Lamination layer

Abstract

The laminated layer is formed on the surface of a substrate, a first dielectric layer, a carbon element-containing layer and a second dielectric layer are sequentially arranged on the surface of the substrate outwards, the first dielectric layer is in direct contact with the surface of the substrate, the first dielectric layer is at least composed of a film layer, and the second dielectric layer is at least composed of a film layer. Thus, the laminate can be subjected to high-temperature heat treatment. The laminated layer can be subjected to heat treatment at the temperature of more than 400 DEG C, more preferably heat treatment at the temperature of more than 500 DEG C, and even heat treatment at the temperature of more than 700 DEG C, which are performances that many existing hydrophilic films do not have.

Description

Technical Field

[0001] This invention relates to the field of laminate technology, and more specifically to a wear-resistant, high-temperature heat-treatable, hydrophilic laminate, its preparation method, and its application. Background Technology

[0002] Self-cleaning coatings can be categorized into hydrophobic and hydrophilic self-cleaning coatings based on their operating principles. The self-cleaning mechanism of hydrophobic self-cleaning coatings is similar to the surface cleaning principle of lotus leaves; the coating surface needs to have moderate roughness and low surface energy. However, hydrophobic surfaces typically only provide waterproofing, not dustproofing. During use, the adhesion of oily contaminants often lowers the hydrophobic angle, preventing water droplets from rolling off. This results in larger water droplets forming larger dust accumulation. The self-cleaning mechanism of hydrophilic self-cleaning coatings refers to the very small water contact angle on the coating surface, typically less than 10°. A small amount of rainwater or dew can form a water film on the substrate surface, preventing dust or contaminants from contacting the material surface. Furthermore, the flow of the water film more easily carries away dust. Even if the substrate surfaces are equally dirty, under the same cleaning conditions, or even relatively poor cleaning conditions, substrates coated with hydrophilic coatings are easier to clean (compared to substrates without hydrophilic coatings). Therefore, hydrophilic self-cleaning coatings are more effective than hydrophobic self-cleaning coatings. However, existing hydrophilic self-cleaning coatings, when used on substrates, typically cause a decrease in the substrate's light transmittance. Furthermore, most hydrophilic self-cleaning coatings contain titanium dioxide, whose refractive index is much higher than that of the substrate glass, causing light reflection. If used on the surface of photovoltaic modules, this would lead to a decrease in the power generation of the photovoltaic modules. Therefore, it is necessary to develop a self-cleaning coating that does not sacrifice the light transmittance of the glass to solve the problems existing in the current technology.

[0003] Fogging is a natural phenomenon caused by the condensation of droplets due to temporary changes in ambient humidity and temperature. After fogging, incident light is strongly scattered by the condensed water droplets, reducing the transparency of windshields, rearview mirrors, goggles, building curtain walls, and other items. Fogging not only inconveniences people's lives but can also have extremely serious consequences. Currently, preparing hydrophilic surfaces to effectively suppress droplet formation is a popular method for solving fogging problems. However, anti-fogging coatings prepared using this method are easily damaged, which can severely impact the performance of the coated components. Furthermore, the surface of anti-fogging coatings prepared using this method is susceptible to contamination by dyes, bacteria, and other substances, affecting optical properties. Moreover, anti-fogging coatings prepared using this method often employ volatile organic solvents, which also pose significant environmental hazards. Therefore, it is necessary to develop an environmentally friendly hydrophilic laminate to solve the fogging problem.

[0004] Carbon-containing coatings possess excellent properties such as extremely high hardness and wear resistance, low coefficient of friction and thermal expansion, high elastic modulus, and good chemical stability, making them widely used in surface protection. However, carbon-containing coatings typically exhibit certain hydrophobic characteristics (contact angle greater than 60°), limiting their application in some hydrophilic hard functional surface protection applications. Some researchers have addressed this by doping the carbon-containing coating with appropriate amounts of Si and O elements during deposition, creating a certain amount of Si-O-Si bonds in the film. Since Si-O-Si bonds are hydrophilic, this allows the carbon-containing coating to achieve a hydrophilic effect. However, this type of coating cannot be subjected to high-temperature heat treatment; if heat-treated, the coating will burn out, and the Si-O-Si bonds will further oxidize, causing the hydrophilic properties to disappear. Furthermore, it is not resistant to immersion in sodium hydroxide solution, as the Si-O-Si bonds react with sodium hydroxide to form sodium silicate, which severely degrades the film's performance. Summary of the Invention

[0005] The purpose of this invention is to solve the problems existing in the above-mentioned hydrophilic film layers by providing a laminate and a subsequent processing method for the laminate to obtain a hydrophilic film layer. The laminate provided by this invention can be subjected to high-temperature heat treatment (such as hot bending, tempering, etc.). The hydrophilic film layer finally obtained by this invention has a certain anti-reflective effect, a certain anti-reflective effect, extremely high hardness and wear resistance, and good chemical stability.

[0006] To achieve the above objectives, the present invention provides a stacked layer formed on at least one surface of a substrate, wherein a first dielectric layer, a carbon-containing layer, and a second dielectric layer are sequentially formed from the substrate surface outwards; the first dielectric layer is in direct contact with the substrate surface and consists of at least one film layer; the second dielectric layer consists of at least two film layers; the first dielectric layer contains oxygen and carbon elements and its coefficient of thermal expansion is ≥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 an existing film layer on its surface. The film layer on the substrate with an existing 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-reflective film layer, and / or an anti-reflective film layer, etc.

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

[0010] The first dielectric 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 first dielectric layer is a compound with a stoichiometric or non-stoichiometric composition, or the first dielectric layer is a mixture of a carbonaceous substance and the aforementioned compounds.

[0011] The second dielectric layer is composed of oxides, nitrides, nitrides, sulfides, sulfur oxides, selenides, selenide oxides, tellurides, telluride oxides, fluorides, and / or fluoride oxides 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 second dielectric layer may also contain a metal film layer, which is composed of elemental form and / or alloys 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 insert at least one layer of film with a certain conductivity, which 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 can be inserted between the carbon-containing layer and the second dielectric layer. This titanium dioxide film only partially covers the surface of the carbon-containing layer; preferably, it covers ≤80% of the carbon-containing layer surface; more preferably, it covers ≤50%; and most preferably, it covers ≤20%. The thickness of the titanium dioxide film is <10 nm, and preferably <5 nm. The stacked layers of this invention can be prepared by methods such as magnetron sputtering, vapor deposition, atomic layer deposition, chemical vapor deposition, and physical vapor deposition.

[0014] The laminate is subjected to heat treatment at a temperature of 350℃-800℃ and a pressure of 0.01 Pa to 2 atmospheres. The heat treatment atmosphere is a reducing atmosphere, an oxidizing atmosphere, an atmospheric atmosphere, and / or an inert atmosphere. The heat-treated laminate is then cleaned with a solution, such as an alkaline solution, an acidic solution, and / or water, to remove the second dielectric layer. After cleaning, the film surface is dried.

[0015] The resulting laminated cleaning solution can be used for automobile windshields, in-vehicle displays and rearview mirrors, train and high-speed rail windshields, ship and aircraft glass, building door and window glass, walls and glass curtain walls, bathroom glass, mirror glass, tile surfaces, 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 present invention:

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

[0018] 2. After cleaning, the laminate of the present invention has certain anti-reflection and anti-reflection functions, which are properties that many existing hydrophilic films do not have; its hydrophilic angle can be less than 5 degrees, and even better, less than 3 degrees; its bonding with the substrate is very strong, and it can resist scratches and wear; it can withstand more than 2 million scratches from car windshield wipers while maintaining its performance basically unchanged.

[0019] 3. After cleaning, the laminate of the present invention can withstand soaking in 2 mol / L hydrochloric acid solution for 24 hours, 2 mol / L sodium hydroxide solution for 24 hours, and saturated sodium chloride solution for 96 hours, while maintaining essentially unchanged performance, indicating that it has excellent chemical stability. Attached Figure Description

[0020] Figure 1 This is a schematic diagram of a layered structure;

[0021] Figure 2 This is a schematic diagram of the second type of stacked structure.

[0022] Figure 3 This is a schematic diagram of the third type of stacked structure.

[0023] Figure 4 This is a schematic diagram of the fourth type of layered structure.

[0024] 1-Substrate, 2-First dielectric layer, 3-Carbon-containing layer, 4-Second dielectric layer, 5-Conductive film layer, 6-Titanium dioxide film layer, 7-Low-emissivity film layer Detailed Implementation

[0025] The present invention will now be further described in conjunction with the accompanying drawings and specific embodiments.

[0026] Existing hydrophilic or self-cleaning films generally have short lifespans and are susceptible to corrosion from hydrochloric acid and sodium hydroxide solutions, exhibiting poor resistance to mechanical scratches and inability to undergo high-temperature heat treatment. The laminate of this invention solves these problems. The technical solution adopted by this invention is to provide a laminate formed on at least one surface of a substrate, comprising, from the substrate surface outwards, a first dielectric layer 2, a carbon-containing layer 3, and a second dielectric layer; the first dielectric layer 2 is in direct contact with the substrate surface and consists of at least one film layer; the second dielectric layer consists of at least two film layers; the first dielectric layer 2 contains oxygen and carbon elements and its coefficient of thermal expansion is ≥8×10. -7 Through numerous experiments, the inventors have surprisingly discovered that using the first dielectric layer 2 of this invention enables the carbon-containing layer 3 to achieve higher film quality during deposition. This improved film quality ultimately reduces the hydrophilic angle of the carbon-containing layer 3, resulting in excellent self-cleaning, easy-to-clean, and anti-fogging properties. Furthermore, during subsequent processing of the laminate, the first dielectric layer 2 effectively prevents elements from the substrate from diffusing into the carbon-containing layer 3. During these subsequent processing, the second dielectric layer effectively protects the carbon-containing layer 3, while some elements in the second dielectric layer react with some elements in the carbon-containing layer 3, further reducing the hydrophilic angle of the carbon-containing layer 3 after processing, thus achieving excellent self-cleaning, easy-to-clean, and anti-fogging properties.

[0027] If the thickness of the carbon-containing layer 3 in the stack of the present invention is greater than 500 nm, the transmittance of the film layer will decrease significantly and the film layer will be more prone to detachment. However, it will not significantly improve the self-cleaning performance of the stack and will increase the manufacturing cost. In the present invention, when the titanium dioxide film layer inserted between the carbon-containing layer 3 and the second dielectric layer covers more than 80% of the surface of the carbon-containing layer 3, it will have an adverse effect on the hydrophilicity after the stacking process, causing a significant increase in the hydrophilic angle. When the thickness of the titanium dioxide film layer is ≥10 nm, the hydrophilicity after the stacking process will also decrease significantly.

[0028] After heat treatment and cleaning, the laminate of this invention exhibits long-term, all-weather self-cleaning and easy-to-clean properties, without requiring ultraviolet light (unlike known titanium dioxide-based self-cleaning films, which require ultraviolet light to function, as ultraviolet light is weak on cloudy days and at night, rendering their self-cleaning function ineffective). After cleaning, the laminate of this invention possesses certain anti-reflective and anti-reflective properties, which are not found in many existing self-cleaning films. Its hydrophilic angle can be less than 5 degrees, and even better, less than 3 degrees. It bonds strongly to the substrate, exhibiting excellent scratch and abrasion resistance. Using a standard grinding wheel (CS-10F) with a force of 250 grams, the performance of the film layer of this invention remained essentially unchanged after 200 revolutions, demonstrating its superior abrasion resistance. It can withstand over 2 million wipes from a car windshield wiper while maintaining essentially unchanged performance.

[0029] After cleaning, the laminate 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 essentially unchanged performance, indicating that it has excellent chemical stability.

[0030] In the following embodiments, each film layer is sequentially deposited on a clean surface of the substrate.

[0031] Example 1

[0032] A first dielectric layer 2, which is a silicon dioxide film with a thickness of 20 nm, is deposited on the surface of a glass substrate. Next, a carbon-containing layer 3, with a thickness of 500 nm, is deposited on the surface of the first dielectric layer 2. Then, a second dielectric layer, which is a 50 nm alumina film, is deposited on the surface of the carbon-containing layer 3. Figure 1 As shown; next, the glass substrate with the deposited film was heat-treated at 350 degrees Celsius under a pressure of 0.01 Pa in an inert atmosphere. After heat treatment, it was cleaned with an alkaline solution to remove the second dielectric layer. After cleaning, the surface hydrophilicity angle of the film was measured to be 3.84 degrees using an instrument for measuring hydrophilicity angle. Abrasion resistance was tested using an abrasion tester. A standard grinding wheel (model CS-10F) was used with a force of 250 grams for 200 revolutions. After cleaning the film surface, the hydrophilicity angle was measured to be 4.01 degrees. The surface of the sample was then wiped with a windshield wiper for 2 million times and cleaned before the hydrophilicity angle was measured to be 3.92 degrees. After immersing the sample in 2 mol / L hydrochloric acid solution for 24 hours, 2 mol / L sodium hydroxide solution for 24 hours, and saturated sodium chloride solution for 96 hours, the hydrophilicity angles measured after cleaning were 3.99 degrees, 3.76 degrees, and 3.8 degrees, respectively.

[0033] Example 2

[0034] A first dielectric layer 2 is deposited on the surface of a glass substrate. The first dielectric layer 2 consists of a 15 nm silicon oxide film and a 10 nm silicon carbide film, wherein the silicon oxide film is in direct contact with the surface of the glass substrate. Next, a carbon-containing layer 3 is deposited on the surface of the first dielectric layer 2. The carbon-containing layer 3 is doped with aluminum and has a thickness of 200 nm. Then, a second dielectric layer is deposited on the surface of the carbon-containing layer 3. The second dielectric layer consists of a 15 nm bismuth oxide film and a 25 nm aluminum nitride film, wherein the bismuth oxide film is in direct contact with the carbon layer. The glass substrate with the deposited films is then subjected to heat treatment at 550 degrees Celsius under 1 atmosphere of atmospheric pressure. After heat treatment, the substrate is cleaned with an acid solution to remove the second dielectric layer. After cleaning, the surface hydrophilicity angle of the film is measured to be 3.16 degrees using an instrument for measuring hydrophilicity angle. Abrasion resistance tests were conducted using an abrasion tester. A standard grinding wheel (CS-10F) was used with a force of 250 grams. After grinding for 200 revolutions, the film surface was cleaned and the hydrophilicity angle was tested, which was found to be 3.41 degrees. The surface of the sample was then wiped with a windshield wiper for 2 million times, cleaned, and the hydrophilicity angle was tested, which was found to be 3.22 degrees. The sample was then immersed in 2 mol / L hydrochloric acid solution for 24 hours, 2 mol / L sodium hydroxide solution for 24 hours, and saturated sodium chloride solution for 96 hours. After cleaning, the hydrophilicity angles were tested to be 3.28 degrees, 3.06 degrees, and 3.11 degrees, respectively.

[0035] Example 3

[0036] A first dielectric layer 2 is deposited on the surface of a glass substrate. The first dielectric layer 2 consists of a 15 nm thick tin oxide film and a 10 nm thick titanium carbide film, wherein the tin oxide film is in direct contact with the surface of the glass substrate. Next, a carbon-containing layer 3 is deposited on the surface of the first dielectric layer 2. The carbon-containing layer 3 has a two-layer structure: a 30 nm thick undoped carbon-containing layer and a 70 nm thick sulfur-doped carbon-containing layer. Then, a second dielectric layer is deposited on the surface of the carbon layer. The second dielectric layer consists of a 60 nm thick zinc oxide film and a 10 nm thick magnesium oxide film, wherein the zinc oxide film is in direct contact with the carbon layer. The glass substrate with the deposited films is then subjected to a heat treatment at 350 degrees Celsius under a reducing atmosphere at 2 atmospheres. After the heat treatment, the substrate is cleaned with an acid solution to remove the second dielectric layer. After cleaning, the surface hydrophilicity angle of the film is measured to be 2.86 degrees using an instrument for measuring hydrophilicity angle. Abrasion resistance tests were conducted using an abrasion tester. A standard grinding wheel (model CS-10F) was used with a force of 250 grams. After grinding for 200 revolutions, the film surface was cleaned and the hydrophilicity angle was tested, which was found to be 2.98 degrees. The surface of the sample was then wiped with a windshield wiper for 2 million times, cleaned, and the hydrophilicity angle was tested, which was found to be 2.92 degrees. The sample was then immersed in 2 mol / L hydrochloric acid solution for 24 hours, 2 mol / L sodium hydroxide solution for 24 hours, and saturated sodium chloride solution for 96 hours. After cleaning, the hydrophilicity angles were tested to be 2.9 degrees, 2.71 degrees, and 2.88 degrees, respectively.

[0037] Example 4

[0038] A first dielectric layer 2 is deposited on the surface of a glass substrate. The first dielectric layer 2 consists of a 15 nm tin oxide film and a 10 nm niobium carbide film, wherein the tin oxide film is in direct contact with the surface of the glass substrate. Next, a carbon-containing layer 3, doped with nitrogen, is deposited on the surface of the first dielectric layer 2. The carbon-containing layer 3 has a thickness of 100 nm. Then, a second dielectric layer is deposited on the surface of the carbon-containing layer 3. The second dielectric layer consists of a 100 nm zinc oxide aluminum-doped film. The glass substrate with the deposited films is then subjected to heat treatment at 550 degrees Celsius under one atmosphere of atmospheric pressure. After heat treatment, the substrate is cleaned with an acid solution to remove the second dielectric layer. After cleaning, the surface hydrophilicity angle of the film is measured to be 2.44 degrees using an instrument for measuring hydrophilicity angle. Abrasion resistance tests were conducted using an abrasion tester. A standard grinding wheel (CS-10F) was used with a force of 250 grams. After grinding for 200 revolutions, the film surface was cleaned and the hydrophilicity angle was tested, which was found to be 2.51 degrees. The surface of the sample was then wiped with a windshield wiper for 2 million times, cleaned, and the hydrophilicity angle was tested, which was found to be 2.64 degrees. The sample was then immersed in 2 mol / L hydrochloric acid solution for 24 hours, 2 mol / L sodium hydroxide solution for 24 hours, and saturated sodium chloride solution for 96 hours. After cleaning, the hydrophilicity angles were tested to be 2.7 degrees, 2.24 degrees, and 2.51 degrees, respectively.

[0039] Example 5

[0040] A first dielectric layer 2 is deposited on the surface of a ceramic substrate 1. The first dielectric layer 2 consists of a 10 nm zirconium oxide film and a 12 nm chromium carbide film, wherein the zirconium oxide film is in direct contact with the surface of the ceramic substrate 1. Next, a carbon-containing layer 3 is deposited on the surface of the first dielectric layer 2. The carbon-containing layer 3 is doped with boron and has a thickness of 80 nm. Then, a second dielectric layer is deposited on the surface of the carbon-containing layer 3. The second dielectric layer consists of a 5 nm magnesium film and an 80 nm zinc oxide aluminum-doped film. The ceramic substrate 1 with the deposited film is then subjected to a heat treatment at 800 degrees Celsius under one atmosphere of atmospheric pressure. After the heat treatment, the substrate is cleaned with an acid solution to remove the second dielectric layer. After cleaning, the surface hydrophilicity angle of the film is measured to be 4.57 degrees using an instrument for measuring hydrophilicity angle. Abrasion resistance tests were conducted using an abrasion tester. A standard grinding wheel (model CS-10F) was used with a force of 250 grams. After grinding for 200 revolutions, the film surface was cleaned and the hydrophilicity angle was tested, which was found to be 4.77 degrees. The surface of the sample was then wiped with a windshield wiper for 2 million times, cleaned, and the hydrophilicity angle was tested, which was found to be 4.95 degrees. The sample was then immersed in 2 mol / L hydrochloric acid solution for 24 hours, 2 mol / L sodium hydroxide solution for 24 hours, and saturated sodium chloride solution for 96 hours. After cleaning, the hydrophilicity angles were found to be 4.59 degrees, 4.36 degrees, and 4.52 degrees, respectively.

[0041] Example 6

[0042] A first dielectric layer 2 is deposited on the surface of a ceramic substrate 1. The first dielectric layer 2 consists of a 10 nm silicon oxynitride film and a 12 nm silicon carbide film, wherein the zirconium oxide film is in direct contact with the surface of the ceramic substrate 1. Next, a carbon-containing layer 3 is deposited on the surface of the first dielectric layer 2. The carbon-containing layer 3 is doped with fluorine and has a thickness of 70 nm. Then, a second dielectric layer is deposited on the surface of the carbon-containing layer 3. The second dielectric layer consists of a 5 nm iron oxide film, a 3 nm zinc-tin alloy film, and an 80 nm zinc oxide magnesium-doped film. The ceramic substrate 1 with the deposited film is then subjected to a heat treatment at 600 degrees Celsius under 1 atmosphere of atmospheric pressure. After the heat treatment, the substrate is cleaned with an acid solution to remove the second dielectric layer. After cleaning, the surface hydrophilicity angle of the film is measured to be 2.81 degrees using an instrument for measuring hydrophilicity angle. Abrasion resistance tests were conducted using an abrasion tester. A standard grinding wheel (CS-10F) was used with a force of 250 grams. After grinding for 200 revolutions, the film surface was cleaned and the hydrophilicity angle was tested, which was found to be 2.96 degrees. The surface of the sample was then wiped with a windshield wiper for 2 million times, and the hydrophilicity angle was cleaned and tested, which was found to be 3.02 degrees. The sample was then immersed in 2 mol / L hydrochloric acid solution for 24 hours, 2 mol / L sodium hydroxide solution for 24 hours, and saturated sodium chloride solution for 96 hours. After cleaning, the hydrophilicity angles were 2.79 degrees, 2.71 degrees, and 2.85 degrees, respectively.

[0043] Example 7

[0044] A glass substrate with a pre-deposited conductive film is used as the substrate. A first dielectric layer 2 is deposited on the surface of the conductive film. The first dielectric layer 2 is a 20 nm thick mixture of silicon oxide and carbon. Next, a carbon-containing layer 3, doped with fluorine and hydrogen, is deposited on the surface of the first dielectric layer 2. The carbon-containing layer 3 has a thickness of 50 nm. Then, a second dielectric layer is deposited on the surface of the carbon-containing layer 3. The second dielectric layer consists of a 3 nm iron oxide film, a 10 nm magnesium-doped zinc oxide film, a 3 nm zinc-tin alloy film, and a 35 nm aluminum-doped zinc oxide film. Figure 2As shown; next, the substrate with the deposited film layer was heat-treated at 550 degrees Celsius under 1 atmosphere of atmospheric pressure. After heat treatment, it was cleaned with an acid solution to remove the second dielectric layer. After cleaning, the surface hydrophilicity angle of the film layer was measured to be 3.92 degrees using an instrument for measuring hydrophilicity angle. Abrasion resistance test was performed using an abrasion tester. A standard grinding wheel (model CS-10F) was used with a force of 250 grams and ground for 200 revolutions. After cleaning the film layer surface, the hydrophilicity angle was measured to be 4.09 degrees. The surface of the sample was then wiped with a windshield wiper for 2 million times and cleaned before the hydrophilicity angle was measured to be 4.04 degrees. After immersing the sample in 2 mol / L hydrochloric acid solution for 24 hours, 2 mol / L sodium hydroxide solution for 24 hours, and saturated sodium chloride solution for 96 hours, the hydrophilicity angles measured after cleaning were 3.91 degrees, 3.81 degrees, and 3.89 degrees, respectively.

[0045] Example 8

[0046] Using a glass substrate with a pre-deposited low-emissivity film, a first dielectric layer 2 is deposited on the undeposited surface of the substrate. The first dielectric layer 2 is a 28 nm thick mixture of silicon oxide and carbon. Next, a carbon-containing layer 3 is deposited on the surface of the first dielectric layer 2. This carbon-containing layer 3 consists of two sublayers: one sublayer is a carbon-containing layer doped with bromine, and the other is a carbon-containing layer doped with nitrogen. The total thickness of the carbon-containing layer 3 is 55 nm. Then, a second dielectric layer is deposited on the surface of the carbon-containing layer 3. This second dielectric layer consists of a 10 nm magnesium-doped zinc oxide film, a 3 nm bismuth metal film, and a 35 nm zinc-tin oxide film. Figure 4 As shown; next, the substrate with the deposited film layer was heat-treated at 580 degrees Celsius under 1 atmosphere of atmospheric pressure. After heat treatment, it was cleaned with an acid solution to remove the second dielectric layer. After cleaning, the surface hydrophilicity angle of the film layer was measured to be 4.11 degrees using an instrument for measuring hydrophilicity angle. Abrasion resistance test was performed using an abrasion tester. A standard grinding wheel (model CS-10F) was used with a force of 250 grams and ground for 200 revolutions. After cleaning the film layer surface, the hydrophilicity angle was measured to be 4.3 degrees. The surface of the sample was then wiped with a windshield wiper for 2 million times and cleaned before the hydrophilicity angle was measured to be 4.24 degrees. After immersing the sample in 2 mol / L hydrochloric acid solution for 24 hours, 2 mol / L sodium hydroxide solution for 24 hours, and saturated sodium chloride solution for 96 hours, the hydrophilicity angles measured after cleaning were 3.97 degrees, 3.84 degrees, and 4.06 degrees, respectively.

[0047] Example 9

[0048] A first dielectric layer 2 is deposited on the surface of a glass substrate. The first dielectric layer 2 consists of a 15 nm silicon oxynitride film and a 10 nm titanium oxide film. Next, a carbon-containing layer 3, doped with nitrogen and hydrogen, is deposited on the surface of the first dielectric layer. The carbon-containing layer 3 has a thickness of 55 nm. Then, a 3 nm titanium dioxide film is deposited on the surface of the carbon-containing layer 3, covering 75% of the surface area. Finally, a second dielectric layer is deposited on the surface of the titanium dioxide film. The second dielectric layer consists of a 10 nm magnesium-doped zinc oxide film, a 3 nm bismuth metal film, and a 35 nm zinc-tin oxide film. Figure 3 As shown; next, the substrate with the deposited film layer was heat-treated at 560 degrees Celsius under 1 atmosphere of atmospheric pressure. After heat treatment, it was cleaned with an acid solution to remove the second dielectric layer. After cleaning, the surface hydrophilicity angle of the film layer was measured to be 4.64 degrees using an instrument for measuring hydrophilicity angle. Abrasion resistance test was performed using an abrasion tester. A standard grinding wheel (model CS-10F) was used with a force of 250 grams and ground for 200 revolutions. After cleaning the film layer surface, the hydrophilicity angle was measured to be 4.71 degrees. The surface of the sample was then wiped with a windshield wiper for 2 million times and cleaned before the hydrophilicity angle was measured to be 4.84 degrees. After immersing the sample in 2 mol / L hydrochloric acid solution for 24 hours, 2 mol / L sodium hydroxide solution for 24 hours, and saturated sodium chloride solution for 96 hours, the hydrophilicity angles measured after cleaning were 4.65 degrees, 4.36 degrees, and 4.79 degrees, respectively.

[0049] The present invention has been described above by way of example with reference to the accompanying drawings. Obviously, the specific implementation of the present invention is not limited to the above-described manner. Any non-substantial improvements made using the inventive concept and technical solution of the present invention, or the direct application of the inventive concept and technical solution of the present invention to other occasions without modification, are all within the protection scope of the present invention.

Claims

1. A stack, characterized by: The stack is formed on at least one surface of a substrate, and the stack comprises, from outside to inside of the substrate surface, a first dielectric layer, a carbon element-containing layer, and a second dielectric layer; the first dielectric layer is in direct contact with the substrate surface; the first dielectric layer comprises at least one film layer; the second dielectric layer comprises at least one film layer; and the first dielectric layer contains oxygen element and carbon element.

2. A laminate according to claim 1, wherein: The carbon element-containing layer is a non-doped layer and / or the carbon element-containing layer can be doped with element A; the element A is at least one of oxygen element, sulfur element, selenium element, tellurium element, nitrogen element, phosphorus element, arsenic element, antimony element, bismuth element, hydrogen element, boron element, aluminum element, gallium element, indium element, fluorine element, chlorine element, bromine element, and / or iodine element.

3. The stack of claim 1, wherein: The substrate is a glass substrate, a ceramic substrate, a metal substrate, a silicon substrate, a polyimide substrate, an organic substrate capable of withstanding temperature greater than 350 DEG C, or a substrate having a film layer on the surface.

4. A laminate according to claim 3, wherein: The film layer is a low-emissivity film layer, a conductive film layer, a color-variable film layer, a head-up display film layer, an ultraviolet-resistant film layer, an infrared-resistant film layer, an antibacterial film layer, an anti-reflection film layer, and / or a transparent film layer.

5. The stack of claim 1, wherein: The carbon element-containing layer comprises at least one film layer, and the thickness of the carbon element-containing layer is less than or equal to 500 nm.

6. The stack of claim 1, wherein: The first dielectric layer can further contain at least one of scandium, yttrium, titanium, zirconium, hafnium, niobium, tantalum, chromium, molybdenum, tungsten, nickel, palladium, platinum, silicon, cerium, gadolinium, tin, fluorine, and / or nitrogen; the first dielectric layer is a stoichiometric or non-stoichiometric compound; or the first dielectric layer is a mixture of a carbon material and the aforementioned compound.

7. The stack of claim 1, wherein: The second dielectric layer is composed of at least one of oxides, nitrides, oxynitrides, sulfides, oxysulfides, selenides, oxyselenides, tellurides, oxotellurides, fluorides, and / or oxyfluorides of boron, aluminum, gallium, indium, magnesium, calcium, strontium, barium, zinc, manganese, carbon, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth, and / or iron; the aforementioned compounds are stoichiometric or non-stoichiometric.

8. The stack of claim 1, wherein: The second dielectric layer can further comprise a metal film layer composed of at least one of elemental aluminum, gallium, indium, magnesium, calcium, strontium, barium, zinc, iron, nickel, chromium, titanium, tin, lead, niobium, antimony, and / or bismuth, and / or an alloy thereof.

9. The stack of claim 1 wherein: The stack can be inserted with at least one film layer having a certain conductivity, which 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.

10. The stack of claim 1, wherein: A titanium dioxide film layer can be inserted between the carbon element-containing layer and the second dielectric layer, and the titanium dioxide film layer only partially covers the surface of the carbon element-containing layer; the titanium dioxide film layer covers less than or equal to 80% of the surface of the carbon element-containing layer; and the thickness of the titanium dioxide film layer is less than 10 nm.

11. A method of heat treating a stack, characterized by: The stack of claims 1-10 is subjected to a heat treatment at a temperature of 350-800°C, a pressure of 0.01 Pa to 2 atm, and in a reducing, oxidizing, atmospheric, and / or inert atmosphere.

12. A method of cleaning a stack, characterized by: After the stack of claims 1-10 is subjected to the heat treatment of claim 11, it is subjected to a cleaning treatment with a solution, which removes the second dielectric layer, the solution being an alkaline, acid, and / or aqueous solution.

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