Lamination layer

Abstract

The utility model discloses a lamination which is formed on the surface of a substrate, a silicon oxycarbide film layer, a carbon element-containing layer and an aluminum oxide film layer are sequentially arranged on the surface of the substrate outwards, the silicon oxycarbide film layer is in direct contact with the surface of the substrate, the silicon oxycarbide film layer 2 is composed of at least one film layer, and the aluminum oxide film layer is composed of at least one film layer. Thus, the laminate can be subjected to high-temperature heat treatment. The laminated layer disclosed by the utility model can resist the soaking of 2mol / L hydrochloric acid solution for 24 hours, the soaking of 2mol / L sodium hydroxide solution for 24 hours and the soaking of saturated concentration sodium chloride solution for 96 hours, and the performance is basically kept unchanged, so that the chemical stability of the laminated layer is very good.

Description

Technical Field

[0001] The utility model relates to the technical field of laminates, and more particularly to a laminate that is wear-resistant, can undergo high-temperature heat treatment, and is hydrophilic. Background Art

[0002] Self-cleaning coatings can be divided into hydrophobic self-cleaning coatings and hydrophilic self-cleaning coatings according to their different principles. The self-cleaning mechanism of hydrophobic self-cleaning coatings is similar to the principle of lotus leaf surface decontamination. The coating surface needs to have moderate roughness and low surface energy. However, hydrophobic surfaces are usually only waterproof and not dustproof. During use, the adhesion of oily pollutants on the surface often reduces the hydrophobic angle and prevents water droplets from rolling off. The formation of large water droplets will cause more dust accumulation. The self-cleaning mechanism of hydrophilic self-cleaning coatings refers to the fact that the water contact angle on the coating surface is very small, usually less than 10°, so that a small amount of rainwater or dew can form a water film on the substrate surface, thereby preventing dust or pollutants from contacting the material surface, and the flow of the water film can more easily carry away dust; and even if the substrate surface is equally dirty, under the same cleaning conditions, or relatively poor cleaning conditions, the substrate coated with the hydrophilic coating is easier to clean (compared with the substrate not coated with the hydrophilic coating). Therefore, compared with hydrophobic self-cleaning coatings, hydrophilic self-cleaning coatings are more effective self-cleaning coatings. However, existing hydrophilic self-cleaning coatings often reduce the substrate's light transmittance when applied to substrates. Furthermore, most hydrophilic self-cleaning coatings incorporate titanium dioxide, which has a refractive index much higher than that of the glass substrate, causing light to reflect. This can reduce the module's power generation if applied to the surface of a photovoltaic module. Therefore, a self-cleaning coating that maintains the glass's light transmittance is needed to address these challenges.

[0003] Fog is a natural phenomenon caused by the condensation of droplets due to temporary changes in ambient humidity and temperature. After fogging, the incident light is strongly scattered by the condensed water droplets, which reduces the transparency of windshields, rearview mirrors, goggles, building curtain walls, etc. The fogging phenomenon not only causes inconvenience to people's lives, but can even cause extremely serious consequences. Among the current methods for solving the fogging problem, preparing a hydrophilic surface to effectively inhibit the formation of fog droplets is a popular method. However, the anti-fog coating prepared by this method is easily damaged, which will have an extremely adverse effect on the performance of the coated parts; in addition, the surface of the anti-fog coating prepared by this method is also easily contaminated by substances such as dyes and bacteria, thereby affecting the optical properties; the anti-fog coating prepared by this method mostly uses volatile organic solvents, which will also cause great harm to the environment. Therefore, it is necessary to develop a hydrophilic laminate prepared by environmentally friendly materials to solve the fogging problem.

[0004] Carbon-containing coatings have excellent properties such as extremely high hardness and wear resistance, low friction coefficient and thermal expansion coefficient, high elastic modulus, and good chemical stability. They are widely used in the field of surface protection. However, carbon-containing coatings usually exhibit certain hydrophobic properties (contact angle greater than 60°), which limits their application in some hydrophilic hard functional surface protection fields. Some people have achieved a hydrophilic effect by doping appropriate amounts of Si and O elements into the film layer during the deposition process of the carbon-containing coating, so that the film layer contains a certain amount of Si-O-Si bonds, which are hydrophilic bonds. However, this type of coating cannot be used for high-temperature heat treatment. If it is subjected to heat treatment, the coating will be burned and the Si-O-Si bonds will be further oxidized, causing its hydrophilic properties to disappear. Moreover, it is not resistant to immersion in sodium hydroxide solution, because the Si-O-Si bonds will react with sodium hydroxide to form sodium silicate, which will seriously ineffective the performance of the film layer. Utility Model Content

[0005] The purpose of the present invention is to provide a laminate to solve the above-mentioned problems existing in the existing hydrophilic film layer. The laminate provided by the present invention can be subjected to high-temperature heat treatment (such as hot bending, tempering, etc.). The present invention has a certain anti-reflection effect, a certain anti-reflection effect, extremely high hardness and wear resistance, and good chemical stability.

[0006] To achieve the above-mentioned object, the technical solution adopted by the present invention is to provide a laminated layer, which is formed on at least one surface of a substrate, and comprises a silicon oxycarbide film layer, a carbon-containing layer, and an aluminum oxide film layer in order from the substrate surface outward; the silicon oxycarbide film layer is in direct contact with the substrate surface, the silicon oxycarbide film layer is composed of at least one film layer; the aluminum oxide film layer is composed of at least two film layers; the silicon oxycarbide film layer contains oxygen and carbon elements and has a thermal expansion coefficient of ≥8◇10 -7 / k.

[0007] The carbon-containing layer is an undoped layer and / or the carbon-containing layer may be doped with element A; the element A is at least one of oxygen, sulfur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony, bismuth, hydrogen, boron, aluminum, gallium, indium, fluorine, chlorine, bromine and / or iodine.

[0008] The substrate is a glass substrate, a ceramic substrate, a metal substrate, a silicon-based substrate, a polyimide substrate, an organic substrate that can withstand temperatures greater than 350°C, or a substrate with a film layer on the surface. The film layer on the substrate with a film layer on the surface is a low-emissivity film layer, a conductive film layer, a color-changing film layer, a head-up display film layer, an anti-ultraviolet film layer, an anti-infrared film layer, an antibacterial film layer, an anti-reflection film layer and / or an anti-reflection film layer, etc.

[0009] The carbon-containing layer is composed of at least one film layer. The thickness of the carbon-containing layer is ≤500 nm, preferably ≤200 nm, and more preferably ≤100 nm.

[0010] The silicon oxycarbide film layer may also contain at least one element selected from scandium, yttrium, titanium, zirconium, hafnium, niobium, tantalum, chromium, molybdenum, tungsten, nickel, palladium, platinum, silicon, cerium, gadolinium, tin, fluorine and / or nitrogen. The silicon oxycarbide film layer is a compound with a stoichiometric composition or a non-stoichiometric composition, or the silicon oxycarbide film layer is a mixture of a carbon substance and the aforementioned compounds.

[0011] The aluminum oxide film layer is composed of an oxide, nitride, oxynitride, sulfide, oxysulfide, selenide, selenide oxide, telluride, tellurium oxide, fluoride, and / or oxyfluoride of at least one element selected from boron, aluminum, gallium, indium, magnesium, calcium, strontium, barium, zinc, manganese, carbon, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth, and / or iron, wherein these compounds are stoichiometric or non-stoichiometric. The aluminum oxide film layer may further include a metal film layer, wherein the metal film layer is composed of a single element and / or an alloy of at least one element selected from aluminum, gallium, indium, magnesium, calcium, strontium, barium, zinc, iron, nickel, chromium, titanium, tin, lead, niobium, antimony, and / or bismuth.

[0012] The stack can be inserted with at least one film layer with a certain conductivity, and the film layer with a certain conductivity is indium oxide doped with tin, tin oxide doped with fluorine, titanium oxide doped with niobium, tin oxide doped with antimony, tin oxide doped with iodine, tin oxide with oxygen vacancies, indium oxide doped with cerium, indium oxide doped with titanium and cerium.

[0013] A titanium dioxide film layer may be inserted between the carbon-containing layer and the aluminum oxide film layer. The titanium dioxide film layer only partially covers the surface of the carbon-containing layer. Preferably, the titanium dioxide film layer covers ≤80% of the surface of the carbon-containing layer; more preferably, the titanium dioxide film layer covers ≤50% of the surface of the carbon-containing layer; and most preferably, the titanium dioxide film layer covers ≤20% of the surface of the carbon-containing layer. The titanium dioxide film layer has a thickness of <10 nm, preferably <5 nm. The laminate of the present invention can be prepared by magnetron sputtering, evaporation, atomic layer deposition, chemical vapor deposition, physical vapor deposition, and other methods.

[0014] The laminate is heat treated at a temperature of 350°C to 800°C, at a pressure of 0.01 Pa to 2 atmospheres, and in a reducing atmosphere, an oxidizing atmosphere, an atmospheric atmosphere, and / or an inert atmosphere. The laminate after heat treatment is cleaned with a solution such as an alkaline solution, an acid solution, and / or water to remove the aluminum oxide film. After cleaning, the film surface is dried to obtain a film structure.

[0015] The film layer structure can be used for automobile windshields, on-board displays and automobile rearview mirrors, train and high-speed rail windshields, ship glass and aircraft glass, building door and window glass, wall surface and glass curtain wall, bathroom glass, mirror glass, tile surface, kitchen window glass, photovoltaic module glass, communication terminal product glass, home appliance product glass, observation window glass and display counter glass, etc.

[0016] Beneficial technical effects of the utility model:

[0017] 1. The laminate of the present invention can be heat treated at a temperature exceeding 400 degrees, more preferably exceeding 500 degrees, and even exceeding 700 degrees, which is a performance that many existing hydrophilic membranes do not have.

[0018] 2. The film structure of the present invention has certain anti-reflection and anti-reflection functions, which are properties not possessed by many existing hydrophilic films; its hydrophilic angle can be less than 5 degrees, and the hydrophilic angle can be less than 3 degrees; its bonding with the substrate is very strong, and it is scratch-resistant and wear-resistant; it can withstand more than 2 million scratches from car wipers while maintaining basically unchanged performance.

[0019] 3. The membrane structure of the present invention can withstand immersion in 2 mol / L hydrochloric acid solution for 24 hours, immersion in 2 mol / L sodium hydroxide solution for 24 hours, and immersion in saturated sodium chloride solution for 96 hours, while maintaining basically unchanged performance, indicating that its chemical stability is very good. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 A schematic diagram of a stacked structure;

[0021] Figure 2 Schematic diagram of the second structure of the stack

[0022] Figure 3 Schematic diagram of the third structure of the stack

[0023] Figure 4 Schematic diagram of the fourth structure of the stack

[0024] Figure 5 Schematic diagram of a membrane structure

[0025] 1-substrate, 2-silicon oxide carbon film layer, 3-carbon element layer, 4-aluminum oxide film layer, 5-conductive film layer, 6-titanium dioxide film layer, 7-low-emissivity film layer DETAILED DESCRIPTION

[0026] The present invention will now be further described with reference to the accompanying drawings and specific implementation methods.

[0027] Existing hydrophilic films or self-cleaning films generally have a short lifespan, are not resistant to corrosion by hydrochloric acid and sodium hydroxide solutions, have poor mechanical scratch resistance, and cannot undergo high-temperature heat treatment. The laminate of the present invention solves the above problems. The technical solution adopted by the present invention is to provide a laminate formed on at least one surface of a substrate, which is composed of a silicon oxycarbide film layer, a carbon-containing layer, and an aluminum oxide film layer from the substrate surface outward; the silicon oxycarbide film layer is in direct contact with the substrate surface, the silicon oxycarbide film layer is composed of at least one film layer; the aluminum oxide film layer is composed of at least two film layers; the silicon oxycarbide film layer contains oxygen and carbon elements and has a thermal expansion coefficient of ≥8◇10 -7 / k. Through numerous experiments, the present invention surprisingly discovered that the use of the present invention's silicon oxycarbide film layer can achieve higher film quality during the deposition process for the carbon-containing layer. This film quality ultimately reduces the hydrophilic angle of the carbon-containing layer, thereby achieving excellent self-cleaning, easy-cleaning, and anti-fog properties. During subsequent processing of the laminate, the silicon oxycarbide film layer can also effectively prevent elements from the substrate from diffusing into the carbon-containing layer. During subsequent processing of the laminate, the aluminum oxide film layer can effectively protect the carbon-containing layer. At the same time, some elements of the aluminum oxide film layer will react with some elements in the carbon-containing layer, reducing the hydrophilic angle of the carbon-containing layer after processing, thereby achieving excellent self-cleaning, easy-cleaning, and anti-fog properties.

[0028] If the thickness of the carbon-containing layer in the laminate of the present invention exceeds 500 nm, the transmittance of the film will be significantly reduced and the film will be easier to remove. This will have little effect on improving the self-cleaning performance of the laminate and will increase manufacturing costs. In the present invention, if the titanium dioxide film layer inserted between the carbon-containing layer and the aluminum oxide film layer covers more than 80% of the surface of the carbon-containing layer, it will adversely affect the hydrophilicity of the laminate after treatment, significantly increasing the hydrophilic angle. When the thickness of the titanium dioxide film layer is ≥10 nm, the hydrophilicity of the laminate after treatment will also be significantly reduced.

[0029] The utility model discloses a film layer structure, which has a long-term all-weather self-cleaning function and an easy-to-clean function, and does not require ultraviolet light to drive it (for example, the known titanium dioxide-based self-cleaning film needs to be driven by ultraviolet light to have a self-cleaning function, and the ultraviolet light on cloudy days and at night is very weak, so its self-cleaning function is ineffective). The utility model discloses a film layer structure, which has certain anti-reflection and anti-reflection functions, which are properties not possessed by many existing self-cleaning films. The hydrophilic angle can be less than 5 degrees, and the hydrophilic angle can be less than 3 degrees more preferably. The combination with the substrate is very firm and can resist scratches and wear. The abrasion tester uses a standard grinding wheel (grinding wheel model CS-10F) with a force of 250 grams. After grinding for 200 revolutions, the performance of the film layer of the present invention remains basically unchanged, indicating that the wear resistance of the film layer of the film layer structure of the utility model is very good; it can withstand more than 2 million scratches by automobile wipers while maintaining basically unchanged performance.

[0030] The membrane layer of the membrane structure of the present invention can withstand immersion in 2 mol / L hydrochloric acid solution for 24 hours, immersion in 2 mol / L sodium hydroxide solution for 24 hours and immersion in saturated sodium chloride solution for 96 hours while maintaining basically unchanged performance, indicating that its chemical stability is very good.

[0031] In the following embodiments, each film layer is deposited sequentially on a clean surface of a substrate.

[0032] Example 1

[0033] A first dielectric layer 2 is deposited on the surface of the glass substrate 1. The first dielectric layer 2 is a silicon oxycarbide film layer with a thickness of 20 nm. A carbon-containing element layer 3 is then deposited on the surface of the first dielectric layer 2. The carbon-containing element layer 3 has a thickness of 500 nm. A second dielectric layer 4 is then deposited on the surface of the carbon-containing element layer 3. The second dielectric layer 4 is a 50 nm aluminum oxide film layer. Figure 1 As shown; then the glass substrate with the film layer deposited thereon is subjected to a heat treatment at 350 degrees under a pressure of 0.01Pa, the heat treatment atmosphere is an inert atmosphere, and after the heat treatment, an alkaline solution is used to clean the second dielectric layer 4 to obtain a film structure, as shown Figure 5As shown; after cleaning, the surface hydrophilic angle of the membrane layer of this membrane structure was tested using a hydrophilic angle measuring instrument and was found to be 3.84 degrees. An abrasion test was performed using an abrasion tester, using a standard grinding wheel (grinding wheel model CS-10F) with a force of 250 grams, grinding for 200 revolutions, and then cleaning the membrane layer surface for a hydrophilic angle test. The hydrophilic angle was measured to be 4.01 degrees. The membrane layer surface of this membrane structure was scraped 2 million times with a wiper and then cleaned and tested for hydrophilic angle, which was found to be 3.92 degrees. The membrane layer of this membrane structure was immersed in 2mol / L hydrochloric acid solution for 24 hours, 2mol / L sodium hydroxide solution for 24 hours, and saturated sodium chloride solution for 96 hours. After cleaning and testing, the hydrophilic angles were 3.99 degrees, 3.76 degrees, and 3.8 degrees, respectively.

[0034] Example 2

[0035] A first dielectric layer 2 is deposited on the surface of a glass substrate 1. The first dielectric layer 2 is composed of a 15nm silicon oxide film layer and a 10nm silicon carbide film layer, wherein the silicon oxide film layer is in direct contact with the surface of the glass substrate 1. A carbon-containing layer 3 is then deposited on the surface of the first dielectric layer 2. The carbon-containing layer 3 is doped with aluminum and has a thickness of 200nm. A second dielectric layer 4 is then deposited on the surface of the carbon-containing layer 3. The second dielectric layer 4 is composed of a 15nm bismuth oxide film layer and a 25nm aluminum nitride film layer, wherein the bismuth oxide film layer is in direct contact with the carbon-containing layer 3. The glass substrate 1 with the film layers deposited thereon is then subjected to a heat treatment at 550 degrees Celsius under 1 atmosphere of pressure in an atmospheric atmosphere. After the heat treatment, the glass substrate 1 is cleaned with an acid solution to remove the second dielectric layer 4, thereby obtaining a film structure. After cleaning, the hydrophilic angle of the film structure is measured using a hydrophilic angle measuring instrument, and the hydrophilic angle is 3.16 degrees. The wear resistance test was carried out using an abrasion tester. A standard grinding wheel (grinding wheel model CS-10F) was used with a force of 250 grams. After grinding for 200 revolutions, the surface of the membrane layer of the membrane structure was cleaned and the hydrophilic angle was tested. The hydrophilic angle was measured to be 3.41 degrees. The surface of the membrane layer of the membrane structure was scraped 2 million times with a wiper and then cleaned and the hydrophilic angle was tested. The hydrophilic angle was measured to be 3.22 degrees. The membrane layer of the membrane structure was immersed in 2mol / L hydrochloric acid solution for 24 hours, 2mol / L sodium hydroxide solution for 24 hours, and saturated sodium chloride solution for 96 hours. After cleaning and testing, the hydrophilic angles were 3.28 degrees, 3.06 degrees, and 3.11 degrees, respectively.

[0036] Example 3

[0037] A first dielectric layer 2 is deposited on the surface of a glass substrate 1. The first dielectric layer 2 is composed of a 15nm thick tin oxide film and a 10nm thick titanium carbide film, wherein the tin oxide film is in direct contact with the surface of the glass substrate 1. A carbon-containing layer 3 is then deposited on the surface of the first dielectric layer 2. The carbon-containing layer 3 has a two-layer structure, comprising a 30nm thick undoped carbon-containing layer and a 70nm thick sulfur-doped carbon-containing layer. A second dielectric layer 4 is then deposited on the surface of the carbon layer 3. The second dielectric layer 4 is composed of a 60nm thick zinc oxide film and a 10nm thick magnesium oxide film, wherein the zinc oxide film is in direct contact with the carbon-containing layer 3. The glass substrate 1 with the film layers deposited thereon is then subjected to a heat treatment at 350 degrees Celsius under 2 atmospheres of pressure in a reducing atmosphere. After the heat treatment, the glass substrate 1 is cleaned with an acid solution to remove the second dielectric layer 4, thereby obtaining a film structure. After cleaning, the surface hydrophilicity angle of the film structure is measured using a hydrophilicity angle measuring instrument, and the hydrophilicity angle is 2.86 degrees. The wear resistance test was carried out using an abrasion tester. A standard grinding wheel (grinding wheel model CS-10F) was used with a force of 250 grams. After grinding for 200 revolutions, the surface of the membrane layer of the membrane structure was cleaned and the hydrophilic angle was tested. The hydrophilic angle was measured to be 2.98 degrees. The surface of the membrane layer of the membrane structure was scraped 2 million times with a wiper and then cleaned and the hydrophilic angle was tested. The hydrophilic angle was measured to be 2.92 degrees. The membrane layer of the membrane structure was immersed in 2mol / L hydrochloric acid solution for 24 hours, 2mol / L sodium hydroxide solution for 24 hours, and saturated sodium chloride solution for 96 hours. After cleaning and testing, the hydrophilic angles were 2.9 degrees, 2.71 degrees, and 2.88 degrees, respectively.

[0038] Example 4

[0039] A first dielectric layer 2 is deposited on the surface of a glass substrate 1. The first dielectric layer 2 is composed of a 15nm tin oxide film layer and a 10nm niobium carbide film layer, wherein the tin oxide film layer is in direct contact with the surface of the glass substrate 1. A carbon-containing layer 3 is then deposited on the surface of the first dielectric layer 2. The carbon-containing layer 3 is doped with nitrogen and has a thickness of 100nm. A second dielectric layer 4 is then deposited on the surface of the carbon-containing layer 3. The second dielectric layer 4 is composed of a 100nm zinc oxide-doped aluminum film layer. The glass substrate 1 with the film layers deposited thereon is then heat-treated at 550 degrees Celsius under 1 atmosphere of pressure in an atmospheric atmosphere. After the heat treatment, the glass substrate 1 is cleaned with an acid solution to remove the second dielectric layer 4, thereby obtaining a film structure. After cleaning, the hydrophilic angle of the film structure is measured using a hydrophilic angle measuring instrument, and the hydrophilic angle is 2.44 degrees. The wear resistance test was carried out using an abrasion tester. A standard grinding wheel (grinding wheel model CS-10F) was used with a force of 250 grams. After grinding for 200 revolutions, the surface of the membrane layer of the membrane structure was cleaned and the hydrophilic angle was tested. The hydrophilic angle was measured to be 2.51 degrees. The surface of the membrane layer of the membrane structure was scraped 2 million times with a wiper and then cleaned and the hydrophilic angle was tested. The hydrophilic angle was measured to be 2.64 degrees. The membrane layer of the membrane structure was immersed in 2mol / L hydrochloric acid solution for 24 hours, 2mol / L sodium hydroxide solution for 24 hours, and saturated sodium chloride solution for 96 hours. After cleaning and testing, the hydrophilic angles were 2.7 degrees, 2.24 degrees, and 2.51 degrees, respectively.

[0040] Example 5

[0041] A first dielectric layer 2 is deposited on the surface of a ceramic substrate 1. The first dielectric layer 2 is composed of a 10nm zirconium oxide film layer and a 12nm chromium carbide film layer, wherein the zirconium oxide film layer is in direct contact with the surface of the ceramic substrate 1. A carbon-containing element layer 3 is then deposited on the surface of the first dielectric layer 2. The carbon-containing element layer 3 is doped with boron and has a thickness of 80nm. A second dielectric layer 4 is then deposited on the surface of the carbon-containing element layer 3. The second dielectric layer 4 is composed of a 5nm magnesium film layer and an 80nm zinc oxide-doped aluminum film layer. The ceramic substrate 1 with the film layer deposited thereon is then subjected to a heat treatment at 800 degrees Celsius under 1 atmosphere of pressure in an atmospheric environment. After the heat treatment, the ceramic substrate 1 is cleaned with an acid solution to remove the second dielectric layer 4, thereby obtaining a film structure. After cleaning, the hydrophilic angle of the film structure is measured using a hydrophilic angle measuring instrument, and the hydrophilic angle is 4.57 degrees. The wear resistance test was carried out using an abrasion tester. A standard grinding wheel (grinding wheel model CS-10F) was used with a force of 250 grams. After grinding for 200 revolutions, the surface of the membrane layer of the membrane structure was cleaned and the hydrophilic angle was tested. The hydrophilic angle was measured to be 4.77 degrees. The surface of the membrane layer of the membrane structure was scraped 2 million times with a wiper and then cleaned and the hydrophilic angle was tested. The hydrophilic angle was measured to be 4.95 degrees. The membrane layer of the membrane structure was immersed in 2mol / L hydrochloric acid solution for 24 hours, 2mol / L sodium hydroxide solution for 24 hours, and saturated sodium chloride solution for 96 hours. After cleaning and testing, the hydrophilic angles were 4.59 degrees, 4.36 degrees, and 4.52 degrees, respectively.

[0042] Example 6

[0043] A first dielectric layer 2 is deposited on the surface of a ceramic substrate 1. The first dielectric layer 2 is composed of a 10nm silicon oxynitride film layer and a 12nm silicon carbide film layer, wherein the zirconium oxide film layer is in direct contact with the surface of the ceramic substrate 1. A carbon-containing element layer 3 is then deposited on the surface of the first dielectric layer 2. The carbon-containing element layer 3 is doped with fluorine and has a thickness of 70nm. A second dielectric layer 4 is then deposited on the surface of the carbon-containing element layer 3. The second dielectric layer 4 is composed of a 5nm iron oxide film layer, a 3nm zinc-tin alloy film layer, and an 80nm zinc oxide-doped magnesium film layer. The ceramic substrate 1 with the film layers deposited thereon is then subjected to a heat treatment at 600 degrees Celsius under 1 atmosphere of pressure in an atmospheric environment. After the heat treatment, the ceramic substrate 1 is cleaned with an acid solution to remove the second dielectric layer 4, thereby obtaining a film structure. After cleaning, the hydrophilic angle of the film structure is measured using a hydrophilic angle measuring instrument, and the hydrophilic angle is 2.81 degrees. The wear resistance test was carried out using an abrasion tester. A standard grinding wheel (grinding wheel model CS-10F) was used with a force of 250 grams. After grinding for 200 revolutions, the surface of the membrane layer of the membrane structure was cleaned and the hydrophilic angle was tested. The hydrophilic angle was measured to be 2.96 degrees. The surface of the membrane layer of the membrane structure was scraped 2 million times with a wiper and then cleaned and the hydrophilic angle was tested. The hydrophilic angle was measured to be 3.02 degrees. The membrane layer of the membrane structure was immersed in 2mol / L hydrochloric acid solution for 24 hours, 2mol / L sodium hydroxide solution for 24 hours, and saturated sodium chloride solution for 96 hours. After cleaning and testing, the hydrophilic angles were 2.79 degrees, 2.71 degrees, and 2.85 degrees, respectively.

[0044] Example 7

[0045] A glass substrate with a film layer 5 having a certain conductivity deposited on its surface is used as a substrate 1. A first dielectric layer 2 is deposited on the surface of the conductive film layer 5. The first dielectric layer 2 is a 20nm thick film layer of a mixture of silicon oxide and carbon. Then, a carbon-containing element layer 3 is deposited on the surface of the first dielectric layer 2. The carbon-containing element layer 3 is doped with fluorine and hydrogen elements and has a thickness of 50nm. Then, a second dielectric layer 4 is deposited on the surface of the carbon-containing element layer 3. The second dielectric layer 4 is composed of a 3nm iron oxide film layer, a 10nm zinc oxide doped with magnesium, a 3nm zinc-tin alloy film layer, and a 35nm zinc oxide doped with aluminum film layer. Figure 2As shown; then the substrate 1 with the film layer deposited thereon is subjected to a heat treatment at 550 degrees under 1 atmosphere of pressure, the heat treatment atmosphere is an atmospheric environment atmosphere, and after the heat treatment, it is cleaned with an acid solution to remove the second dielectric layer 4, thereby obtaining a film layer structure; after cleaning, the hydrophilic angle of the film layer surface of the film layer structure is tested using a hydrophilic angle measuring instrument to find that it is 3.92 degrees. The wear resistance test was carried out using an abrasion tester. A standard grinding wheel (grinding wheel model CS-10F) was used with a force of 250 grams. After grinding for 200 revolutions, the surface of the membrane layer of the membrane structure was cleaned and the hydrophilic angle was tested. The hydrophilic angle was measured to be 4.09 degrees. The surface of the membrane layer of the membrane structure was scraped 2 million times with a wiper and then cleaned and the hydrophilic angle was tested. The hydrophilic angle was measured to be 4.04 degrees. The membrane layer of the membrane structure was immersed in 2mol / L hydrochloric acid solution for 24 hours, 2mol / L sodium hydroxide solution for 24 hours, and saturated sodium chloride solution for 96 hours. After cleaning and testing, the hydrophilic angles were 3.91 degrees, 3.81 degrees, and 3.89 degrees, respectively.

[0046] Example 8

[0047] A glass substrate with a low-emissivity film layer 7 deposited on its surface is used as substrate 1. A first dielectric layer 2 is deposited on another surface of substrate 1 without a film layer deposited thereon. The first dielectric layer 2 is a 28nm thick silicon oxide and carbon mixture film layer. A carbon-containing element layer 3 is then deposited on the surface of the first dielectric layer 2. The carbon-containing element layer 3 consists of two sublayers, one sublayer being a carbon-containing element layer doped with bromine and the other being a carbon-containing element layer 3 doped with nitrogen. The total thickness of the carbon-containing element layer 3 is 55nm. A second dielectric layer 4 is then deposited on the surface of the carbon-containing element layer 3. The second dielectric layer 4 consists of a 10nm zinc oxide doped with magnesium, a 3nm bismuth metal film layer, and a 35nm zinc tin oxide film layer. Figure 4 As shown; then the substrate 1 with the film layer deposited thereon is subjected to a heat treatment at 580 degrees under 1 atmosphere of pressure, the heat treatment atmosphere is an atmospheric environment atmosphere, and after the heat treatment, it is cleaned with an acid solution to clean the second dielectric layer 4, thereby obtaining a film layer structure; after cleaning, the hydrophilic angle of the film layer surface of the film layer structure is tested using a hydrophilic angle measuring instrument to find that it is 4.11 degrees. The wear resistance test was carried out using an abrasion tester. A standard grinding wheel (grinding wheel model CS-10F) was used with a force of 250 grams. After grinding for 200 revolutions, the surface of the membrane layer of the membrane structure was cleaned and the hydrophilic angle was tested. The hydrophilic angle was measured to be 4.3 degrees. The surface of the membrane layer of the membrane structure was scraped 2 million times with a wiper and then cleaned and the hydrophilic angle was tested. The hydrophilic angle was measured to be 4.24 degrees. The membrane layer of the membrane structure was immersed in 2mol / L hydrochloric acid solution for 24 hours, 2mol / L sodium hydroxide solution for 24 hours, and saturated sodium chloride solution for 96 hours. After cleaning and testing, the hydrophilic angles were 3.97 degrees, 3.84 degrees, and 4.06 degrees, respectively.

[0048] Example 9

[0049] A first dielectric layer 2 is deposited on the surface of a glass substrate 1. The first dielectric layer 2 is composed of a 15nm silicon oxynitride film layer and a 10nm titanium oxycarbide film layer. Then, a carbon-containing layer 3 is deposited on the surface of the first dielectric layer 2. The carbon-containing layer 3 is doped with nitrogen and hydrogen elements and has a thickness of 55nm. Then, a 3nm titanium dioxide film 6 is deposited on the surface of the carbon-containing layer 3. The titanium dioxide film 6 covers 75% of the surface of the carbon-containing layer 3. Then, a second dielectric layer 4 is deposited on the surface of the titanium dioxide film 6. The second dielectric layer 4 is composed of a 10nm zinc oxide doped with magnesium, a 3nm bismuth metal film, and a 35nm zinc tin oxide film. Figure 3 As shown; then the substrate 1 with the film layer deposited thereon is subjected to a heat treatment at 560 degrees under 1 atmosphere of pressure, the heat treatment atmosphere is an atmospheric environment atmosphere, and after the heat treatment, it is cleaned with an acid solution to clean the second dielectric layer 4, thereby obtaining a film layer structure; after cleaning, the hydrophilic angle of the film layer surface of the film layer structure is tested using a hydrophilic angle measuring instrument to find that it is 4.64 degrees. The wear resistance test was carried out using an abrasion tester. A standard grinding wheel (grinding wheel model CS-10F) was used with a force of 250 grams. After grinding for 200 revolutions, the surface of the membrane layer of the membrane structure was cleaned and the hydrophilic angle was tested. The hydrophilic angle was measured to be 4.71 degrees. The surface of the membrane layer of the membrane structure was scraped 2 million times with a wiper and then cleaned and the hydrophilic angle was tested. The hydrophilic angle was measured to be 4.84 degrees. The membrane layer of the membrane structure was immersed in 2mol / L hydrochloric acid solution for 24 hours, 2mol / L sodium hydroxide solution for 24 hours, and saturated sodium chloride solution for 96 hours. After cleaning and testing, the hydrophilic angles were 4.65 degrees, 4.36 degrees, and 4.79 degrees, respectively.

[0050] The present invention is described above by way of example in conjunction with the accompanying drawings. It is obvious that the specific implementation of the present invention is not limited to the above-mentioned method. As long as various non-substantial improvements are made using the method concept and technical solution of the present invention, or the concept and technical solution of the present invention are directly applied to other occasions without improvement, they are all within the scope of protection of the present invention.

Claims

1. A laminate, characterized in that: The stack is formed on at least one surface of a substrate, and is composed of a silicon oxycarbide film layer, a carbon element-containing layer, and an aluminum oxide film layer in order from the surface of the substrate outward; the silicon oxycarbide film layer is in direct contact with the surface of the substrate, and the silicon oxycarbide film layer is composed of at least one film layer; the aluminum oxide film layer is composed of at least one film layer.

2. A laminate according to claim 1, characterized in that: The substrate is a glass substrate, a ceramic substrate, a metal substrate, a silicon-based substrate, a polyimide substrate, an organic substrate capable of withstanding temperatures greater than 350° C., or a substrate having a film layer on its surface.

3. A laminate according to claim 2, characterized in that: The film layer is a low-emissivity film layer, a conductive film layer, a color-changing film layer, a head-up display film layer, an anti-ultraviolet film layer, an anti-infrared film layer, an antibacterial film layer, an anti-reflection film layer and / or an anti-reflection film layer.

4. A laminate according to claim 1, characterized in that: The carbon-containing element layer is composed of at least one film layer, and the thickness of the carbon-containing element layer is ≤500nm.

5. A laminate according to claim 1, characterized in that: The aluminum oxide film layer may further include a metal film layer.

6. A laminate according to claim 1, characterized in that: The stack may include at least one film layer having a certain conductivity.

7. A laminate according to claim 1, characterized in that: A titanium dioxide film layer can be formed on the surface of the carbon-containing element layer, and the titanium dioxide film layer partially covers the surface of the carbon-containing element layer; the titanium dioxide film layer covers ≤80% of the surface of the carbon-containing element layer; the thickness of the titanium dioxide film layer is <10nm.

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