Low-e coated glass for automobile front windshield and preparation method thereof

Abstract

The application provides a kind of Low-E coated glass for automobile front and preparation method thereof, it is related to glass technical field, the coated glass includes glass substrate and composite coating structure arranged on glass substrate;The composite coating structure includes at least two functional layers and at least nickel-chromium alloy layer arranged on the silver functional layer away from the glass substrate;Wherein, the silver functional layer away from the glass substrate is continuous silver layer with roughness Ra not less than 0.8nm, the nickel-chromium alloy layer is not higher than 0.8nm thick and discontinuous layer structure, nickel-chromium alloy particles in the nickel-chromium alloy layer are distributed in the recess of the silver functional layer away from the glass substrate.The application also provides a preparation method of coated glass.The application improves the problem that high visible light transmittance and haze cannot be compatible in the prior art.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of glass materials, in particular to a Low-E coated glass for automobile front windshield and a preparation method thereof. BACKGROUND

[0002] Low-E coated glass is a kind of coated glass with multiple metal or other compound film on the surface of glass, which can not only allow solar energy and visible light to pass through, but also reflect infrared light, especially medium and far infrared light back, so as to control sunlight, save energy and heat, and improve the environment, such as controlling the proportion of visible light and infrared light entering the car to adjust the temperature and light in the car.

[0003] Among them, the automobile front windshield is the main visual path for the people inside the car to observe the outside environment, so the researchers usually mainly focus on the visible light transmittance to avoid rapid temperature rise and large air conditioning energy consumption in the car. Therefore, the Low-E coated glass for automobile front windshield with low emissivity, high thermal conductivity and high visible light transmittance has become the main research direction. In order to maintain high visible light transmittance and low air conditioning energy consumption, the haze of the automobile front windshield is usually controlled in a lower range. However, the automobile front windshield with ultra-low haze (<0.3%) is easy to produce glare in the car, especially in summer with strong sunlight, the driver's visual fatigue is fast, which affects the driving safety. However, increasing the haze of the coated glass will lead to the decrease of the visible light transmittance of the glass, which is not conducive to the safety of driving in low light intensity such as cloudy, rainy and foggy days. SUMMARY

[0004] The purpose of the present application is to provide a Low-E coated glass for automobile front windshield, which improves the problem that high visible light transmittance and haze cannot be compatible in the prior art, and provides a coated glass with high visible light transmittance, relatively high haze and low emissivity.

[0005] Another purpose of the present application is to provide a preparation method of the Low-E coated glass for automobile front windshield.

[0006] In a first aspect, the present application provides a Low-E coated glass for automobile front windshield, comprising a glass substrate and a composite coating structure arranged on the glass substrate.

[0007] The composite coating structure comprises at least two functional layers and a nickel-chromium alloy layer arranged on the silver functional layer away from the glass substrate.

[0008] The silver functional layer away from the glass substrate is a continuous silver layer with a roughness Ra of no less than 0.8 nm, the nickel-chromium alloy layer is a layer structure with a thickness of no more than 0.8 nm and is discontinuous, and the nickel-chromium alloy particles in the nickel-chromium alloy layer are distributed in the recesses of the silver functional layer away from the glass substrate.

[0009] Further, in some embodiments of the present application, an intermediate medium layer is arranged between the silver functional layer away from the glass substrate and other silver functional layers; a second nickel-chromium alloy layer is arranged on the side of the intermediate medium layer close to the silver functional layer away from the glass substrate; and the second nickel-chromium alloy layer is a continuous nickel-chromium alloy layer.

[0010] Further, in some embodiments of the present application, a top medium layer is arranged on the nickel-chromium alloy layer; the top medium layer comprises a continuous or discontinuous layer structure formed by high-refractive-index crystals with a refractive index of no less than 2.3 under light with a wavelength of 550 nm; and the doping amount of the high-refractive-index crystals in the top medium layer is 5-10% by mass fraction.

[0011] Further, in some embodiments of the present application, the top medium layer is a titanium dioxide layer with a rutile crystal form.

[0012] Further, in some embodiments of the present application, the thickness of the top medium layer is 20-60 nm.

[0013] Further, in some embodiments of the present application, the composite coating structure comprises two functional layers: a first silver layer and a second silver layer; and the silver functional layer away from the glass substrate is the second silver layer.

[0014] The sum of the thicknesses of the first silver layer and the second silver layer is no less than 15 nm and no more than 25 nm.

[0015] Further, in some embodiments of the present application, an intermediate medium layer arranged between the first silver layer and the second silver layer comprises ZnAlO x layers, ZnSnO x layers, and ZnAlO x layers arranged in a stack.

[0016] Further, in some embodiments of the present application, the composite coating structure comprises three functional layers: a first silver layer, a second silver layer, and a third silver layer; and the silver functional layer away from the glass substrate is the third silver layer.

[0017] The thickness of the third silver layer is lower than that of the second silver layer, and the thickness of the first silver layer is lower than that of the second silver layer.

[0018] Furthermore, in some embodiments of this application, the thickness of the first silver layer is not higher than 10 nm; the thickness of the second silver layer is not lower than 13 nm and not higher than 18 nm; and the thickness of the third silver layer is not higher than 13 nm.

[0019] Furthermore, in some embodiments of this application, a first intermediate dielectric layer is disposed between the first silver layer and the second silver layer, the first dielectric layer comprising stacked ZnAlO x Layer, ZnSnO x Layer, ZnAlO x A second intermediate dielectric layer is disposed between the second silver layer and the third silver layer, the second dielectric layer comprising stacked ZnAlO x Layer, ZnSnO x Layer, ZnAlO x layer.

[0020] Furthermore, in some embodiments of this application, the composite coating structure includes four functional layers: a first silver layer, a second silver layer, a third silver layer, and a fourth silver layer; the silver functional layer furthest from the glass substrate is the fourth silver layer;

[0021] The thickness of the first silver layer is not higher than 10 nm; the thickness of the second and fourth silver layers is not lower than 10 nm and not higher than 13 nm; the thickness of the third silver layer is not lower than 13 nm and not higher than 18 nm.

[0022] Furthermore, in some embodiments of this application, a first intermediate dielectric layer is disposed between the first silver layer and the second silver layer, the first dielectric layer comprising stacked ZnAlO x Layer, ZnSnO x Layer, ZnAlO x A second intermediate dielectric layer is disposed between the second silver layer and the third silver layer, the second dielectric layer comprising stacked ZnAlO x Layer, ZnSnO x Layer, ZnAlO x A third intermediate dielectric layer is disposed between the third silver layer and the fourth silver layer, the third dielectric layer comprising stacked ZnAlO x Layer, ZnSnO x Layer, ZnAlO x layer.

[0023] Furthermore, in some embodiments of this application, the composite coating structure further includes a bottom protective layer and a top protective layer;

[0024] The bottom protective layer is selected from SiAlZrN x ZrO x NbO x SiNx ZnSnO x SiZrN x At least one of the following;

[0025] The top protective layer includes a protective layer and a top dielectric layer; the protective layer is selected from ZrO. x NbO x At least one of the following; the top dielectric layer is selected from SiAlZrN x SiZrN x SiN x At least one of them.

[0026] Furthermore, in some embodiments of this application, a seed layer is also provided between the bottom protective layer and the first silver layer.

[0027] Secondly, this application also provides a method for preparing Low-E coated glass for automotive windshields. The method involves forming a bottom protective layer, a seed layer, a first silver layer, a first intermediate dielectric layer, a second silver layer, a second intermediate dielectric layer, a nickel-chromium alloy layer, a third silver layer, a nickel-chromium alloy layer, a top dielectric layer, and a protective layer sequentially on a glass substrate using vacuum magnetron sputtering. The third silver layer is a continuous silver layer with a roughness Ra of not less than 0.8 nm, and the nickel-chromium alloy layer is a discontinuous layer structure with a thickness of not more than 0.8 nm.

[0028] Furthermore, in some embodiments of this application, after the sacrificial layer is formed by magnetron sputtering, the coated glass is heat-treated by annealing at 600~690°C for 8~15 minutes and then for 3~8 minutes.

[0029] Thirdly, this application also provides a method for preparing Low-E coated glass for automotive windshields, wherein a bottom protective layer, a seed layer, a nickel-chromium alloy layer, a first silver layer, a nickel-chromium alloy layer, an intermediate dielectric layer, a nickel-chromium alloy layer, a second silver layer, a nickel-chromium alloy layer, a top dielectric layer, and a protective layer are sequentially formed on a glass substrate by vacuum magnetron sputtering. The second silver layer is a continuous silver layer with a roughness Ra of not less than 0.8 nm, and the nickel-chromium alloy layer is a discontinuous layer structure with a thickness of not more than 0.8 nm.

[0030] Furthermore, in some embodiments of this application, after the sacrificial layer is formed by magnetron sputtering, the coated glass is heat-treated at 600~690°C for 3~8 minutes.

[0031] In a fourth aspect, the application further provides a preparation method of the Low-E coated glass for automobile front windshield. The vacuum magnetron sputtering coating method is used to form, on a glass substrate, a bottom protective layer, a seed layer, a first silver layer, a first intermediate medium layer, a second silver layer, a second intermediate medium layer, a third silver layer, a third intermediate medium layer, a nickel-chromium alloy layer, a fourth silver layer, a nickel-chromium alloy layer, a top medium layer and a protective layer in sequence, so that the fourth silver layer is a continuous silver layer with a roughness Ra not less than 0.8 nm, and the nickel-chromium alloy layer is a layer structure with a thickness not higher than 0.8 nm and discontinuous.

[0032] Further, in some embodiments of the application, after the magnetron sputtering coating forms the sacrificial layer, the coated glass is heat treated at 600-690 ℃ for 3-8 min.

[0033] The Low-E coated glass for automobile front windshield provided by the embodiments of the application uses the uppermost silver layer with high roughness and sets the nickel-chromium alloy layer arranged on the upper silver functional layer with high roughness as a discontinuous nickel-chromium alloy layer, without reducing the thickness of the silver functional layer, so as to ensure the emissivity of the coated glass, and at the same time, the high visible light transmittance of the coated glass is ensured by using the discontinuous nickel-chromium alloy layer, and the haze of the coated glass is improved by using the uppermost silver layer with high roughness. In addition, the coated glass provided by the application can further have a top medium layer with high refractive index arranged on the discontinuous functional layer, which is used to amplify the scattering rate of the coated glass, so that the coated glass formed thereby can better maintain high visible light transmittance and low emissivity while maintaining relatively high haze, further improves the effect of high haze, high visible light transmittance and low emissivity, so that when the coated glass is applied to the automobile front windshield, the visual of the people in the vehicle is maintained, and glare is not easy to occur even under high light, causing rapid fatigue of the eyes of the people in the vehicle, and the low heat insulation effect is also maintained. In addition, compared with the conventional coated glass with high haze provided by surface roughening, the coated surface of the Low-E coated glass provided by the application can still maintain high smoothness, which is more conducive to subsequent processing and improves the defect that the coated surface of the conventional high-haze coated glass is easy to fog.

[0034] The Low-E coated glass for automotive windshields provided in this application, when featuring two layers of silver functional layers, achieves a visible light transmittance of over 74% and an emissivity of <0.05 for the laminated glass; the haze can be controlled between 0.5% and 0.8%. When featuring three layers of silver functional layers, the laminated glass achieves a visible light transmittance of over 72% and an emissivity of <0.03; the haze can be controlled between 0.5% and 0.8%. When featuring four layers of silver functional layers, the laminated glass achieves a visible light transmittance of over 70% and an emissivity of <0.02; the haze can be controlled between 0.5% and 0.8%. Attached Figure Description

[0035] Figure 1 A schematic diagram of the structure of the double-silver Low-E coated glass provided in this application;

[0036] Figure 2 This is a schematic diagram of the structure of the triple silver Low-E coated glass provided in this application;

[0037] Figure 3 This is a schematic diagram of the structure of the four-silver Low-E coated glass provided in this application. Detailed Implementation

[0038] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0039] According to the Motor Vehicle Running Safety Technical Conditions (GB7258-2017), the visible light transmittance of the front windshield and side window glass used in the driver's viewing area shall not be less than 70%, so as to ensure the clear vision of the driver and ensure the safety of driving. Therefore, the current researchers pay more attention to the high visible light transmittance and low emissivity of the front windshield of the automobile. In order to ensure the visible light transmittance, radiation and other properties of the coated glass, the existing technology usually pursues lower haze. However, the applicant finds that at very low haze, although the visible light transmittance is high (≥70%) and the infrared reflectivity is high, it is beneficial to the vision of the person inside the car and the temperature environment inside the car, but high visible light transmittance is easy to cause glare and rapid visual fatigue of the driver, and is not conducive to the clear side view. And increasing the haze (≥1%) of the coated glass will make it difficult for the coated glass to have a visible light transmittance of more than 70%; and using glass without coating will make it difficult to maintain the comfortable temperature inside the car and reduce energy consumption. Based on this technical problem, the present application provides a kind of Low-E coated glass with high visible light transmittance, high haze and low radiation, which realizes the combination of high visible light transmittance, high haze and low radiation, and meets the demand of front windshield with high light transmittance, soft light and energy-saving thermal insulation.

[0040] The specific technical solutions are as follows:

[0041] A kind of Low-E coated glass for automobile front windshield, comprising a glass substrate and a composite coating structure disposed on the glass substrate;

[0042] The composite coating structure comprises at least two functional layers and a nickel-chromium alloy layer disposed on the silver functional layer away from the glass substrate;

[0043] Wherein, the silver functional layer away from the glass substrate is a continuous silver layer with a roughness Ra not less than 0.8 nm, and the nickel-chromium alloy layer is a layer structure with a thickness not higher than 0.8 nm and discontinuous, and the nickel-chromium alloy particles in the nickel-chromium alloy layer are distributed in the recesses of the silver functional layer away from the glass substrate.

[0044] In this application, the "silver functional layer away from the glass substrate" should be understood as: the silver functional layer farthest from the glass substrate in the multi-layer silver functional layer, i.e. the uppermost silver functional layer. At least two silver functional layers are stacked and have intermediate medium layers therebetween; the silver functional layer close to the glass substrate has a bottom protective layer between the silver functional layer and the glass substrate.

[0045] It should be noted that the "high haze" described in the present application is a relatively high haze compared to the prior art, in which the haze of Low-E glass is usually controlled below 1% in order to achieve high visible light transmittance, rather than increasing the haze of Low-E glass to a very high level, such as increasing the haze to 5% or even more than 10%. Therefore, the high haze described in the present application is a relative high haze, rather than an absolute high haze.

[0046] In the present application, the silver functional layer away from the glass substrate is a continuous silver layer with a roughness Ra of not less than 0.8 nm, and the thickness of the silver layer is not more than 18 nm, preferably 10-15 nm; the nickel-chromium alloy particles in the nickel-chromium alloy layer can be distributed in clusters or in a linear shape on the surface of the rough silver functional layer, and the width of the clusters or linear nickel-chromium alloy is preferably 0.2-1 nm, so that a discontinuous nickel-chromium alloy layer is formed on the silver functional layer, and a number of silver functional layer regions not covered by the nickel-chromium alloy are exposed, and the maximum width of these silver functional layer regions not covered by the nickel-chromium alloy is generally concentrated in the range of 1-5 nm.

[0047] Applicants have found that the visible light transmittance of the Low-E coated glass provided in the present application can reach more than 70%, and the haze can be controlled below 0.8%, which may be due to the fact that the present application uses a relatively thin uppermost silver functional layer and a discontinuous nickel-chromium alloy layer to improve the visible light transmittance of the coated glass, while using a rough upper silver functional layer to increase the haze of the coated glass, so as to present a relatively high haze and maintain good infrared reflectivity and low emissivity.

[0048] In some preferred embodiments, a top dielectric layer is further provided on the nickel-chromium alloy layer; the top dielectric layer comprises a continuous or discontinuous layer structure formed by high-refractive-index crystals with a refractive index of not less than 2.3 under light of 550 nm wavelength; the doping amount of the high-refractive-index crystals in the top dielectric layer is 5-10% by mass fraction, and the use of high-refractive-index dielectric increases the amplification of the coating scattering rate, further improves the haze of the coating, and maintains a relatively high visible light transmittance. Illustratively, the high-refractive-index crystals are rutile-type titanium dioxide; the thickness of the top dielectric layer is 20-60 nm, preferably 30-45 nm.

[0049] In some embodiments, an intermediate dielectric layer is provided between the silver functional layer away from the glass substrate and other silver functional layers; a second nickel-chromium alloy layer is provided on the intermediate dielectric layer close to the silver functional layer away from the glass substrate; the second nickel-chromium alloy layer is a continuous nickel-chromium alloy layer, which serves as a barrier layer. The thickness of the second nickel-chromium alloy layer can be higher than that of the nickel-chromium alloy layer, or equal to that of the nickel-chromium alloy layer.

[0050] The automobile front windshield Low-E coated glass provided by the application can be double-silver Low-E coated glass, triple-silver Low-E coated glass or quadruple-silver Low-E coated glass. When the automobile front windshield Low-E coated glass is double-silver Low-E coated glass, the composite coating structure comprises two functional layers, i.e., a first silver layer and a second silver layer. The silver functional layer far from the glass substrate is the second silver layer. The sum of the thicknesses of the first silver layer and the second silver layer is not less than 15 nm and not more than 25 nm. The thickness of the first silver layer is 10-15 nm, and the thickness of the second silver layer is 10-15 nm. The thickness of the first silver layer should not be too high or too low. Similarly, the thickness of the second silver layer should not be too high or too low. If either of the thicknesses is too high or too low, it is not conducive to maintaining high visible light transmittance and high infrared reflectance.

[0051] The intermediate medium layer arranged between the first silver layer and the second silver layer further comprises a ZnAlO x layer, a ZnSnO x layer and a ZnAlO x layer arranged in layers.

[0052] When the automobile front windshield Low-E coated glass is triple-silver Low-E coated glass, the composite coating structure comprises three functional layers, i.e., a first silver layer, a second silver layer and a third silver layer. The silver functional layer far from the glass substrate is the third silver layer. The thickness of the third silver layer is lower than that of the second silver layer, and the thickness of the first silver layer is lower than that of the second silver layer. A first intermediate medium layer is arranged between the first silver layer and the second silver layer. The first intermediate medium layer comprises a ZnAlO x layer, a ZnSnO x layer and a ZnAlO x layer arranged in layers. A second intermediate medium layer is arranged between the second silver layer and the third silver layer. The second intermediate medium layer comprises a ZnAlO x layer, a ZnSnO x layer and a ZnAlO x layer arranged in layers, to form a Fabry-Perot interference cavity and improve optical performance. At the same time, the silver layer is protected during the strengthening process.

[0053] In the application, the intermediate medium layer comprises a ZnAlO x layer conducive to silver layer growth and a medium layer, i.e., a ZnSnO x layer, between the ZnAlO x layer. The ZnSnO x layer has good chemical stability, high visible light transmittance and a refractive index of 2-2.2, can better adjust the refractive index and make the film layer maintain higher visible light transmittance. In the application, x in the ZnAlO x and the ZnSnO x is independently selected from any number in the range of 1-3.

[0054] In addition, it also needs to be explained that ZnAlO x , ZnSnO x In ZnO, Zn and Al, Zn and Sn are not in the atomic molar ratio of 1:1, but a certain amount of Al2O3 is doped in ZnO, and a certain amount of SnO2 is doped in ZnO. The addition amount of Al2O3 and SnO2 can be adjusted as needed, preferably; the doping amount of Al2O3 and SnO2 in ZnO is 1-5%, 40-60% respectively, and the doping amount should not be too much. If the doping amount of Al2O3 is too much, Al2O3 is easy to form local insulation and cause the surface resistance to rise. The doping amount of SnO2 should not be too much, which is easy to cause color deviation.

[0055] The thickness of the first silver layer is not higher than 10nm; the thickness of the second silver layer is not lower than 13nm and not higher than 18nm, and is further preferably not higher than 15nm; the thickness of the third silver layer is not higher than 13nm.

[0056] In the present application, the thickness of the three silver layers of the triple silver coated glass presents a trend of thin-thick-thinner from the glass substrate to the top layer, wherein the thickness of the silver layer close to the glass substrate is the thinnest to provide higher infrared reflection; the thickness of the second silver layer is the thickest to provide better near-infrared reflectance and keep the visible light transmittance at a higher level; and the thickness of the third silver layer is between the thicknesses of the first silver layer and the second silver layer and close to the thickness of the second silver layer, which improves the infrared radiation while maintaining the stability of the surface and provides a certain basis for the stability of subsequent glass strengthening. Meanwhile, in the present application, on the basis of meeting the above thickness relationship, the thickness ranges of the first silver layer, the second silver layer and the third silver layer need to be further controlled, because the applicant has found that a too thick first silver layer can improve the infrared reflectance to some extent, but will cause the visible light transmittance of the coated glass to decrease more obviously; preferably, the thickness of the first silver layer is 7 nm to 12 nm; a lower first silver layer thickness can make the visible light transmittance of the coated glass rise, but will cause the surface resistance of the coating to rise sharply and the emissivity to rise instead. The applicant has also found that a too thick second silver layer can improve the reflectance of near-infrared light, but is difficult to maintain the transmittance of visible light and will cause color deviation, which is difficult to maintain the neutral color of the coated glass and is not conducive to the color selectivity of the coated glass; therefore, the thickness of the second silver layer can be further reduced to below 15 nm in the present application to maintain a higher visible light transmittance in the triple silver coated glass; meanwhile, the thickness of the second silver layer should not be too low, and a too low second silver layer thickness will cause the emissivity to increase, which is not conducive to the visible light transmittance and the emissivity. In addition, the applicant has also found that a lower second silver layer thickness is also not conducive to the visible light transmittance, and the possible reason may be that the light interference in the Fabry-Perot interference cavity formed by the second silver layer, the first silver layer and the third silver layer through the dielectric combination layer is easy to shift at a lower second silver layer thickness, color deviation is more obvious, and the transmittance of visible light decreases. The thickness of the third silver layer is between the thicknesses of the first silver layer and the second silver layer, and is preferably 11 nm to 13 nm.

[0057] In some preferred embodiments, the thickness of the second silver layer is 1.6 to 2 times the thickness of the first silver layer, and the thickness of the first silver layer is not less than 7 nm;

[0058] The thickness of the second silver layer is 1.05 to 1.2 times the thickness of the third silver layer.

[0059] As mentioned above, the thickness of the third silver layer is between the thickness of the first silver layer and the thickness of the second silver layer, and preferably close to the thickness of the second silver layer, because the applicant has found that when the thickness of the third silver layer is too low, the infrared reflectivity will decrease significantly, and it is not conducive to the combination with the top dielectric layer, affecting the stability of the coated structure; while the third silver layer is too thick, it will affect the visible light transmittance of the coated glass.

[0060] When it is a four-silver Low-E coated glass, the composite coated structure comprises four functional layers: a first silver layer, a second silver layer, a third silver layer and a fourth silver layer; the silver functional layer far from the glass substrate is the fourth silver layer.

[0061] The thickness of the first silver layer is not higher than 10 nm; the thickness of the second silver layer and the fourth silver layer is not lower than 10 nm and not higher than 13 nm; the thickness of the third silver layer is not lower than 13 nm and not higher than 18 nm.

[0062] The first silver layer and the second silver layer are provided with a first intermediate dielectric layer therebetween, the first dielectric layer comprises ZnAlO x layer, ZnSnO x layer and ZnAlO x layer arranged in layers; the second silver layer and the third silver layer are provided with a second intermediate dielectric layer therebetween, the second dielectric layer comprises ZnAlO x layer, ZnSnO x layer and ZnAlO x layer arranged in layers; the third silver layer and the fourth silver layer are provided with a third intermediate dielectric layer therebetween, the third dielectric layer comprises ZnAlO x layer, ZnSnO x layer and ZnAlO x layer arranged in layers.

[0063] In the present application, the thickness of the four silver layers of the four-silver-coated glass is distributed in a "thin-middle-thick-middle" gradient, which achieves efficient reflection of the full infrared spectrum, ultimately resulting in better heat insulation and sun-shading effects. The first silver layer directly contacts the bottom oxide layer, and excessive thickness can easily lead to coarse crystalline particles and poor continuity of the silver layer, thereby reducing the reflection efficiency. Controlling the thickness within 10 nm can form a uniform and dense initial reflection layer, providing a stable substrate for the subsequent silver layer, while also initially reflecting part of the near-infrared radiation. The second and fourth silver layers are located in the middle and outer positions of the film layer, with a moderate and consistent or nearly consistent thickness, which can specifically reflect the mid-infrared band (the main band of heat transfer). Using this specific thickness, it avoids the sudden drop in discontinuous film reflectivity caused by excessive thinness (<10 nm) and the material waste and increased visible light absorption caused by excessive thickness (>13 nm). The third silver layer adopts a specific higher thickness of 13-18 nm, which can specifically reflect the far-infrared band and the remaining mid-infrared band, complementing the second and fourth layers to significantly improve the overall infrared reflectivity; at the same time, as it is wrapped by the front and rear oxide layers, there is no need to worry about its surface flatness.

[0064] The first silver layer has a thickness not higher than 10 nm; the second silver layer and the fourth silver layer have a thickness not lower than 10 nm and not higher than 13 nm; and the third silver layer has a thickness not lower than 13 nm and not higher than 18 nm.

[0065] In some embodiments, the composite coated structure further comprises a bottom protective layer and a top protective layer.

[0066] The bottom protective layer is selected from at least one of at least one of SiAlZrN x , ZrO x , NbO x , SiN x , ZnSnO x , SiZrN x .

[0067] The top protective layer comprises a sacrificial layer and a top dielectric layer; the sacrificial layer is selected from at least one of ZrO x , NbO x ; and the top dielectric layer is selected from at least one of SiAlZrN x , SiZrN x , SiN x , with high-refractive-crystal-doped in the above-mentioned top dielectric layer material. Preferably, the sacrificial layer is ZrO x , which has very high hardness, excellent acid and alkali resistance, excellent weather resistance, and excellent scratch resistance and other mechanical properties, which is beneficial to the optimization of the processing performance of the coated glass. Among them, SiAlZrN x , ZrO x , NbOx SiN x ZnSnO x SiZrN x x in the above formula is independently selected from any number between 1 and 5. The thickness of the top protective layer is not higher than 30 nm and not lower than 20 nm, which does not have obvious adverse effects on the optical performance of the coated glass while maintaining its protective effect and strength.

[0068] In some embodiments, the thickness of the top protective layer is not higher than 30 nm and not lower than 20 nm.

[0069] In some embodiments, a seed layer is further provided between the bottom protective layer and the first silver layer; the seed layer can be at least one of ZnAlO x ZnSnO x

[0070] In a second aspect, the application further provides a preparation method of a Low-E coated glass for automobile front windshield based on double silver, which comprises sequentially forming a bottom protective layer, a seed layer, a first silver layer, an intermediate medium layer, a second silver layer, a nickel-chromium alloy layer, a top medium layer and a sacrificial layer on a glass substrate by vacuum magnetron sputtering coating, so that the second silver layer is a continuous silver layer with a roughness Ra not lower than 0.8 nm, and the nickel-chromium alloy layer is a layer structure with a thickness not higher than 0.8 nm and not continuous.

[0071] In a third aspect, the application further provides a preparation method of a Low-E coated glass for automobile front windshield based on triple silver, which comprises sequentially forming a bottom protective layer, a seed layer, a first silver layer, a first intermediate medium layer, a second silver layer, a second intermediate medium layer, a nickel-chromium alloy layer, a third silver layer, a nickel-chromium alloy layer, a top medium layer and a sacrificial layer on a glass substrate by vacuum magnetron sputtering coating, so that the third silver layer is a continuous silver layer with a roughness Ra not lower than 0.8 nm, and the nickel-chromium alloy layer is a layer structure with a thickness not higher than 0.8 nm and not continuous.

[0072] In a fourth aspect, the application further provides a preparation method of a Low-E coated glass for automobile front windshield based on quadruple silver, which comprises sequentially forming a bottom protective layer, a seed layer, a first silver layer, a first intermediate medium layer, a second silver layer, a second intermediate medium layer, a third silver layer, a third intermediate medium layer, a nickel-chromium alloy layer, a fourth silver layer, a nickel-chromium alloy layer, a top medium layer and a protective layer on a glass substrate by vacuum magnetron sputtering coating, so that the fourth silver layer is a continuous silver layer with a roughness Ra not lower than 0.8 nm, and the nickel-chromium alloy layer is a layer structure with a thickness not higher than 0.8 nm and not continuous.

[0073] ​It should be noted that the glass substrate needs to be strictly cleaned before magnetron sputtering coating to clean the surface of the glass substrate and avoid introducing impurities to affect the performance of the film layer and the adhesion to the glass substrate. The specific steps are all prior art, such as conventional dust removal, oil removal and other processes, so they will not be described in detail in this application, which does not affect the understanding and implementation of the scheme by those skilled in the art.

[0074] In addition, in the preparation method provided in the present application, according to the difference of the material and the thickness of each layer, the selected raw materials, the atmosphere environment and the coating time are adjusted when the corresponding film layer is formed by vacuum magnetron sputtering coating, but the magnetron sputtering chamber needs to be vacuumized before coating, and the coated glass is heat treated at 600-690℃ for 3-8min after magnetron sputtering coating to improve the density of the coating, and improve the adhesion and hardness of the coating to the glass substrate.

[0075] Exemplarily, the preparation method of the double-silver Low-E coated glass comprises the following steps:

[0076] S1: Glass pretreatment: strictly clean the glass raw piece to remove dust, oil stains and other impurities.

[0077] S2: Load glass: convey the cleaned glass into the vacuum chamber of the coating equipment.

[0078] S3: Vacuumizing: start the vacuum system to extract the chamber to the required high vacuum state.

[0079] S4: Target preparation: install and prepare SiN x , ZnSnO x , Ag, NiCr, TiO x , ZrO x , ZnAlO x , SiZrN x and other targets for forming high-performance coated glass for automobiles.

[0080] S5: Pre-sputtering: briefly pre-sputter the target to remove oxides, impurities and other impurities on the surface of the target to ensure the quality of the coating.

[0081] S6: Coating process: turn on the magnetron sputtering power supply to make the target atoms or ions be sputtered and deposited on the glass surface to form a coating layer. During the coating process, the sputtering power, gas flow and other parameters are accurately controlled to obtain the required coating thickness and performance.

[0082] According to the design requirements, SiN x , ZnAlO x , NiCr, Ag, NiCr, ZnAlO xZnSnO x ZnAlO x NiCr, Ag, NiCr, TiO x SiZrAlN x ZrO x Different target materials are used to form a multilayer structure of thin films, such as Figure 1 .

[0083] S7: Post-processing. Heat treatment at 600-690℃ for 3-8min.

[0084] The preparation method of the triple silver Low-E coated glass comprises the following steps:

[0085] S1: Glass pretreatment: Strict cleaning of the glass raw sheet to remove dust, oil stains and other impurities.

[0086] S2: Load glass: Transfer the cleaned glass to the vacuum chamber of the coating equipment.

[0087] S3: Vacuum pumping: Start the vacuum system and pump the chamber to the required high vacuum state.

[0088] S4: Target preparation: Install and prepare the SiN x ZnSnO x Ag, NiCr, TiO x ZrO x ZnAlO x SiZrN x and other targets for forming high-performance coated glass for automobiles.

[0089] S5: Pre-sputtering: Briefly pre-sputter the target to remove oxides, impurities and other impurities on the surface of the target to ensure the quality of the coating.

[0090] S6: Coating process: Turn on the magnetron sputtering power source, so that the target atoms or ions are sputtered and deposited on the glass surface to form a coating layer; during the coating process, the sputtering power, gas flow and other parameters are accurately controlled to obtain the required coating thickness and performance.

[0091] According to the design requirements, SiN x ZnAlO x Ag, ZnAlO x ZnSnO x ZnAlO x Ag, ZnAlO x ZnSnO x ZnAlO x NiCr, Ag, NiCr, TiO x SiZrAlNx , ZrO x Different target materials are used to form a multilayer structure of thin films, such as Figure 2 as shown.

[0092] S7: Post-processing. Heat treatment at 600-690℃ for 3-8min.

[0093] The preparation method of the four-silver Low-E coated glass comprises the following steps:

[0094] S1: Glass pretreatment: Strict cleaning of the glass raw sheet to remove dust, oil stains and other impurities.

[0095] S2: Load glass: Transfer the cleaned glass to the vacuum chamber of the coating equipment.

[0096] S3: Vacuum pumping: Start the vacuum system and pump the chamber to the required high vacuum state.

[0097] S4: Target preparation: Install and prepare the SiN x , ZnSnO x , Ag, NiCr, TiO x , ZrO x , ZnAlO x , SiZrN x , etc. targets for forming high-performance coated glass for automobiles.

[0098] S5: Pre-sputtering: Short pre-sputtering of the target to remove oxides, impurities, etc. on the surface of the target to ensure the quality of the coating.

[0099] S6: Coating process: Turn on the magnetron sputtering power source, so that the target atoms or ions are sputtered and deposited on the glass surface to form a coating layer; during the coating process, the sputtering power, gas flow and other parameters are precisely controlled to obtain the required coating thickness and performance.

[0100] According to the design requirements, SiN x , ZnAlO x , Ag, ZnAlO x , ZnSnO x , ZnAlO x , Ag, ZnAlO x , ZnSnO x , ZnAlO x , Ag, ZnAlO x , ZnSnO x , ZnAlO x , NiCr, Ag, NiCr, TiO x , SiZrAlN x , ZrOx Different target materials are used to form multilayer thin films, such as Figure 3 As shown.

[0101] S7: Post-treatment: Heat treatment at 600~690℃ for 3~8 minutes.

[0102] In the first silver layer sputtering process of each coated glass, the sputtering atmosphere for the first silver layer is argon 400-800 sccm; the sputtering process pressure is 2-4 × 10⁻⁴ sq m. -3 mbar. It should be noted that the sputtering atmosphere and pressure for the first silver layer should not be too high or too low. If the pressure is too low, the sputtered atoms will have relatively high energy, resulting in a dense film with insufficient surface roughness. As the sputtering pressure increases, the sputtered atoms experience more scattering as they fly towards the substrate, resulting in reduced energy upon arrival and decreased migration ability, thus reducing the film density. Excessively high sputtering pressure causes particles to collide with a large number of argon atoms, significantly reducing their own energy. This results in a reduced film deposition rate and decreased surface migration energy input to the substrate, ultimately preventing the formation of a dense film structure.

[0103] To facilitate understanding of the innovative aspects of this application by those skilled in the art, some preferred embodiments are provided below in conjunction with the accompanying drawings to illustrate the above technical solutions.

[0104] Example 1

[0105] This embodiment provides a method for preparing Low-E coated glass for automotive windshields based on double silver, such as... Figure 1 As shown, from bottom to top, the layers include a glass substrate, a silicon nitride layer (30nm), a zinc aluminum oxide layer (10nm), a nickel-chromium alloy layer (0.5nm), a first silver layer (11nm), a nickel-chromium alloy layer (0.5nm), a zinc aluminum oxide layer (11nm), a zinc tin oxide layer (75nm), a zinc aluminum oxide layer (11nm), a nickel-chromium alloy layer (0.8nm), a second silver layer (14nm), a nickel-chromium alloy layer (0.5nm), titanium dioxide (13nm), silicon aluminum zirconium nitride (20nm), and a zirconium oxide layer (5nm). The fabrication process is achieved using vacuum magnetron sputtering deposition technology, and the specific steps are as follows:

[0106] S1: Glass pretreatment: The original glass sheet is thoroughly cleaned to remove dust, oil and other impurities.

[0107] S2: Loading Glass: Transfer the cleaned glass into the vacuum chamber of the coating equipment.

[0108] S3: Vacuuming: Start the vacuum system to evacuate the chamber to the required high vacuum level.

[0109] S4: Target preparation: Install and prepare the target materials required for the silicon nitride layer, zinc aluminum oxide layer, silver layer, zinc tin oxide layer, nickel chromium alloy layer, titanium dioxide, silicon zirconium nitride layer, and zirconium oxide layer of high-performance coated glass for new energy vehicles.

[0110] S5: Pre-sputtering: The target is briefly pre-sputtered to remove oxides, impurities, and other contaminants from the target surface, ensuring film quality.

[0111] S6: Coating process: Turn on the magnetron sputtering power to make target atoms or ions sputtered and deposited on the glass surface to form a coating layer. During the coating process, the sputtering power, gas flow, and other parameters are precisely controlled to obtain the desired film thickness and performance.

[0112] S61: Use rotating silicon aluminum as the target material to sputter on the surface of the glass substrate to form a silicon nitride layer. The sputtering atmosphere for the silicon nitride layer is argon:nitrogen = 450:650 sccm.

[0113] S62: Use aluminum-doped zinc oxide as the target material to sputter on the surface of the silicon nitride layer to form an aluminum zinc oxide layer. The sputtering atmosphere for the aluminum zinc oxide layer is argon:oxygen = 800:40 sccm.

[0114] S63: Use 20% Ni, 80% Cr nickel chromium as the target material to sputter on the surface of the aluminum zinc oxide layer to form a nickel chromium alloy layer. The sputtering atmosphere for the nickel chromium alloy layer is argon 600 sccm.

[0115] S64: Use silver as the target material to sputter on the surface of the aluminum zinc oxide layer to form a first silver layer. The sputtering atmosphere for the first silver layer is argon 600 sccm, and the sputtering process gas pressure is 2.5 x 10 -3 mbar.

[0116] S65: Use 20% Ni, 80% Cr nickel chromium as the target material to sputter on the surface of the aluminum zinc oxide layer to form a nickel chromium alloy layer. The sputtering atmosphere for the nickel chromium alloy layer is argon 600 sccm.

[0117] S66: Use aluminum-doped zinc oxide as the target material to sputter on the surface of the first silver layer to form an aluminum zinc oxide layer. The sputtering atmosphere for the aluminum zinc oxide layer is argon:oxygen = 800:40 sccm.

[0118] S67: Use 52% ZnO, 48% SnO2 zinc tin oxide as the target material to sputter on the surface of the aluminum zinc oxide layer to form a zinc tin oxide layer. The sputtering atmosphere for the zinc tin oxide layer is argon:oxygen = 700:40 sccm.

[0119] S68: Use aluminum-doped zinc oxide as the target material to sputter on the surface of the zinc tin oxide layer to form an aluminum zinc oxide layer. The sputtering atmosphere for the aluminum zinc oxide layer is argon:oxygen = 800:40 sccm.

[0120] S69: Nickel-chromium with 20% Ni and 80% Cr is used as target material to form a nickel-chromium alloy layer on the surface of the zinc aluminum oxide layer, and the sputtering atmosphere of the nickel-chromium alloy layer is argon 600 sccm;

[0121] S610: Silver is used as target material to form a second silver layer on the surface of the nickel-chromium alloy layer, and the sputtering atmosphere of the second silver layer is argon 600 sccm;

[0122] S611: Nickel-chromium with 20% Ni and 80% Cr is used as target material to form a nickel-chromium alloy layer on the surface of the silver layer, and the sputtering atmosphere of the nickel-chromium alloy layer is argon 600 sccm;

[0123] S612: Titanium oxide is used as target material to form a continuous or discontinuous titanium dioxide layer on the surface of the nickel-chromium alloy layer, and the sputtering atmosphere of the titanium dioxide layer is argon:oxygen = 800:30 sccm;

[0124] S613: A mixed alloy of silicon, zirconium and aluminum is used as target material to form a silicon zirconium aluminum nitride on the surface of the continuous or discontinuous titanium dioxide layer, and the sputtering atmosphere of the silicon zirconium aluminum nitride is argon:nitrogen = 450:650 sccm;

[0125] S614: Zirconium oxide is used as target material to form a zirconium oxide layer on the surface of the silicon zirconium aluminum nitride, and the sputtering atmosphere of the zirconium oxide layer is argon:oxygen = 800:20 sccm.

[0126] S7: The coated glass is heat treated at 600-690℃ for 3-8min.

[0127] Example 2

[0128] Example 2 also provides a preparation method of a silver-based Low-E coated glass for automobile front windshield, and the difference between the preparation method and the embodiment is that when the thickness of the layer formed by sputtering is different, the magnetron sputtering time is adjusted according to the thickness of the layer to obtain a corresponding film layer with different thickness, and the rest of the preparation method is the same as that of Example 1, thereby obtaining a corresponding preparation method of a silver-based Low-E coated glass for automobile front windshield, and the thickness of each layer of the coated glass obtained is shown in Table 1.

[0129] Example 3

[0130] This embodiment provides a preparation method of a silver-based Low-E coated glass for automobile front windshield, and the difference between the preparation method and the embodiment is that when the thickness of the layer formed by sputtering is different, the magnetron sputtering time is adjusted according to the thickness of the layer to obtain a corresponding film layer with different thickness, and the rest of the preparation method is the same as that of Example 1, thereby obtaining a corresponding preparation method of a silver-based Low-E coated glass for automobile front windshield, and the thickness of each layer of the coated glass obtained is shown in Table 1. Figure 2As shown, from bottom to top, it includes a glass substrate, a silicon nitride layer (35 nm), an aluminum zinc oxide layer (12 nm), a first silver layer (7.5 nm), an aluminum zinc oxide layer (12 nm), a zinc tin oxide layer (50 nm), an aluminum zinc oxide layer (12 nm), a second silver layer (14 nm), an aluminum zinc oxide layer (12 nm), a zinc tin oxide layer (60 nm), an aluminum zinc oxide layer (12 nm), a nichrome layer (0.3 nm), a third silver layer (12 nm), a nichrome layer (0.6 nm), a titanium dioxide layer (13 nm), a silicon zirconium aluminum nitride layer (20 nm), and a zirconium oxide layer (5 nm). The preparation is realized by vacuum magnetron sputtering coating technology, and the specific steps are as follows:

[0131] S1: Glass pretreatment: The glass wafer is strictly cleaned to remove dust, oil stains and other impurities.

[0132] S2: Load glass: The cleaned glass is transported into the vacuum chamber of the coating equipment.

[0133] S3: Vacuum pumping: Start the vacuum system to pump the chamber to the required high vacuum state.

[0134] S4: Target preparation: Install and prepare the target materials required for the silicon nitride layer, aluminum zinc oxide layer, silver layer, zinc tin oxide layer, nichrome layer, titanium dioxide, silicon zirconium nitride layer, and zirconium oxide layer of the high-performance coated glass for new energy vehicles.

[0135] S5: Pre-sputtering: Pre-sputter the target for a short time to remove oxides, impurities and other impurities on the surface of the target to ensure the quality of the coating.

[0136] S6: Coating process: Turn on the magnetron sputtering power to make the target atoms or ions sputtered and deposited on the glass surface to form a coating layer. During the coating process, the sputtering power, gas flow and other parameters are accurately controlled to obtain the required coating thickness and performance.

[0137] S61: Use rotating silicon aluminum as target material to sputter on the surface of the glass substrate to form a silicon nitride layer. The sputtering atmosphere of the silicon nitride layer is argon:nitrogen=450:650sccm;

[0138] S62: Use aluminum-doped zinc oxide as target material to sputter on the surface of the silicon nitride layer to form an aluminum zinc oxide layer. The sputtering atmosphere of the aluminum zinc oxide layer is argon:oxygen=800:40sccm;

[0139] S63: Use silver as target material to sputter on the surface of the aluminum zinc oxide layer to form a first silver layer. The sputtering atmosphere of the first silver layer is argon 600sccm, and the sputtering process pressure is 2.5x10 -3 mbar;

[0140] S64: Aluminum-doped zinc oxide is used as a target material to sputter on the surface of the first silver layer to form a zinc aluminum oxide layer, and the sputtering atmosphere of the zinc aluminum oxide layer is argon: oxygen = 800:40sccm;

[0141] S65: Zinc tin oxide with 52% ZnO and 48% SnO2 is used as a target material to sputter on the surface of the zinc aluminum oxide layer to form a zinc tin oxide layer, and the sputtering atmosphere of the zinc tin oxide layer is argon: oxygen = 700:40sccm;

[0142] S66: Aluminum-doped zinc oxide is used as a target material to sputter on the surface of the zinc tin oxide layer to form a zinc aluminum oxide layer, and the sputtering atmosphere of the zinc aluminum oxide layer is argon: oxygen = 800:40sccm;

[0143] S67: Silver is used as a target material to sputter on the surface of the zinc aluminum oxide layer to form a second silver layer, and the sputtering atmosphere of the second silver layer is argon 600sccm;

[0144] S68: Aluminum-doped zinc oxide is used as a target material to sputter on the surface of the second silver layer to form a zinc aluminum oxide layer, and the sputtering atmosphere of the zinc aluminum oxide layer is argon: oxygen = 800:40sccm;

[0145] S69: Zinc tin oxide with 52% ZnO and 48% SnO2 is used as a target material to sputter on the surface of the zinc aluminum oxide layer to form a zinc tin oxide layer, and the sputtering atmosphere of the zinc tin oxide layer is argon: oxygen = 700:40sccm;

[0146] S610: Aluminum-doped zinc oxide is used as a target material to sputter on the surface of the zinc tin oxide layer to form a zinc aluminum oxide layer, and the sputtering atmosphere of the zinc aluminum oxide layer is argon: oxygen = 800:40sccm;

[0147] S611: Nickel-chromium with 20% Ni and 80% Cr is used as a target material to sputter on the surface of the zinc aluminum oxide layer to form a nickel-chromium alloy layer, and the sputtering atmosphere of the nickel-chromium alloy layer is argon 600sccm;

[0148] S612: Silver is used as a target material to sputter on the surface of the nickel-chromium alloy layer to form a third silver layer, and the sputtering atmosphere of the third silver layer is argon 600sccm;

[0149] S613: Nickel-chromium with 20% Ni and 80% Cr is used as a target material to sputter on the surface of the third silver layer to form a nickel-chromium alloy layer, and the sputtering atmosphere of the nickel-chromium alloy layer is argon 600sccm;

[0150] S614: Titanium oxide is used as a target material to sputter on the surface of the nickel-chromium alloy layer to form a continuous or discontinuous titanium dioxide layer, and the sputtering atmosphere of the titanium dioxide layer is argon: oxygen = 800:30sccm;

[0151] S615: A silicon-zirconium-aluminum mixed alloy is used as the target material to sputter on the surface of a continuous or discontinuous titanium dioxide layer to form silicon-zirconium-aluminum nitride. The sputtering atmosphere of silicon-zirconium-aluminum nitride is argon:nitrogen = 450:650 sccm.

[0152] S616: Zirconia is used as the target material to sputter on the surface of silicon zirconium aluminum nitride to form a zirconium oxide layer. The sputtering atmosphere of the zirconium oxide layer is argon:oxygen = 800:20 sccm.

[0153] S7: Heat-treat the coated glass at 600~690℃ for 3~8 minutes.

[0154] Example 4

[0155] Example 4 also provides a method for preparing Low-E coated glass for automotive windshields based on triple silver. The method differs from the example in that when the thickness of the sputtered layer is different, the magnetron sputtering time is adjusted according to the layer thickness to obtain corresponding film layers of different thicknesses. The rest of the preparation method is the same as in Example 3, and the corresponding method for preparing Low-E coated glass for automotive windshields based on triple silver is obtained. The thickness of each layer of the obtained coated glass is shown in Table 1.

[0156] Example 5

[0157] This embodiment provides a method for preparing Low-E coated glass for automotive windshields based on tetrasilver coating, such as... Figure 3 As shown, from bottom to top, the layers include a glass substrate, a silicon nitride layer (40nm), a zinc-aluminum oxide layer (12nm), a first silver layer (9nm), a zinc-aluminum oxide layer (12nm), a zinc-tin oxide layer (55nm), a zinc-aluminum oxide layer (12nm), a second silver layer (12nm), a zinc-aluminum oxide layer (12nm), a zinc-tin oxide layer (45nm), a zinc-aluminum oxide layer (12nm), a third silver layer (14nm), a zinc-aluminum oxide layer (12nm), a zinc-tin oxide layer (50nm), a zinc-aluminum oxide layer (12nm), a nickel-chromium alloy layer (0.2nm), a fourth silver layer (11nm), a nickel-chromium alloy layer (0.2nm), titanium dioxide (13nm), silicon-zirconium-aluminum nitride (30nm), and a zirconium oxide layer (5nm). The fabrication process is achieved using vacuum magnetron sputtering deposition technology, and the specific steps are as follows:

[0158] S1: Glass pretreatment: The original glass sheet is thoroughly cleaned to remove dust, oil and other impurities.

[0159] S2: Loading Glass: Transfer the cleaned glass into the vacuum chamber of the coating equipment.

[0160] S3: Vacuuming: Start the vacuum system to evacuate the chamber to the required high vacuum level.

[0161] S4: Target preparation: Install and prepare the target materials required for the silicon nitride layer, zinc aluminum oxide layer, silver layer, zinc tin oxide layer, nickel chromium alloy layer, titanium dioxide layer, silicon zirconium nitride layer, and zirconium oxide layer of high-performance coated glass for new energy vehicles.

[0162] S5: Pre-sputtering: The target is briefly pre-sputtered to remove oxides, impurities, and other impurities on the surface of the target, ensuring the quality of the coating.

[0163] S6: Coating process: Turn on the magnetron sputtering power, and the target atoms or ions are sputtered and deposited on the glass surface to form a coating layer. During the coating process, the sputtering power, gas flow, and other parameters are precisely controlled to obtain the desired coating thickness and performance.

[0164] S61: Use rotating silicon aluminum as the target material to sputter on the surface of the glass substrate to form a silicon nitride layer. The sputtering atmosphere for the silicon nitride layer is argon:nitrogen = 450:650 sccm.

[0165] S62: Use aluminum-doped zinc oxide as the target material to sputter on the surface of the silicon nitride layer to form an aluminum zinc oxide layer. The sputtering atmosphere for the aluminum zinc oxide layer is argon:oxygen = 800:40 sccm.

[0166] S63: Use silver as the target material to sputter on the surface of the aluminum zinc oxide layer to form a first silver layer. The sputtering atmosphere for the first silver layer is argon 600 sccm.

[0167] S64: Use aluminum-doped zinc oxide as the target material to sputter on the surface of the first silver layer to form an aluminum zinc oxide layer. The sputtering atmosphere for the aluminum zinc oxide layer is argon:oxygen = 800:40 sccm.

[0168] S65: Use 52% ZnO, 48% SnO2 zinc tin oxide as the target material to sputter on the surface of the aluminum zinc oxide layer to form a zinc tin oxide layer. The sputtering atmosphere for the zinc tin oxide layer is argon:oxygen = 700:40 sccm.

[0169] S66: Use aluminum-doped zinc oxide as the target material to sputter on the surface of the zinc tin oxide layer to form an aluminum zinc oxide layer. The sputtering atmosphere for the aluminum zinc oxide layer is argon:oxygen = 800:40 sccm.

[0170] S67: Use silver as the target material to sputter on the surface of the aluminum zinc oxide layer to form a second silver layer. The sputtering atmosphere for the second silver layer is argon 600 sccm.

[0171] S68: Use aluminum-doped zinc oxide as the target material to sputter on the surface of the second silver layer to form an aluminum zinc oxide layer. The sputtering atmosphere for the aluminum zinc oxide layer is argon:oxygen = 800:40 sccm.

[0172] S69: Zinc tin oxide with 52% ZnO, 48% SnO2 is used as target material to sputter on the surface of the zinc aluminum oxide layer to form a zinc tin oxide layer, the sputtering atmosphere of the zinc tin oxide layer is argon: oxygen = 700:40 sccm;

[0173] S610: Aluminum doped zinc oxide is used as target material to sputter on the surface of the zinc tin oxide layer to form a zinc aluminum oxide layer, the sputtering atmosphere of the zinc aluminum oxide layer is argon: oxygen = 800:40 sccm;

[0174] S611: Silver is used as target material to sputter on the surface of the zinc aluminum oxide layer to form a third silver layer, the sputtering atmosphere of the third silver layer is argon 600 sccm;

[0175] S612: Aluminum doped zinc oxide is used as target material to sputter on the surface of the third silver layer to form a zinc aluminum oxide layer, the sputtering atmosphere of the zinc aluminum oxide layer is argon: oxygen = 800:40 sccm;

[0176] S613: Zinc tin oxide with 52% ZnO, 48% SnO2 is used as target material to sputter on the surface of the zinc aluminum oxide layer to form a zinc tin oxide layer, the sputtering atmosphere of the zinc tin oxide layer is argon: oxygen = 700:40 sccm;

[0177] S614: Aluminum doped zinc oxide is used as target material to sputter on the surface of the zinc tin oxide layer to form a zinc aluminum oxide layer, the sputtering atmosphere of the zinc aluminum oxide layer is argon: oxygen = 800:40 sccm;

[0178] S615: Nickel chromium with 20% Ni, 80% Cr is used as target material to sputter on the surface of the zinc aluminum oxide layer to form a nickel chromium alloy layer, the sputtering atmosphere of the nickel chromium alloy layer is argon 600 sccm;

[0179] S616: Silver is used as target material to sputter on the surface of the nickel chromium alloy layer to form a fourth silver layer, the sputtering atmosphere of the fourth silver layer is argon 600 sccm, the sputtering process pressure is 2.5x10 -3 mbar;

[0180] S617: Nickel chromium with 20% Ni, 80% Cr is used as target material to sputter on the surface of the fourth silver layer to form a nickel chromium alloy layer, the sputtering atmosphere of the nickel chromium alloy layer is argon 600 sccm;

[0181] S618: Titanium oxide is used as target material to sputter on the surface of the nickel chromium alloy layer to form a continuous or discontinuous titanium dioxide layer, the sputtering atmosphere of the titanium dioxide layer is argon: oxygen = 800:30 sccm;

[0182] S619: using silicon, zirconium and aluminum mixed alloy as target material, sputtering on the surface of continuous or discontinuous titanium dioxide layer to form silicon zirconium aluminum nitride, the sputtering atmosphere of silicon zirconium aluminum nitride is argon: nitrogen = 450: 650 sccm;

[0183] S620: using zirconium oxide as target material, sputtering on the surface of silicon zirconium aluminum nitride to form zirconium oxide layer, the sputtering atmosphere of zirconium oxide layer is argon: oxygen = 800: 20 sccm.

[0184] S7: heat treating the coated glass at 600-690℃ for 3-8min.

[0185] Example 6

[0186] Example 6 also provides a preparation method of Low-E coated glass for automobile front windshield based on four silver, the difference between the preparation method and example is that when the thickness of the layer formed by sputtering is different, the magnetron sputtering time is adjusted according to the thickness of the layer to obtain corresponding film layers with different thicknesses, and the rest of the preparation method is the same as example 5, to obtain the corresponding preparation method of Low-E coated glass for automobile front windshield based on four silver, and the thickness of each layer of the coated glass obtained is shown in table 1.

[0187] Comparative example 1-comparative example 9

[0188] Comparative example 1-comparative example 9 also provides a Low-E coated glass for automobile front windshield, the preparation of the coated glass and the thickness of each layer are shown in table 2 and table 3.

[0189] Table 1

[0190]

[0191] Table 2

[0192]

[0193] Table 3

[0194]

[0195] The coated glass obtained by the above examples 1-6 and comparative examples 1-9 is respectively prepared into laminated glass with white glass with a thickness of 6mm, the laminated thickness is 2.1mm, and the optical performance is detected, and the test results are shown in table 4.

[0196] Table 4

[0197]

[0198] As can be seen from Table 4, the coated glass provided by the present application can improve the haze to the range of 0.5% to 0.8%, and can also ensure high visible light transmittance (double silver ≥ 74%, triple silver ≥ 72%, quadruple silver ≥ 70%) and low emissivity (≤ 0.05%), meeting the requirements of the front windshield of the automobile, and solving the technical problems that it is difficult to achieve high visible light transmittance and low emissivity at a high haze in the prior art, and avoiding the problems of glare and eye fatigue of the person inside the vehicle caused by high visible light transmittance.

[0199] In addition, as can be seen from Example 1, Example 3, Example 5, Comparative Example 7, Comparative Example 8 and Comparative Example 9, the doping of titanium dioxide in the silicon zirconium nitride can not only further enhance the haze of the coated glass, but also reduce the surface resistance of the coated glass.

[0200] In addition, as can be seen from Example 1 and Comparative Example 2, when the thickness of the silver layer in the double silver coated glass is higher than 25 nm, the visible light transmittance thereof is obviously decreased, and when the thickness of the silver layer is lower than 15 nm, although the visible light transmittance can meet the requirements, the emissivity and the surface resistance thereof are obviously increased, and it is difficult to meet the requirements of environmental temperature and energy saving;

[0201] In addition, as can be seen from Comparative Example 3, in the three-layer coated glass, when the thickness of the second silver layer is too low, the emissivity and the surface resistance thereof are obviously increased, and it is difficult to meet the requirements of environmental temperature and energy saving;

[0202] In addition, as can be seen from Comparative Example 4, in the three-layer coated glass, when the thickness of the first silver layer is too high, not only the visible light transmittance thereof is decreased, but also it is difficult to meet the requirement of high visible light transmittance; and when the thickness of the third silver layer is too high, the visible light transmittance thereof is also decreased, and it is difficult to meet the requirement of high visible light transmittance.

[0203] In addition, as can be seen from Comparative Example 5, in the four silver coated glass, when the thicknesses of the second silver layer, the third silver layer and the fourth silver layer are too low, the emissivity and the surface resistance thereof are obviously increased, and it is difficult to meet the requirements of environmental temperature and energy saving;

[0204] In addition, as can be seen from Comparative Example 5, in the four silver coated glass, when the thicknesses of the first silver layer, the second silver layer, the third silver layer and the fourth silver layer are too high, not only the visible light transmittance thereof is decreased, but also it is difficult to meet the requirement of high visible light transmittance.

[0205] The above merely illustrates the specific embodiments of the present application, but the protection scope of the present application is not limited thereto, and any changes or replacements within the technical range disclosed by the present application can be easily thought by those skilled in the art, and should be covered in the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A Low-E coated glass for automobile front windshields, characterized in that, The composite coating structure comprises a glass substrate and a composite coating structure arranged on the glass substrate; The composite coating structure comprises at least two functional layers and a nickel-chromium alloy layer arranged on a silver functional layer away from the glass substrate; The silver functional layer away from the glass substrate is a continuous silver layer with a roughness Ra not less than 0.8 nm, and the nickel-chromium alloy layer is a layer structure with a thickness not higher than 0.8 nm and discontinuous, and nickel-chromium alloy particles in the nickel-chromium alloy layer are distributed in recesses of the silver functional layer away from the glass substrate; A top dielectric layer is arranged on the nickel-chromium alloy layer; The top dielectric layer comprises a continuous or discontinuous layer structure formed by high-refractive-index crystals with a refractive index not less than 2.3 under light with a wavelength of 550 nm; the high-refractive-index crystals are rutile titanium dioxide; The composite coating structure comprises two functional layers: a first silver layer and a second silver layer; the silver functional layer away from the glass substrate is the second silver layer; The sum of the thicknesses of the first silver layer and the second silver layer is not less than 15 nm and not higher than 25 nm.

2. The Low-E coated glass for automotive front windshields according to claim 1, characterized in that, An intermediate dielectric layer is arranged between the silver functional layer away from the glass substrate and other silver functional layers; a second nickel-chromium alloy layer is arranged on the intermediate dielectric layer close to the silver functional layer away from the glass substrate; the second nickel-chromium alloy layer is a continuous nickel-chromium alloy layer.

3. The Low-E coated glass for automotive front windshields according to claim 1, characterized in that, The doping amount of the high-refractive-index crystals in the top dielectric layer is 5-10% in mass fraction.

4. The Low-E coated glass for automobile front windshields according to claim 3, characterized in that, The thickness of the top dielectric layer is 20-60 nm.

5. The Low-E coated glass for automotive front windshields according to claim 1, characterized in that, The intermediate medium layer arranged between the first silver layer and the second silver layer further comprises a ZnAlO x layer, a ZnSnO x layer, a ZnAlO x layer.

6. The Low-E coated glass for automotive front windshields according to claim 1, characterized in that, The composite coating structure further comprises a bottom protective layer and a top protective layer; The bottom protective layer is selected from at least one of SiZrN x , ZrO x , NbO x , SiN x , ZnSnO x , SiZrAlN x . The top protective layer includes a protective layer and a top medium layer; the protective layer is selected from at least one of ZrO x , NbO x ; the top medium layer is selected from at least one of SiZrAlN x , SiZrN x , SiN x , TiO2, SiO x , ZnAlO x .

7. The Low-E coated glass for automotive front windshields according to claim 6, characterized in that, A seed layer is further arranged between the bottom protective layer and the first silver layer.

8. A Low-E coated glass for automotive front windshields, characterized in that, The composite coating structure comprises a glass substrate and a composite coating structure arranged on the glass substrate; The composite coating structure comprises at least two functional layers and a nickel-chromium alloy layer arranged on a silver functional layer away from the glass substrate; The silver functional layer away from the glass substrate is a continuous silver layer with a roughness Ra not less than 0.8 nm, and the nickel-chromium alloy layer is a layer structure with a thickness not higher than 0.8 nm and discontinuous, and nickel-chromium alloy particles in the nickel-chromium alloy layer are distributed in recesses of the silver functional layer away from the glass substrate; A top dielectric layer is arranged on the nickel-chromium alloy layer; The top dielectric layer comprises a continuous or discontinuous layer structure formed by high-refractive-index crystals with a refractive index not less than 2.3 under light with a wavelength of 550 nm; the high-refractive-index crystals are rutile titanium dioxide; The composite coating structure comprises three functional layers: a first silver layer, a second silver layer and a third silver layer; the silver functional layer away from the glass substrate is the third silver layer; The thickness of the third silver layer is lower than that of the second silver layer, and the thickness of the first silver layer is lower than that of the second silver layer; the thickness of the first silver layer is not higher than 10 nm; the thickness of the second silver layer is not less than 13 nm and not higher than 18 nm; the thickness of the third silver layer is not higher than 13 nm.

9. The Low-E coated glass for automotive front windshields of claim 8, characterized in that, An intermediate medium layer is arranged between the silver functional layer far from the glass substrate and other silver functional layers; a second nickel-chromium alloy layer is arranged on the side of the intermediate medium layer close to the silver functional layer far from the glass substrate; and the second nickel-chromium alloy layer is a continuous nickel-chromium alloy layer.

10. The Low-E coated glass for automotive front windshields according to claim 8, characterized in that, The doping amount of the high-refractive-index crystal in the top medium layer is 5-10% in mass fraction.

11. The Low-E coated glass for automobile front windshield according to claim 8, characterized in that, The thickness of the top medium layer is 20-60 nm.

12. The Low-E coated glass for automotive front windshields according to claim 8, characterized in that, The composite coating structure further comprises a bottom protective layer and a top protective layer. The bottom protective layer is selected from at least one of SiZrN x , ZrO x , NbO x , SiN x , ZnSnO x , SiZrAlN x . The top protective layer includes a protective layer and a top dielectric layer; the protective layer is selected from at least one of ZrO x , NbO x ; the top dielectric layer is selected from at least one of SiZrAlN x , SiZrN x , SiN x , TiO2, SiO x , ZnAlO x .

13. The Low-E coated glass for automotive front windshields according to claim 12, characterized in that, A seed layer is further arranged between the bottom protective layer and the first silver layer.

14. The Low-E coated glass for automotive front windshields according to claim 8, characterized in that, The first silver layer and the second silver layer are provided with a first intermediate medium layer, the first medium layer comprises a ZnAlO x layer, a ZnSnO x layer, a ZnAlO x layer stacked; the second silver layer and the third silver layer are provided with a second intermediate medium layer, the second medium layer comprises a ZnAlO x layer, a ZnSnO x layer, a ZnAlO x layer stacked.

15. A Low-E coated glass for automotive front windshields, characterized in that, The composite coating structure further comprises a bottom protective layer and a top protective layer. The composite coating structure further comprises a bottom protective layer and a top protective layer. The nickel-chromium alloy layer is a layer structure with a thickness not higher than 0.8 nm and discontinuous, and the nickel-chromium alloy particles in the nickel-chromium alloy layer are distributed in the recesses of the silver functional layer far from the glass substrate. The top medium layer comprises a continuous or discontinuous layer structure formed by high-refractive-index crystals with a refractive index not lower than 2.3 under light with a wavelength of 550 nm; and the high-refractive-index crystals are rutile-type titanium dioxide. The composite coating structure comprises four functional layers: a first silver layer, a second silver layer, a third silver layer, and a fourth silver layer; and the silver functional layer far from the glass substrate is the fourth silver layer. The thickness of the first silver layer is not higher than 10 nm; the thickness of the second silver layer and the fourth silver layer is not lower than 10 nm and not higher than 13 nm; and the thickness of the third silver layer is not lower than 13 nm and not higher than 18 nm. An intermediate medium layer is arranged between the silver functional layer far from the glass substrate and other silver functional layers; a second nickel-chromium alloy layer is arranged on the side of the intermediate medium layer close to the silver functional layer far from the glass substrate; and the second nickel-chromium alloy layer is a continuous nickel-chromium alloy layer.

16. The Low-E coated glass for automotive front windshields of claim 15, wherein, The doping amount of the high-refractive-index crystal in the top medium layer is 5-10% in mass fraction.

17. The Low-E coated glass for automotive front windshields according to claim 15, wherein, 18. The Low-E coated glass for automobile front windshield according to claim 15, characterized in that, The thickness of the top medium layer is 20-60 nm. The composite coating structure further comprises a bottom protective layer and a top protective layer.

19. The Low-E coated glass for automotive front windshields of claim 15, wherein, The first silver layer and the second silver layer are provided with a first intermediate medium layer, the first medium layer comprises a ZnAlO x layer, a ZnSnO x layer and a ZnAlO x layer which are arranged in a stack; the second silver layer and the third silver layer are provided with a second intermediate medium layer, the second medium layer comprises a ZnAlO x layer, a ZnSnO x layer and a ZnAlO x layer which are arranged in a stack; the third silver layer and the fourth silver layer are provided with a third intermediate medium layer, the third medium layer comprises a ZnAlO x layer, a ZnSnO x layer and a ZnAlO x layer which are arranged in a stack.

20. The Low-E coated glass for automotive front windshields of claim 15, wherein, A seed layer is further arranged between the bottom protective layer and the first silver layer. The bottom protective layer is selected from at least one of SiZrN x , ZrO x , NbO x , SiN x , ZnSnO x , SiZrAlN x . The top protective layer includes a protective layer and a top dielectric layer; the protective layer is selected from at least one of ZrO x , NbO x ; the top dielectric layer is selected from at least one of SiZrAlN x , SiZrN x , SiN x , TiO2, SiO x , ZnAlO x .

21. The Low-E coated glass for automotive front windshields according to claim 20, wherein, A bottom protective layer, a seed layer, a first silver layer, a first intermediate medium layer, a second silver layer, a second intermediate medium layer, a nickel-chromium alloy layer, a third silver layer, a nickel-chromium alloy layer, a top medium layer, and a protective layer are sequentially formed on the glass substrate by vacuum magnetron sputtering coating; the third silver layer is a continuous silver layer with a roughness Ra not lower than 0.8 nm, and the nickel-chromium alloy layer is a layer structure with a thickness not higher than 0.8 nm and discontinuous; 22. A method for manufacturing a Low-E coated glass for an automobile front windshield, characterized in that, ​ The top medium layer is formed into a continuous or discontinuous layer structure containing high refractive index crystals with a refractive index not less than 2.3 under light with a wavelength of 550 nm; the high refractive index crystals are rutile titanium dioxide; the thickness of the first silver layer is not higher than 10 nm; the thickness of the second silver layer is not less than 13 nm and not higher than 18 nm; and the thickness of the third silver layer is not higher than 13 nm.

23. The method for preparing Low-E coated glass for automotive windshields according to claim 22, characterized in that, After forming the sacrificial layer by magnetron sputtering, the coated glass is heat treated at 600-690 ℃ for 3-8 min.

24. A method for manufacturing a Low-E coated glass for an automobile front windshield, characterized in that, The bottom protective layer, seed layer, nickel-chromium alloy layer, first silver layer, nickel-chromium alloy layer, intermediate medium layer, nickel-chromium alloy layer, second silver layer, nickel-chromium alloy layer, top medium layer and protective layer are formed on the glass substrate by vacuum magnetron sputtering in sequence, so that the second silver layer is a continuous silver layer with a roughness Ra not less than 0.8 nm, and the nickel-chromium alloy layer is a discontinuous layer structure with a thickness not higher than 0.8 nm; The top medium layer is formed into a continuous or discontinuous layer structure containing high refractive index crystals with a refractive index not less than 2.3 under light with a wavelength of 550 nm; the high refractive index crystals are rutile titanium dioxide; and the sum of the thicknesses of the first silver layer and the second silver layer is not less than 15 nm and not higher than 25 nm.

25. The method for preparing Low-E coated glass for automotive windshields according to claim 24, characterized in that, After forming the sacrificial layer by magnetron sputtering, the coated glass is heat treated at 600-690 ℃ for 3-8 min.

26. A method for manufacturing a Low-E coated glass for an automobile front windshield, characterized in that, The bottom protective layer, seed layer, first silver layer, first intermediate medium layer, second silver layer, second intermediate medium layer, third silver layer, third intermediate medium layer, nickel-chromium alloy layer, fourth silver layer, nickel-chromium alloy layer, top medium layer and protective layer are formed on the glass substrate by vacuum magnetron sputtering in sequence, so that the fourth silver layer is a continuous silver layer with a roughness Ra not less than 0.8 nm, and the nickel-chromium alloy layer is a discontinuous layer structure with a thickness not higher than 0.8 nm; The top medium layer is formed into a continuous or discontinuous layer structure containing high refractive index crystals with a refractive index not less than 2.3 under light with a wavelength of 550 nm; the high refractive index crystals are rutile titanium dioxide; the thickness of the first silver layer is not higher than 10 nm; the thicknesses of the second silver layer and the fourth silver layer are not less than 10 nm and not higher than 13 nm; and the thickness of the third silver layer is not less than 13 nm and not higher than 18 nm.

27. The method for preparing Low-E coated glass for automotive windshields according to claim 26, characterized in that, After forming the sacrificial layer by magnetron sputtering, the coated glass is heat treated at 600-690 ℃ for 3-8 min.

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