Magnetron Sputtering Coated Glass and Its Preparation Process

Abstract

The present invention discloses a magnetron sputtering coated glass and its preparation process, relating to the technical field of low-emissivity glass. The magnetron sputtering coated glass includes a glass substrate, and the following film layers are sequentially stacked on the upper surface of the glass substrate from bottom to top: a first film layer of silicon nitride layer, a second film layer of titanium oxide layer, a third film layer of aluminum zinc oxide layer, a fourth film layer of metallic silver layer, a fifth film layer of metallic titanium layer, a sixth film layer of titanium oxide layer, a seventh film layer of aluminum zinc oxide layer, an eighth film layer of metallic silver layer, a ninth film layer of metallic titanium layer, a tenth film layer of titanium oxide layer, an eleventh film layer of aluminum zinc oxide layer, a twelfth film layer of metallic silver layer, a thirteenth film layer of metallic titanium layer, a fourteenth film layer of titanium oxide layer, a fifteenth film layer of zinc oxide silicon layer, and a sixteenth film layer of silicon nitride. By using magnetron sputtering deposition to set multiple dielectric films, interface films and metal films on the surface of the glass matrix, the present invention forms a low-emissivity film system, realizing the transmission of visible light and the reflection of infrared light by the coated glass.

Description

Technical Field

[0001] The present invention relates to the technical field of low-emissivity glass, specifically magnetron sputtering coated glass and its preparation process. Background Technique

[0002] Coated glass, also known as reflective glass, has a layer or multiple layers of metal, alloy or metal compound thin films coated on the glass surface to change the optical properties of the glass and meet certain specific requirements. According to product characteristics, it can be divided into heat-reflective glass, low-emissivity (LOW-E) glass, conductive film glass, etc. The most widely used coated glasses are heat-reflective glass and low-emissivity glass. Basically, two production methods, namely vacuum magnetron sputtering method and chemical vapor deposition method, are adopted.

[0003] Among them, heat-reflective glass generally has a layer or multiple layers of metals such as metal chromium, metal titanium or stainless steel or their compounds coated on the glass surface, having an appropriate transmittance to visible light, a relatively high reflectance to infrared light, and a relatively high absorption rate to ultraviolet light. Therefore, it is also called sunlight control glass and is mainly applied to fields such as building facades and glass facades.

[0004] Low-emissivity glass has multiple layers of metals such as silver, copper or tin or their compounds coated on the glass surface, having a relatively high transmittance to visible light and a very high reflectance to infrared light, which gives it good heat insulation performance and is mainly applied in buildings, automobiles and ships. However, for some existing low-emissivity glass products, their light transmittance is insufficient, which affects the natural lighting effect inside the glass, especially in times or regions with insufficient light, resulting in dim indoor light. Therefore, we propose magnetron sputtering coated glass and its preparation process. Summary of the Invention

[0005] The purpose of the present invention is to provide magnetron sputtering coated glass and its preparation process to solve the problems raised in the above background technique.

[0006] To solve the above technical problems, the present invention provides the following technical solution: Magnetron sputtering coated glass, including a glass substrate, and a dielectric film, an interface film and a metal film are provided on the upper surface of the glass substrate.

[0007] Further, the dielectric film is a metal oxide or silicon nitride, zirconium nitride, and the metal oxide includes one or more of titanium oxide, silicon oxide, vanadium oxide, nickel chromium oxide, zirconium oxide, zinc oxide, aluminum zinc oxide, tin zinc oxide, bismuth oxide, tin oxide, indium tin oxide, cobalt oxide, niobium oxide, cadmium oxide, indium oxide.

[0008] Further, the interface film includes one or more of zinc oxide, aluminum zinc oxide, titanium oxide, nickel chromium oxide, nickel chromium, metal titanium, indium tin oxide.

[0009] Further, the metal film includes, but is not limited to, one or more of silver, copper, gold, and aluminum.

[0010] Further, the following film layers are sequentially stacked on the upper surface of the glass substrate from bottom to top: the first film layer is a silicon nitride layer with a thickness of 15 - 25 nm; silicon nitride has excellent acid and alkali resistance characteristics and scratch resistance. Coating it on the surface of the glass substrate can play a role in blocking the diffusion of impurities, prevent the diffusion of ions in the glass substrate, and avoid affecting the film layer characteristics. However, the affinity between silicon nitride and the metal silver layer is very poor, and an interface layer needs to be added between them.

[0011] The second film layer is a titanium oxide layer with a thickness of 20 - 30 nm; adding a titanium oxide layer on the surface of the silicon nitride layer to form a composite film layer can coordinate its mechanical properties and thermal stability, protect the glass substrate, and enable the prepared coated glass to have more excellent comprehensive properties.

[0012] The third film layer is a zinc aluminum oxide layer with a thickness of 5 - 10 nm; zinc oxide has a smooth property, and the zinc aluminum oxide layer (AZO) is zinc oxide doped with aluminum. It not only has the characteristics of a smooth surface and a dense structure but also has a high refractive index and good sputtering efficiency. It can make the silver layer coated on it more uniform. As a seed layer for the metal silver layer, it has a good growth condition and more excellent comprehensive properties. It can reduce the reflectivity of the metal silver layer, enhance the visible light transmittance and emissivity of the film system, and improve its heat insulation performance.

[0013] The fourth film layer is a metal silver layer with a thickness of 8 - 10 nm; silver is one of the substances with the lowest emissivity in nature. Coating a silver layer on the glass surface can effectively reduce the emissivity of the glass and achieve high reflection of infrared light. The nanoscale silver layer can allow visible light to pass through and has relatively low absorption of visible light, making it have good spectral transmittance and reflectance characteristics. However, the chemical and thermal properties of the metal silver layer are unstable, and its performance will deteriorate under the action of thermal oxidation and corrosion.

[0014] The fifth film layer is a metal titanium layer with a thickness of 1 - 3 nm; setting the titanium layer as a stable barrier layer can protect the metal silver layer from the invasion of oxygen and other pollutants in subsequent processes, improve the adhesion between the silver layer and the dielectric layer; and through the combination of the metal silver layer and the titanium layer and the control of their thicknesses, it helps the prepared coated glass to maintain its visible light transmittance while improving its infrared light reflection performance, thereby improving its heat insulation effect.

[0015] The sixth film layer is a titanium oxide layer with a thickness of 8 - 15 nm. Titanium oxide has good acid and alkali resistance, can effectively block the diffusion of impurities, has good adhesion to the silver layer coated with metallic titanium, has good surface wettability, can relieve interface stress and improve the connection strength. At the same time, it has a good refractive index, can improve the light transmittance, and is suitable as a dielectric film. However, due to its high refractive index, a slight change in the film thickness of the titanium oxide layer caused by scratching will have a large optical impact. Therefore, the titanium oxide layer is not suitable as the top dielectric film of coated glass.

[0016] The seventh film layer is a zinc aluminum oxide layer with a thickness of 5 - 10 nm;

[0017] The eighth film layer is a metallic silver layer with a thickness of 6 - 12 nm;

[0018] The ninth film layer is a metallic titanium layer with a thickness of 1 - 3 nm;

[0019] The tenth film layer is a titanium oxide layer with a thickness of 20 - 30 nm;

[0020] The eleventh film layer is a zinc aluminum oxide layer with a thickness of 5 - 10 nm;

[0021] The twelfth film layer is a metallic silver layer with a thickness of 5 - 13 nm. The coated glass in this application is provided with three silver layers, which has an extremely low surface emissivity compared with double - silver and single - silver coated glass, and has stronger thermal energy blocking ability.

[0022] The thirteenth film layer is a metallic titanium layer with a thickness of 1 - 3 nm;

[0023] The fourteenth film layer is a titanium oxide layer with a thickness of 20 - 30 nm;

[0024] The fifteenth film layer is a zinc silicon oxide layer with a thickness of 10 - 20 nm;

[0025] The sixteenth film layer is silicon nitride with a thickness of 8 - 15 nm. Silicon - doped zinc oxide can enhance the strength and stability of the film layer. Cooperating with the outermost protective layer (the sixteenth film layer), it improves the scratch resistance, wear resistance and chemical corrosion resistance of the surface film layer of the coated glass; and can improve the reflection and scattering of the film layer to ultraviolet rays, and improve the heat insulation performance of the coated glass.

[0026] The preparation process of magnetron - sputtered coated glass includes the following process steps:

[0027] (1) Using argon as the working gas, nitrogen as the reaction gas, and silicon as the target, direct - current magnetron sputtering is carried out to deposit a silicon nitride layer; the sputtering power is 100 - 120 W, the air pressure is 0.005 - 0.008 mbar, and the ratio of argon to nitrogen is 1:(1.4 - 1.6);

[0028] (2) Using argon as the working gas and titanium dioxide as the target, direct current magnetron sputtering is carried out to deposit a titanium oxide layer; the sputtering power is 150 - 200 W, and the gas pressure is 0.003 - 0.005 mbar;

[0029] (3) Using argon as the working gas and aluminum zinc oxide as the target, direct current magnetron sputtering is carried out to deposit an aluminum zinc oxide layer; the sputtering power is 80 - 100 W, and the gas pressure is 0.003 - 0.005 mbar;

[0030] (4) Using argon as the working gas and silver as the target, alternating current magnetron sputtering is carried out to deposit a silver metal layer; the sputtering power is 70 - 90 W, and the gas pressure is 0.002 - 0.003 mbar;

[0031] (5) Using argon as the working gas and hydrogen as the reaction gas, and titanium as the target, alternating current magnetron sputtering is carried out to deposit a titanium metal layer; the sputtering power is 45 - 55 W, the gas pressure is 0.002 - 0.004 mbar, and the ratio of argon to nitrogen is 1:(0.1 - 0.5);

[0032] When magnetron sputtering is carried out with titanium as the target to deposit a titanium metal layer, while serving as a barrier layer for the silver metal layer, by introducing hydrogen during the magnetron sputtering process, hydrogen enters the lattice of the titanium layer to form an unsaturated TiHx film layer, making it more metallic. The real part of the infrared light is reduced and the imaginary part is increased, and the change in visible light is not significant. This increases the absorption of infrared light by the glass and slows down its propagation, being able to significantly reduce the irradiation of infrared light, thereby improving the heat insulation ability of the coated glass. And compared with acid-etched hydrogenated and saturated hydrogenated titanium, its strength is relatively higher, the morphology is better, and it has a better bonding ability with the titanium oxide layer set on its surface, improving the overall strength of the prepared coated glass.

[0033] (6) Using argon as the working gas and titanium dioxide as the target, direct current magnetron sputtering is carried out to deposit a titanium oxide layer; the sputtering power is 150 - 200 W, and the gas pressure is 0.003 - 0.005 mbar;

[0034] The oxide film of titanium is relatively stable and can serve as an effective barrier for hydrogen permeation; and it has good heat resistance, being able to alleviate the thermal influence brought by the strong near-infrared absorption ability of the titanium metal layer.

[0035] (7) Repeat the operations in steps (3) - (6) twice to successively form aluminum zinc oxide layers, silver metal layers, titanium metal layers and titanium oxide layers, aluminum zinc oxide layers, silver metal layers, titanium metal layers and titanium oxide layers;

[0036] (8) Using argon as the working gas and zinc silicon oxide as the target, direct current magnetron sputtering is carried out to deposit a zinc silicon oxide layer; the sputtering power is 80 - 120 W, and the gas pressure is 0.003 - 0.005 mbar;

[0037] (9) Using argon as the working gas, nitrogen as the reaction gas, and silicon as the target, direct current magnetron sputtering is carried out to deposit a silicon nitride layer;

[0038] The sputtering power is 100 - 120 W, the air pressure is 0.005 - 0.008 mbar, and the ratio of argon to nitrogen is 1:(1.4 - 1.6) to obtain coated glass.

[0039] Furthermore, step (6) can be replaced by the following process:

[0040] Using argon as the working gas, trifluoromethane as the reaction gas, and composite silica as the target, direct current magnetron sputtering is carried out to deposit a silicon oxide doped layer;

[0041] The sputtering power is 50 - 70 W, the air pressure is 0.018 - 0.025 mbar, and the ratio of argon to trifluoromethane is 1:(0.4 - 0.6).

[0042] Furthermore, the target, composite silica, is prepared by the following process:

[0043] Mix tetraethyl orthosilicate, ethanol, and ammonium fluoride, adjust the pH to 3.5 - 4.5 with hydrochloric acid, and let it stand for hydrolysis for 8 - 24 h to obtain a colloidal solution;

[0044] Ball - mill silicon dioxide and graphite, add the hydrolyzed solution and mix to prepare a mixture; hot - press and sinter to obtain composite silica.

[0045] Furthermore, the mixture includes the following mass components: 20 - 35 parts of graphite, 65 - 80 parts of silicon dioxide, and 10 - 30 parts of the colloidal solution;

[0046] In the colloidal solution, the molar ratio of tetraethyl orthosilicate to ammonium fluoride is 10:(0.5 - 1.2);

[0047] The ratio of tetraethyl orthosilicate to ethanol is (1 - 3) g / 10 mL; the concentration of ethanol is 70 - 90 v%;

[0048] The concentration of hydrochloric acid is 1 M.

[0049] Furthermore, the process conditions for hot - press sintering are: evacuate to below 100 Pa, heat up to 150 - 180 °C, keep warm for 30 - 60 min; heat up to 660 - 700 °C, keep warm for 60 - 90 min; heat up to 750 - 820 °C, keep warm for 60 - 90 min; apply pressure up to 20 - 30 MPa, keep warm and under pressure for 90 - 120 min.

[0050] In the above technical solution, tetraethyl orthosilicate is hydrolyzed in ethanol to form a colloidal solution. Silicon dioxide and graphite are mixed and hot-pressed and sintered to prepare a target. The colloidal solution contains ammonium fluoride. The radius of its fluoride ion is similar to that of the hydroxyl ion, making it easy for the Si-OH generated by the hydrolysis of tetraethyl orthosilicate to undergo a substitution reaction with ammonium fluoride, resulting in more fluoride ions existing in the form of HF and overflowing at the high temperature of hot-pressing and sintering, catalyzing the hydrolysis and polymerization of tetraethyl orthosilicate, reducing the content of hydroxyl groups and water in the colloidal solution, promoting the composite between silicon dioxide and graphite particles, reducing target defects, and being beneficial to the uniformity and stability of the properties of the prepared target. And some fluoride ions enter the network during sintering to form Si-F bonds, which helps to increase the fluorine content in the prepared silicon dioxide doped layer and improve its optical properties.

[0051] The silicon dioxide target contains graphite and can deposit to form a fluorinated diamond-like structure under the action of magnetron sputtering and the gas source trifluoromethane, making the formed film layer a diamond-like composite film layer of silicon dioxide and doped with fluorine, denoted as a silicon dioxide doped layer. Compared with titanium dioxide, it has a wider bandgap width, a relatively lower refractive index, and a higher infrared reflection and absorption ability.

[0052] In the above technical solution, the hydrogenation of the titanium metal layer increases the real part of its ultraviolet light, which promotes the faster propagation of ultraviolet light in the glass. Compared with titanium oxide, the silicon dioxide doped layer can increase the absorption, reflection and scattering of ultraviolet light by the coated glass, reduce the ultraviolet light irradiation, and endow it with good anti-radiation ability.

[0053] The silicon dioxide doped layer has better infrared light reflection and absorption properties and good high-temperature resistance, can effectively reduce the heat conduction in the coated glass, and thus improves the heat insulation ability of the prepared coated glass. And its bandgap width is relatively wider, the absorption of light is weakened, and it has higher visible light transmittance. And it can improve the refractive uniformity of the titanium metal layer, ensure optical stability, and improve the stability and uniformity of the optical properties of the prepared coated glass.

[0054] The silicon dioxide doped layer has a uniform and high refractive index, which ensures the stable optical properties of the coated glass. Compared with titanium dioxide, the silicon dioxide doped layer has a lower refractive index, lower than that of the adjacent metal film layer and higher than that of zinc oxide silicon, thus forming a film layer system with a gradually increasing and cyclic refractive index (metal silver layer - titanium metal layer - silicon dioxide doped layer - zinc oxide aluminum layer), reducing light reflection and scattering, improving the transmission efficiency of visible light, reducing the refractive index difference between film layers, alleviating the reflection and refraction of visible light between film layers, reducing reflection loss, and further improving the visible light transmittance.

[0055] The sputter deposition of the silicon dioxide doped layer can bind the fluorine free radicals in the fluorine doped silica glass, avoiding the erosion of adjacent film layers; and it can also serve as a barrier to hydrogen permeation, blocking the hydrogenation effect of the titanium metal layer, so as to meet the design requirements of the coated glass.

[0056] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0057] 1. The magnetron sputtered coated glass and its preparation process described in the present invention form a low-emissivity film system by using magnetron sputtering to deposit multiple dielectric films, interface films and metal films on the surface of the glass substrate, realizing the transmission of visible light and the reflection of infrared light by the coated glass.

[0058] 2. The magnetron sputtered coated glass and its preparation process described in the present invention increase the absorption of infrared light by the glass and slow down its propagation by setting an unsaturated hydrogenated titanium metal layer on the surface of the silver metal layer, which can greatly reduce the irradiation of infrared light and improve the heat insulation ability of the coated glass.

[0059] 3. The magnetron sputtered coated glass and its preparation process described in the present invention are doped with diamond-like composite film layers and fluorine by setting a silicon dioxide doped layer on the surface of the titanium metal layer, which has a wider band gap width, a relatively lower refractive index and a higher infrared reflection and absorption ability, further improving the light transmission and heat insulation ability of the coated glass. Specific Embodiments

[0060] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of them. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0061] In the following specific embodiments,

[0062] The glass substrate is soda-lime glass with a thickness of 1.2 mm, sourced from Sinopharm Chemical Reagent Co., Ltd.;

[0063] Silicon dioxide: RDB-BC-SiO2, with a purity of 4N, sourced from Shanghai Yanbei New Materials Technology Co., Ltd.;

[0064] Graphite: with a purity of 99.98%, a particle size of 3 - 10 μm, sourced from Qingdao Tianshengda Graphite Co., Ltd.;

[0065] The purity of the gas is 99.995%;

[0066] Target materials: The purity of silicon, silver, and titanium is 5N, and the purity of titanium dioxide is 4N, all sourced from Beijing Zhongjinyan New Materials Co., Ltd.;

[0067] Aluminum-doped zinc oxide: with a purity of 4N and an Al doping amount of w(Al2O3) of 2.0%, sourced from Zhongnuo New Materials (Beijing) Technology Co., Ltd.;

[0068] Silicon-doped zinc oxide: with a purity of 4N and an Si doping amount of w(SiO2) of 25%, sourced from Jiangxi Ketai New Materials Co., Ltd.

[0069] Example 1: Preparation process of magnetron sputtering coated glass, including the following process steps:

[0070] (1) Using argon as the working gas and nitrogen as the reaction gas, with silicon as the target, direct current magnetron sputtering is carried out to deposit a silicon nitride layer with a thickness of 15 nm; the sputtering power is 100 W, the gas pressure is 0.005 mbar, and the ratio of argon to nitrogen is 1:1.4;

[0071] (2) Using argon as the working gas, with titanium dioxide as the target, direct current magnetron sputtering is carried out to deposit a titanium oxide layer with a thickness of 20 nm; the sputtering power is 150 W, the gas pressure is 0.003 mbar;

[0072] (3) Using argon as the working gas, with aluminum-doped zinc oxide as the target, direct current magnetron sputtering is carried out to deposit a zinc oxide-aluminum layer with a thickness of 5 nm; the sputtering power is 80 W, the gas pressure is 0.003 mbar;

[0073] (4) Using argon as the working gas, with silver as the target, alternating current magnetron sputtering is carried out to deposit a silver metal layer with a thickness of 8 nm; the sputtering power is 70 W, the gas pressure is 0.002 mbar;

[0074] (5) Using argon as the working gas and hydrogen as the reaction gas, with titanium as the target, alternating current magnetron sputtering is carried out to deposit a titanium metal layer with a thickness of 1 nm; the sputtering power is 45 W, the gas pressure is 0.002 mbar, and the ratio of argon to nitrogen is 1:0.1;

[0075] (6) Mix tetraethyl orthosilicate, 70v% ethanol, and ammonium fluoride, adjust the pH to 3.5 with 1M hydrochloric acid, and let it stand for hydrolysis for 8 h to obtain a colloidal solution; the molar ratio of tetraethyl orthosilicate to ammonium fluoride is 10:0.5; the ratio of tetraethyl orthosilicate to ethanol is 1 g / 10 mL;

[0076] Grind silicon dioxide and graphite, add the hydrolysis solution and mix to prepare a mixture; hot press sintering, the process is: evacuate to below 100 Pa, heat up to 150 °C, hold for 30 min; heat up to 660 °C, hold for 60 min; heat up to 750 °C, hold for 60 min; apply pressure to 20 MPa, hold and maintain pressure for 120 min to obtain composite silicon dioxide; the mixture includes the following mass components: 20 parts of graphite, 80 parts of silicon dioxide, and 10 parts of colloidal solution;

[0077] Using argon as the working gas, trifluoromethane as the reaction gas, and composite silica as the target, direct current magnetron sputtering is carried out to deposit a silica-doped layer; the sputtering power is 50 W, the air pressure is 0.018 mbar, and the ratio of argon to trifluoromethane is 1:0.4;

[0078] (7) Repeat the operations in steps (3)-(6) twice to successively form an aluminum zinc oxide layer, a silver metal layer, a titanium metal layer and a titanium oxide layer, an aluminum zinc oxide layer, a silver metal layer, a titanium metal layer and a titanium oxide layer;

[0079] (8) Using argon as the working gas and zinc oxide silicon as the target, direct current magnetron sputtering is carried out to deposit a zinc oxide silicon layer with a thickness of 10 nm; the sputtering power is 80 W and the air pressure is 0.003 mbar;

[0080] (9) Using argon as the working gas and nitrogen as the reaction gas, and silicon as the target, direct current magnetron sputtering is carried out to deposit a silicon nitride layer with a thickness of 8 m; the sputtering power is 100 W, the air pressure is 0.005 mbar, and the ratio of argon to nitrogen is 1:1.4 to obtain a coated glass.

[0081] Example 2: The preparation process of magnetron sputtering coated glass includes the following process steps:

[0082] (1) Using argon as the working gas and nitrogen as the reaction gas, and silicon as the target, direct current magnetron sputtering is carried out to deposit a silicon nitride layer with a thickness of 20 nm; the sputtering power is 110 W, the air pressure is 0.006 mbar, and the ratio of argon to nitrogen is 1:1.5;

[0083] (2) Using argon as the working gas and titanium dioxide as the target, direct current magnetron sputtering is carried out to deposit a titanium oxide layer with a thickness of 25 nm; the sputtering power is 180 W and the air pressure is 0.004 mbar;

[0084] (3) Using argon as the working gas and aluminum zinc oxide as the target, direct current magnetron sputtering is carried out to deposit an aluminum zinc oxide layer with a thickness of 8 nm; the sputtering power is 90 W and the air pressure is 0.004 mbar;

[0085] (4) Using argon as the working gas and silver as the target, alternating current magnetron sputtering is carried out to deposit a silver metal layer with a thickness of 9 nm; the sputtering power is 80 W and the air pressure is 0.002 mbar;

[0086] (5) Using argon as the working gas and hydrogen as the reaction gas, and titanium as the target, alternating current magnetron sputtering is carried out to deposit a titanium metal layer with a thickness of 2 nm; the sputtering power is 50 W, the air pressure is 0.003 mbar, and the ratio of argon to nitrogen is 1:0.3;

[0087] (6) Mix tetraethyl orthosilicate, 80 v% ethanol and ammonium fluoride, adjust the pH to 4 with 1 M hydrochloric acid, and let it stand for hydrolysis for 16 h to obtain a colloidal solution; the molar ratio of tetraethyl orthosilicate to ammonium fluoride is 10:0.8; the ratio of tetraethyl orthosilicate to ethanol is 2 g / 10 mL;

[0088] Ball-mill silicon dioxide and graphite, add the hydrolysis solution and mix to prepare a mixed material; perform hot-pressing sintering, and the process is as follows: evacuate to below 100 Pa, heat up to 165 °C, and keep the temperature for 45 min; heat up to 680 °C, keep the temperature for 75 min; heat up to 785 °C, keep the temperature for 75 min; apply pressure up to 25 MPa, keep the pressure for 105 min to obtain composite silicon dioxide; the mixed material includes the following mass components: 28 parts of graphite, 72 parts of silicon dioxide and 20 parts of colloidal solution;

[0089] Using argon as the working gas, trifluoromethane as the reaction gas, and composite silicon dioxide as the target, perform DC magnetron sputtering to deposit and form a silicon dioxide doped layer; the sputtering power is 60 W, the gas pressure is 0.021 mbar, and the ratio of argon to trifluoromethane is 1:0.5;

[0090] (7) Repeat the operations in steps (3)-(6) twice to successively form aluminum zinc oxide layers, silver metal layers, titanium metal layers and titanium oxide layers, aluminum zinc oxide layers, silver metal layers, titanium metal layers and titanium oxide layers;

[0091] (8) Using argon as the working gas and zinc oxide silicon as the target, perform DC magnetron sputtering to deposit and form a zinc oxide silicon layer with a thickness of 15 nm; the sputtering power is 100 W, and the gas pressure is 0.004 mbar;

[0092] (9) Using argon as the working gas and nitrogen as the reaction gas, and silicon as the target, perform DC magnetron sputtering to deposit and form a silicon nitride layer with a thickness of 12 nm; the sputtering power is 110 W, the gas pressure is 0.006 mbar, and the ratio of argon to nitrogen is 1:1.5 to obtain a coated glass.

[0093] Example 3: The preparation process of magnetron sputtering coated glass includes the following process steps:

[0094] (1) Using argon as the working gas and nitrogen as the reaction gas, and silicon as the target, perform DC magnetron sputtering to deposit and form a silicon nitride layer with a thickness of 25 nm; the sputtering power is 120 W, the gas pressure is 0.008 mbar, and the ratio of argon to nitrogen is 1:1.6;

[0095] (2) Using argon as the working gas and titanium dioxide as the target, perform DC magnetron sputtering to deposit and form a titanium oxide layer with a thickness of 30 nm; the sputtering power is 200 W, and the gas pressure is 0.005 mbar;

[0096] (3) Using argon as the working gas and aluminum zinc oxide as the target, direct current magnetron sputtering is carried out to deposit an aluminum zinc oxide layer with a thickness of 10 nm; the sputtering power is 100 W and the air pressure is 0.005 mbar;

[0097] (4) Using argon as the working gas and silver as the target, alternating current magnetron sputtering is carried out to deposit a silver metal layer with a thickness of 10 nm; the sputtering power is 90 W and the air pressure is 0.003 mbar;

[0098] (5) Using argon as the working gas and hydrogen as the reaction gas, titanium as the target, alternating current magnetron sputtering is carried out to deposit a titanium metal layer with a thickness of 3 nm; the sputtering power is 55 W, the air pressure is 0.004 mbar, and the ratio of argon to nitrogen is 1:0.5;

[0099] (6) Mix tetraethyl orthosilicate, 90 v% ethanol and ammonium fluoride, adjust the pH to 4.5 with 1 M hydrochloric acid, and let it stand for hydrolysis for 24 h to obtain a colloidal solution; the molar ratio of tetraethyl orthosilicate to ammonium fluoride is 10:1.2; the ratio of tetraethyl orthosilicate to ethanol is 3 g / 10 mL;

[0100] Ball-mill silicon dioxide and graphite, add the hydrolyzed solution and mix to prepare a mixture; hot press and sinter, the process is: evacuate to below 100 Pa, heat up to 180 °C, hold for 60 min; heat up to 700 °C, hold for 90 min; heat up to 820 °C, hold for 90 min; pressurize to 30 MPa, hold the pressure for 120 min to obtain composite silicon dioxide; the mixture includes the following mass components: 35 parts of graphite, 65 parts of silicon dioxide and 30 parts of colloidal solution;

[0101] Using argon as the working gas and trifluoromethane as the reaction gas, composite silicon dioxide as the target, direct current magnetron sputtering is carried out to deposit a silicon dioxide doped layer; the sputtering power is 70 W, the air pressure is 0.025 mbar, and the ratio of argon to trifluoromethane is 1:0.6;

[0102] (7) Repeat the operations in steps (3)-(6) twice to successively form aluminum zinc oxide layers, silver metal layers, titanium metal layers and titanium oxide layers, aluminum zinc oxide layers, silver metal layers, titanium metal layers and titanium oxide layers;

[0103] (8) Using argon as the working gas and zinc silicon oxide as the target, direct current magnetron sputtering is carried out to deposit a zinc silicon oxide layer with a thickness of 20 nm; the sputtering power is 120 W and the air pressure is 0.005 mbar;

[0104] (9) Using argon as the working gas and nitrogen as the reaction gas, silicon as the target, direct current magnetron sputtering is carried out to deposit a silicon nitride layer with a thickness of 15 nm; the sputtering power is 120 W, the air pressure is 0.008 mbar, and the ratio of argon to nitrogen is 1:1.6 to obtain the coated glass.

[0105] Comparative Example 1: The preparation process of magnetron sputtering coated glass includes the following process steps:

[0106] (6) Using argon as the working gas and titanium dioxide as the target, direct current magnetron sputtering is carried out to deposit a titanium oxide layer with a thickness of 8 nm; the sputtering power is 150 W, and the air pressure is 0.003 mbar;

[0107] Steps (1-4), (7-9) are the same as those in Example 1 to obtain the coated glass.

[0108] Experiment: Take the coated glass obtained in Examples 1-3 and Comparative Example 1, prepare specimens, and detect their properties respectively and record the detection results:

[0109] Use an ultraviolet-visible spectrometer to detect the transmittance of the coated glass specimen in the wavelength range of 380 nm - 800 nm;

[0110] Use a Fourier transform infrared spectrometer to detect the infrared reflectance R of the coated glass specimen and calculate its emissivity (1 - R);

[0111] Use a thermal conductivity meter to detect the thermal conductivity of the coated glass specimen.

[0112] Visible light transmittance (%) Emissivity Thermal conductivity (W / m·K) Example 1 89.2 0.34 0.63 Example 2 91.4 0.30 0.50 Example 3 87.7 0.27 0.45 Comparative Example 1 79.8 0.42 1.23

[0113] According to the data in the above table, the following conclusions can be clearly obtained:

[0114] The coated glass obtained in Examples 1-3 is compared with the coated glass obtained in Comparative Example 1. From the detection results,

[0115] Compared with the comparative example, the coated glass obtained in Examples 1-3 has higher visible light transmittance and lower emissivity and thermal conductivity data. This fully demonstrates that the present invention realizes the improvement of the light transmission and heat insulation capabilities of the prepared coated glass.

[0116] The same as Example 1, Comparative Example 1 replaces the silicon oxide doping layer with a titanium dioxide layer. Its visible light transmittance is lower, and the emissivity and thermal conductivity data are higher. It can be seen that the setting of the film layer and its process of the coated glass in the present invention can promote the improvement of its light transmission and heat insulation capabilities.

[0117] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and without departing from the spirit or basic characteristics of the present invention, the present invention can be implemented in other specific forms. Therefore, in any aspect, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, it is intended to include all changes falling within the meaning and scope of the equivalent elements of the claims in the present invention.

Claims

1. Preparation process of magnetron sputtering coated glass, characterized in that: It includes the following technological steps: (1) Using argon as the working gas, nitrogen as the reaction gas, and silicon as the target, perform direct current magnetron sputtering to deposit a silicon nitride layer; (2) Using argon as the working gas and titanium dioxide as the target, perform direct current magnetron sputtering to deposit a titanium oxide layer; (3) Using argon as the working gas and aluminum zinc oxide as the target, perform direct current magnetron sputtering to deposit an aluminum zinc oxide layer; (4) Using argon as the working gas and silver as the target, perform alternating current magnetron sputtering to deposit a silver metal layer; (5) Using argon as the working gas, hydrogen as the reaction gas, and titanium as the target, perform alternating current magnetron sputtering to deposit a titanium metal layer; (6) Using argon as the working gas, trifluoromethane as the reaction gas, and composite silica as the target, perform direct current magnetron sputtering to deposit a silicon oxide doped layer; (7) Repeat the operations of steps (3)-(6) twice to successively form an aluminum zinc oxide layer, a silver metal layer, a titanium metal layer, a silicon oxide doped layer, an aluminum zinc oxide layer, a silver metal layer, a titanium metal layer, and a silicon oxide doped layer; (8) Using argon as the working gas and zinc silicon oxide as the target, perform direct current magnetron sputtering to deposit a zinc silicon oxide layer; (9) Using argon as the working gas, nitrogen as the reaction gas, and silicon as the target, perform direct current magnetron sputtering to deposit a silicon nitride layer to obtain a coated glass; For the target, the composite silica is prepared by the following process: Mix tetraethyl orthosilicate, ethanol, and ammonium fluoride, adjust the pH to 3.5-4.5 with hydrochloric acid, and let it stand for hydrolysis for 8-24 h to obtain a colloidal solution; Ball-mill silicon dioxide and graphite, add the hydrolyzed solution and mix to prepare a mixed material; perform hot-pressing sintering to obtain composite silica.

2. The preparation process of the magnetron sputtering coated glass according to claim 1, characterized in that: In step (1), the sputtering power is 100-120 W, the air pressure is 0.005-0.008 mbar, and the ratio of argon to nitrogen is 1:(1.4-1.6); In step (2), the sputtering power is 150-200 W, and the air pressure is 0.003-0.005 mbar; In step (3), the sputtering power is 80-100 W, and the air pressure is 0.003-0.005 mbar; In step (4), the sputtering power is 70-90 W, and the air pressure is 0.002-0.003 mbar.

3. The preparation process of the magnetron sputtering coated glass according to claim 1, characterized in that: In step (5), the sputtering power is 45-55 W, and the air pressure is 0.002-0.004 mbar; In step (6), the sputtering power is 150-200 W, and the air pressure is 0.003-0.005 mbar; In step (8), the sputtering power is 80-120 W, and the air pressure is 0.003-0.005 mbar; In step (9), the sputtering power is 100-120 W, the air pressure is 0.005-0.008 mbar, and the ratio of argon to nitrogen is 1:(1.4-1.6).

4. The preparation process of the magnetron sputtering coated glass according to claim 1, characterized in that: In step (6), the technological conditions of magnetron sputtering are: the sputtering power is 50-70 W, the air pressure is 0.018-0.025 mbar, and the ratio of argon to trifluoromethane is 1:(0.4-0.6).

5. The preparation process of the magnetron sputtering coated glass according to claim 1, characterized in that: The mixed material includes the following mass components: 20-35 parts of graphite, 65-80 parts of silicon dioxide, and 10-30 parts of colloidal solution.

6. The preparation process of the magnetron sputtering coated glass according to claim 1, characterized in that: In the glue solution, the molar ratio of tetraethyl orthosilicate to ammonium fluoride is 10:(0.5 - 1.2).

7. The preparation process of the magnetron sputtering coated glass according to claim 1, characterized in that: The process conditions for hot press sintering are as follows: evacuate, heat up to 150 - 180 °C, keep warm for 30 - 60 min; heat up to 660 - 700 °C, keep warm for 60 - 90 min; heat up to 750 - 820 °C, keep warm for 60 - 90 min; apply pressure up to 20 - 30 MPa, keep warm and hold pressure for 90 - 120 min.

8. The magnetron sputtering coated glass prepared by the preparation process according to any one of claims 1-7, characterized in that: It includes a glass substrate, and the following film layers are sequentially stacked on the upper surface of the glass substrate from bottom to top: the first film layer of silicon nitride layer, the second film layer of titanium oxide layer, the third film layer of aluminum zinc oxide layer, the fourth film layer of silver metal layer, the fifth film layer of titanium metal layer, the sixth film layer of silicon oxide doped layer, the seventh film layer of aluminum zinc oxide layer, the eighth film layer of silver metal layer, the ninth film layer of titanium metal layer, the tenth film layer of silicon oxide doped layer, the eleventh film layer of aluminum zinc oxide layer, the twelfth film layer of silver metal layer, the thirteenth film layer of titanium metal layer, the fourteenth film layer of silicon oxide doped layer, the fifteenth film layer of zinc silicon oxide layer, the sixteenth film layer of silicon nitride.