 before and after high-temperature heat treatment were measured. The overall appearance and edge appearance of the coated glass 1001 of Comparative Examples 7-9 and Example 13 after high-temperature heat treatment were observed. The haze of the coated glass 1001 of Comparative Examples 7-9 and Example 13 after high-temperature heat treatment was also measured. The measurement results are recorded in Table 2.

[0088] Table 2: Measurement results of coated glass 1001 of Comparative Examples 7-9 and Example 13

[0089] The sheet resistance R, pencil hardness, and alcohol wiping test results of the coating structures 200 of Examples 14-17 before and after the high-temperature heat treatment were measured. The overall appearance and edge appearance of the coated glass 1001 of Examples 14-17 after the high-temperature heat treatment were observed. The haze of the coated glass 1001 of Examples 14-17 after the high-temperature heat treatment was also measured. The measurement results are recorded in Table 3.

[0090] Table 3: Measurement results of coated glass 1001 of Examples 14-17

[0091] From Table 2 and Table 3 we can see that:

[0092] In comparative example 7, a medium-frequency magnetron sputtering power source (MF) was used to deposit an AZO layer (n=1.94, k=0.04041) as the first upper dielectric layer in the first stack, the second upper dielectric layer in the second stack, and the third upper dielectric layer in the third stack. The coating structure 200 showed film shedding after only 10 alcohol wiping tests before high-temperature heat treatment, indicating that the film adhesion was poor, which was not conducive to subsequent deep processing. Moreover, the coating structure 200 showed slight fogging after the high-temperature heat treatment.

[0093] In Comparative Example 8, a medium-frequency magnetron sputtering power source (MF) was used to deposit an AZO layer (n=1.94, k=0.04041) as the first upper dielectric layer in the first stack, the second upper dielectric layer in the second stack, and the third upper dielectric layer in the third stack, and a NiCr layer (n=2.55, k=1.22) was added between each metal layer and the upper dielectric layer as a barrier layer. The coating structure 200 met the requirements of the alcohol wiping test before the high-temperature heat treatment and reduced the haze after the high-temperature heat treatment. However, because the extinction coefficient k of the AZO layer and the NiCr layer was much larger than 0.0001, the local edge area of ​​the coated glass 1001 absorbed more heat due to the dark ink during the high-temperature heat treatment, ultimately resulting in a reddish appearance of the edge.

[0094] In Comparative Example 9, a medium-frequency magnetron sputtering power source (MF) was used to deposit an AZO layer (n=1.94, k=0.04041) as the first upper dielectric layer in the first stack, the second upper dielectric layer in the second stack, and the third upper dielectric layer in the third stack, and a NiCrOx layer (n=2.90, k=1.42) was added between each metal layer and the upper dielectric layer as a barrier layer. The coating structure 200 met the requirements of the alcohol wiping test before the high-temperature heat treatment and reduced the haze after the high-temperature heat treatment. However, because the extinction coefficient k of the AZO layer and the NiCr layer was much greater than 0.0001, the local edge area of ​​the coated glass 1001 absorbed more heat due to the dark ink during the high-temperature heat treatment, ultimately resulting in a reddish appearance at the edge.

[0095] In Example 13, a high-power pulsed magnetron sputtering power source (HiPIMS) was used to deposit a ZrOx layer (n=2.10, k=0.00002) as the first upper dielectric layer in the first stack, the second upper dielectric layer in the second stack, and the third upper dielectric layer in the third stack. The coating structure 200 met the requirements of the alcohol wiping test before the high-temperature heat treatment and reduced the haze after the high-temperature heat treatment, so that the haze of the coated glass 1001 after the high-temperature heat treatment was less than 0.25%, and the overall appearance was uniform, and there was no redness on the edge appearance.

[0096] In Example 14, a high-power pulsed magnetron sputtering power source (HiPIMS) was used to deposit a ZrOx layer (n=2.11, k=0.00002), and a medium-frequency magnetron sputtering power source (MF) was used to deposit an AZO layer (n=1.976, k=0.00047) as the first upper dielectric layer in the first stack, the second upper dielectric layer in the second stack, and the third upper dielectric layer in the third stack. The ZrOx layer (n=2.11, k=0.00002) in each upper dielectric layer was in direct contact with the metal layer, and the AZO layer in each upper dielectric layer was located on the side of the ZrOx layer (n=2.11, k=0.00002) facing away from the metal layer. The coating structure 200 met the requirements of the alcohol wiping test before the high-temperature heat treatment and reduced the haze after the high-temperature heat treatment, so that the haze of the coated glass 1001 after the high-temperature heat treatment was less than or equal to 0.20%, and the overall appearance was uniform, and there was no redness on the edge appearance.

[0097] Example 15: A high power pulsed magnetron sputtering power source (HiPIMS) was used to deposit a ZrOx layer (n = 2.15, k = 0.00005) and a ZrOx layer (n = 2.09, k = 0.00002) as the first upper dielectric layer in the first stack, the second upper dielectric layer in the second stack, and the third upper dielectric layer in the third stack. The ZrOx layer (n = 2.15, k = 0.00005) in each upper dielectric layer was directly adjacent to the metal layer. The ZrOx layer (n=2.09, k=0.00002) in each upper dielectric layer is located on the side of the ZrOx layer (n=2.15, k=0.00005) away from the metal layer. The coating structure 200 meets the requirements of the alcohol wiping test before high-temperature heat treatment and reduces the haze after high-temperature heat treatment, so that the haze of the coated glass 1001 after high-temperature heat treatment is less than 0.25%, and the overall appearance is uniform, and there is no redness on the edge.

[0098] In Example 16, a high power pulsed magnetron sputtering power source (HiPIMS) was used to deposit a ZrOx layer (n = 2.08, k = 0.00002) and a medium frequency magnetron sputtering power source (MF) was used to deposit a TiOx layer (n = 2.48, k = 0.00095) as the first upper dielectric layer in the first stack and the second upper dielectric layer in the second stack, and a high power pulsed magnetron sputtering power source (HiPIMS) was used to deposit a ZrOx layer (n = 2.09, k = 0.00002) as the second upper dielectric layer in the third stack. There are three upper dielectric layers, and the ZrOx layer (n=2.08, k=0.00002) in each upper dielectric layer is in direct contact with the metal layer. The TiOx layer in the upper dielectric layer is located on the side of the ZrOx layer (n=2.08, k=0.00002) facing away from the metal layer. The coating structure 200 meets the requirements of the alcohol wiping test before high-temperature heat treatment and reduces the haze after high-temperature heat treatment. The haze of the coated glass 1001 after high-temperature heat treatment is less than 0.25%, and the overall appearance is uniform, with no redness on the edge.

[0099] In Example 17, a high power pulsed magnetron sputtering power source (HiPIMS) was used to deposit a ZrOx layer (n = 2.09, k = 0.00002) as the first upper dielectric layer in the first stack, the second upper dielectric layer in the second stack, and the third upper dielectric layer in the third stack, and a medium frequency magnetron sputtering power source (MF) was used to deposit an AZO layer (n = 1.976, k = 0.00047), a high power pulsed magnetron sputtering power source (HiPIMS) was used to deposit a ZrOx layer (n = 2.12, k = 0.00002) as the first upper dielectric layer in the first stack, the second upper dielectric layer in the second stack, and the third upper dielectric layer in the third stack. The AZO layer in each lower dielectric layer of the first lower dielectric layer, the second lower dielectric layer in the second stack, and the third lower dielectric layer in the third stack are in direct contact with the metal layer. The ZrOx layer (n=2.12, k=0.00002) in each lower dielectric layer is located on the side of the AZO layer facing away from the metal layer. The coating structure 200 meets the requirements of the alcohol wiping test before high-temperature heat treatment and reduces the haze after high-temperature heat treatment. The haze of the coated glass 1001 after high-temperature heat treatment is less than or equal to 0.20%, and the overall appearance is uniform, with no redness on the edges.

[0100] In Tables 2 and 3, the sheet resistance R of the coating structures 200 of Examples 13-17 after high-temperature heat treatment can be reduced to less than or equal to 1.1 Ω / □. The alcohol wiping test before and after the high-temperature heat treatment meets the requirements. The pencil hardness before and after the high-temperature heat treatment is improved compared with Comparative Examples 7-9. The pencil hardness of Example 17 after the high-temperature heat treatment even reaches 9H. This proves that the use of a high-power pulsed magnetron sputtering power source (HiPIMS) not only promotes the ionization of the ZrOy ceramic target to increase the sputtering rate, but also has the advantages of a dense structure and a smooth surface. The ZrOx layer with an extinction coefficient k less than or equal to 0.0001 is more stable during the high-temperature heat treatment and can effectively isolate the external high-temperature heat from being conducted to the metal layer, allowing the coated glass to withstand higher-temperature heat treatment. The ZrOx layer with an extinction coefficient k less than or equal to 0.0001 can also better isolate the diffusion of oxygen ions into the metal layer, resulting in extremely mild fogging of the coating structure after the heat treatment and no edge redness. In addition, the ZrOx layer with an extinction coefficient k less than or equal to 0.0001 has better film-base bonding strength, thereby preventing separation from the glass due to weak connection strength between the film layers during processing, thereby improving the overall mechanical stability of the coating structure.

[0101] Comparative Example 10 and Examples 18-20

[0102] In the present application, a 2.1 mm thick transparent glass substrate is prepared, and the coating structure 200 of Comparative Example 10 and Examples 18-20 is deposited on the surface of the transparent glass substrate by a magnetron sputtering process. The coating structure 200 has four functional stacks, specifically including an innermost adhesion layer 210, a first lower dielectric layer 221, a first metal layer 222, a first upper dielectric layer 223, a first intermediate layer 260, a second lower dielectric layer 231, a second metal layer 232, a second upper dielectric layer 233, a second intermediate layer 270, a third lower dielectric layer 241, a third metal layer 242, a third upper dielectric layer 243, a third intermediate layer 280, a fourth lower dielectric layer 251, a fourth metal layer 252, a fourth upper dielectric layer 253 and an outermost protective layer 290, which are stacked in sequence. At least one of the first upper dielectric layer 223, the second upper dielectric layer 233, the third upper dielectric layer 243 and the fourth upper dielectric layer 253 includes 1-3 ZrOx layers (HiPIMS).

[0103] The sheet resistance R, pencil hardness, and alcohol wiping test results of the coating structures 200 of Comparative Example 10 and Examples 18-20 before and after high-temperature heat treatment were measured. The overall appearance and edge appearance of the coated glass 1001 of Comparative Example 10 and Examples 18-20 after high-temperature heat treatment were observed. The haze of the coated glass 1001 of Comparative Example 10 and Examples 18-20 after high-temperature heat treatment was also measured. The measurement results are recorded in Table 4.

[0104] Table 4: Measurement results of coated glass 1001 of Comparative Example 10 and Examples 18-20

[0105] From Table 4 we can see that:

[0106] In Comparative Example 10, a medium-frequency magnetron sputtering power source (MF) was used to deposit AZO layers (n=1.94, k=0.04041) as the first upper dielectric layer in the first stack, the second upper dielectric layer in the second stack, the third upper dielectric layer in the third stack, and the fourth upper dielectric layer in the fourth stack. After high-temperature heat treatment, the pencil hardness of the coating structure 200 decreased, and slight fogging occurred, indicating that its heat treatment stability was poor and it was difficult to meet the requirements of the self-weight bending process or press bending process for producing automotive glass.

[0107] In Example 18, a high-power pulsed magnetron sputtering power source (HiPIMS) was used to deposit a ZrOx layer (n=2.09, k=0.00002) as the first upper dielectric layer in the first stack, the second upper dielectric layer in the second stack, the third upper dielectric layer in the third stack, and the fourth upper dielectric layer in the fourth stack. The pencil hardness of the coating structure 200 after high-temperature heat treatment did not decrease, and the haze after high-temperature heat treatment was reduced, so that the haze of the coated glass 1001 after high-temperature heat treatment was equal to 0.25%, and the overall appearance was uniform and the edge appearance was normal.

[0108] Example 19 A high power pulsed magnetron sputtering power source (HiPIMS) was used to deposit a ZrOx layer (n=2.12, k=0.00002) and a ZrOx layer (n=2.10, k=0.00002) as the first upper dielectric layer in the first stack, the second upper dielectric layer in the second stack, the third upper dielectric layer in the third stack, and the fourth upper dielectric layer in the fourth stack. The ZrOx layer (n=2.12, k=0.00002) in each upper dielectric layer 02) is in direct contact with the metal layer, the ZrOx layer (n=2.10, k=0.00002) in each upper dielectric layer is located on the side of the ZrOx layer (n=2.12, k=0.00002) away from the metal layer, the pencil hardness of the coating structure 200 after high-temperature heat treatment does not decrease and the haze after high-temperature heat treatment is reduced, so that the haze of the coated glass 1001 after high-temperature heat treatment is less than 0.25%, and the overall appearance is uniform and the edge appearance is normal.

[0109] In Example 20, a high-power pulsed magnetron sputtering power source (HiPIMS) was used to deposit a ZrOx layer (n=2.08, k=0.00002) as the first upper dielectric layer in the first stack, the second upper dielectric layer in the second stack, the third upper dielectric layer in the third stack, and the fourth upper dielectric layer in the fourth stack, and a medium-frequency magnetron sputtering power source (MF) was used to deposit an AZO layer (n=1.976, k=0.00047), a high-power pulsed magnetron sputtering power source (HiPIMS) was used to deposit a ZrOx layer (n=2.09, k=0.00002) as the first upper dielectric layer, the second upper dielectric layer in the second stack, the third upper dielectric layer in the third stack, and the fourth upper dielectric layer in the fourth stack. In the first lower dielectric layer of the stack, the second lower dielectric layer of the second stack, the third lower dielectric layer of the third stack, and the fourth lower dielectric layer of the fourth stack, the AZO layer in each lower dielectric layer is in direct contact with the metal layer, and the ZrOx layer (n=2.09, k=0.00002) in each lower dielectric layer is located on the side of the AZO layer facing away from the metal layer. The coating structure 200 has an improved pencil hardness and reduced haze after high-temperature heat treatment, resulting in a haze of less than 0.25% for the coated glass 1001 after high-temperature heat treatment, and a uniform overall appearance with normal edge appearance.

[0110] In Table 4, the sheet resistance R of the coating structures 200 of Examples 18-20 after high-temperature heat treatment can be reduced to less than or equal to 0.8Ω / □, or even less than or equal to 0.75Ω / □, and the alcohol wiping before and after high-temperature heat treatment meets the requirements. The pencil hardness before and after high-temperature heat treatment is improved compared with that of Comparative Example 10. In fact, the pencil hardness of Example 20 after high-temperature heat treatment reaches more than 9H, which proves that the use of high-power pulsed magnetron sputtering power supply (HiPIMS) can not only promote the ZrOy ceramic Target ionization increases the sputtering rate, while the resulting ZrOx layer exhibits advantages such as a dense structure and smooth surface. A ZrOx layer with an extinction coefficient k less than or equal to 0.0001 exhibits greater stability during high-temperature heat treatment, effectively isolating the external high-temperature heat transfer to the metal layer, enabling the coated glass to withstand higher-temperature heat treatments. Furthermore, a ZrOx layer with an extinction coefficient k less than or equal to 0.0001 effectively isolates oxygen ions from diffusing into the metal layer, resulting in minimal post-heat treatment fogging and no edge reddening. Furthermore, a ZrOx layer with an extinction coefficient k less than or equal to 0.0001 exhibits improved film-to-substrate bonding, preventing separation from the glass during processing due to weak interlayer bonding, thereby improving the overall mechanical stability of the coating structure.

[0111] The embodiments of the present application are described in detail above. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only intended to help understand the method and core concept of the present application. At the same time, those skilled in the art may vary in the specific implementation methods and application scope based on the concept of the present application. In summary, the contents of this specification should not be construed as limiting the present application.

Claims

1. A coated glass, characterized in that: include: a first substrate; and A coating structure, wherein the coating structure is arranged on at least one surface of the first substrate, the coating structure includes at least one functional stack, each of the functional stack includes a lower dielectric layer, a metal layer and an upper dielectric layer stacked in sequence, at least one of the lower dielectric layer and the upper dielectric layer includes a ZrOx layer, wherein x satisfies 1<x≤2, and the extinction coefficient k of the ZrOx layer is less than or equal to 0.0001.

2. The coated glass according to claim 1, characterized in that: The haze of the coated glass is less than or equal to 0.25%.

3. The coated glass according to claim 1, characterized in that: The refractive index n of the ZrOx layer satisfies the range of 2.00≤n≤2.

18.

4. The coated glass according to claim 1, characterized in that: 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-20nm.

5. The coated glass according to claim 1, characterized in that: The upper dielectric layer includes two ZrOx layers, wherein the refractive index of one ZrOx layer is greater than the refractive index of the other ZrOx layer.

6. The coated glass according to claim 1, characterized in that: The number of the functional stack is one, the coating structure comprises an innermost adhesion layer, a lower dielectric layer, a metal layer, an upper dielectric layer and an outermost protective layer stacked in sequence, and the upper dielectric layer comprises 1-3 ZrOx layers.

7. The coated glass according to claim 1, characterized in that: The number of the functional stacks is two, the two functional stacks are respectively the first stack and the second stack, the coating structure comprises an innermost adhesion layer, the first stack, an intermediate layer, the second stack and an outermost protective layer stacked in sequence, and at least one of the upper dielectric layer of the first stack and the upper dielectric layer of the second stack comprises 1-3 ZrOx layers.

8. The coated glass according to claim 1, characterized in that: The number of the functional stacks is three, the three functional stacks are respectively a first stack, a second stack and a third stack, the coating structure also includes two intermediate layers, the two intermediate layers are respectively a first intermediate layer and a second intermediate layer, the coating structure includes an innermost adhesion layer, the first stack, the first intermediate layer, the second stack, the second intermediate layer, the third stack and an outermost protective layer which are stacked in sequence, and at least one of the upper dielectric layer of the first stack, the upper dielectric layer of the second stack and the upper dielectric layer of the third stack includes 1-3 ZrOx layers.

9. The coated glass according to claim 1, characterized in that: The number of the functional stacks is four, and the four functional stacks are respectively a first stack, a second stack, a third stack and a fourth stack. The coating structure also includes three intermediate layers, and the three intermediate layers are respectively a first intermediate layer, a second intermediate layer and a third intermediate layer. The coating structure includes an innermost adhesion layer, the first stack, the first intermediate layer, the second stack, the second intermediate layer, the third stack, the third intermediate layer, the fourth stack and an outermost protective layer which are stacked in sequence. At least one of the upper dielectric layer of the first stack, the upper dielectric layer of the second stack, the upper dielectric layer of the third stack and the upper dielectric layer of the fourth stack includes 1-3 ZrOx layers.

10. The coated glass according to any one of claims 6 to 9, characterized in that: The ZrOx layer in the upper dielectric layer is in direct contact with the metal layer, or a barrier layer is provided between the ZrOx layer and the metal layer, the barrier layer is in direct contact with the metal layer, the physical thickness of the barrier layer is less than or equal to 5 nm, and the material of the barrier layer is selected from at least one metal or metal alloy of Ti, Ni, Cr, Nb, and W.

11. The coated glass according to any one of claims 6 to 9, characterized in that: The upper dielectric layer also includes an upper dielectric sublayer, which is located on the side of the ZrOx layer away from the metal layer, and the material of the upper dielectric sublayer includes an oxide of at least one metal or metal alloy selected from the group consisting of Zr, Zn, Mg, Sn, Ti, Nb, Ni, In, Al, Ce, W, Mo, Sb, and Bi.

12. The coated glass according to any one of claims 6 to 9, characterized in that: The lower dielectric layer includes a first sublayer directly in contact with the metal layer, and the material of the first sublayer includes an oxide of at least one metal or metal alloy selected from the group consisting of Zn, Mg, Sn, Ti, Nb, Ni, In, Al, Ce, W, Mo, Sb, and Bi.

13. The coated glass according to claim 12, characterized in that: The lower dielectric layer also includes a second sublayer, which is located on a side of the first sublayer away from the metal layer, and the second sublayer is the ZrOx layer.

14. The coated glass according to any one of claims 6 to 9, characterized in that: The physical thickness of the innermost adhesion layer is 10nm-40nm, the physical thickness of the upper dielectric layer or the lower dielectric layer is 5nm-30nm, the physical thickness of the intermediate layer is 30nm-70nm, and the physical thickness of the outermost protective layer is 5nm-70nm.

15. The coated glass according to any one of claims 6 to 9, characterized in that: The specific structure of the outermost protective layer is: TiOx layer / ZnSnOx layer / outermost sublayer, the physical thickness of the outermost sublayer is 5nm-50nm, and the material of the outermost sublayer includes at least one of SiAlZrNx, SiZrNx, SiNx, SiZrOx and SiAlZrOx.

16. A laminated glass, characterized in that: It comprises a second substrate, an adhesive layer and the coated glass according to any one of claims 1 to 15, 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.

17. The laminated glass according to claim 16, 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%.

18. A method for preparing coated glass, characterized in that: include: 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 at least one functional stack, each of which includes a lower dielectric layer, a metal layer and an upper dielectric layer stacked in sequence, at least one of the lower dielectric layer and the upper dielectric layer includes a ZrOx layer, wherein x satisfies 1<x≤2, and the extinction coefficient k of the ZrOx layer is less than or equal to 0.0001.

19. The method for preparing coated glass according to claim 18, characterized in that: The target power supply for magnetron sputtering the ZrOx layer is a high-power pulsed magnetron sputtering power supply, and 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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