Preparation method for preparing diamond-like carbon protective film on glass surface, diamond-like carbon protective film and glass

Abstract

The invention provides a preparation method for preparing a diamond-like carbon protective film on the surface of glass, the diamond-like carbon protective film and the glass.The preparation method for preparing the diamond-like carbon protective film on the surface of the glass comprises the steps that mixed gas of silane, acetylene and argon with the flow ratio being 10: 5: 1-20: 10: 1 is introduced into a reaction chamber; the pressure intensity in the reaction chamber is adjusted to 0.1-10 Pa; the power of a pulse ionization power supply is set to be 100-2000 W; the plasma auxiliary voltage is set to be 10-1000 V; and depositing the diamond-like carbon protective film with Si-H functional groups on the surface of the glass under the conditions that the deposition temperature is 50-200 DEG C and the deposition time is 10-120 minutes. By applying the technical scheme provided by the invention, the problems of poor hydrophobicity and light transmission of glass in the prior art can be effectively solved.

Description

Technical Field

[0001] The present invention relates to the technical field of glass preparation, and in particular to a method for preparing a diamond-like protective film on a glass surface, the diamond-like protective film and glass. Background Art

[0002] Glass, as a material with a long history and wide application, plays an indispensable role in many fields such as construction, automobile manufacturing, electronic display, optical instruments, etc. due to its transparent and hard properties. However, the inherent characteristics of the glass surface limit its use and maintenance efficiency in certain environments. On the one hand, the high surface energy of the glass surface makes it easy to absorb dust, grease and various pollutants in the air, which not only affects the aesthetics and optical properties of the glass, but also may accelerate the corrosion of the glass surface and reduce its transparency and durability. On the other hand, the hardness and wear resistance of the glass itself are relatively low, and it is easily scratched and worn, especially in high-traffic areas or outdoor environments, which not only affects the appearance of the glass, but also may damage its structural integrity and shorten its service life.

[0003] In order to solve the above problems, researchers have tried many methods to improve the surface properties of glass. Among them, diamond-like carbon (DLC) is regarded as an ideal surface modification material due to its high hardness, good chemical stability and optical transparency. Diamond-like carbon is an amorphous carbon material with physical and chemical properties similar to natural diamond, but its structure is closer to amorphous carbon, which allows it to maintain high strength while maintaining good transparency. Through chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), magnetron sputtering and other methods, a layer of diamond-like carbon film can be deposited on the glass surface to enhance its hardness and wear resistance.

[0004] However, traditional diamond-like carbon films are deficient in terms of hydrophobicity and adhesion. In order to improve the hydrophobicity, fluorine-containing compounds such as trifluoromethane (CHF3) are introduced in the prior art, which are co-deposited with carbon source gases (such as methane CH4) through processes such as CVD to form a diamond-like carbon film with enhanced hydrophobicity. Although this method can improve the hydrophobicity of the glass surface to a certain extent, there are technical problems such as poor film uniformity, possible long-term effects of fluorine on the environment and human health, and decreased light transmittance. Summary of the invention

[0005] The main purpose of the present invention is to provide a method for preparing a diamond-like protective film on a glass surface, a diamond-like protective film and glass, so as to solve the problems of poor hydrophobicity and light transmittance of glass in the prior art.

[0006] In order to achieve the above-mentioned purpose, one aspect of the present application provides a method for preparing a diamond-like protective film on a glass surface, comprising: introducing a mixed gas of silane, acetylene and argon with a flow ratio of 10:5:1-20:10:1 into a reaction chamber; adjusting the pressure in the reaction chamber to 0.1-10Pa; setting the power of the pulsed ionization power supply to 100-2000W; setting the plasma auxiliary voltage to 10-1000V; and depositing a diamond-like protective film having Si-H functional groups on the glass surface under the conditions of a deposition temperature of 50-200°C and a deposition time of 10-120min.

[0007] Furthermore, the silane is one of monosilane, hexamethylsilane, dimethylsilane and monomethylsilane.

[0008] Furthermore, before the mixed gas is introduced into the reaction chamber, the preparation method further includes: pre-treating the glass to remove impurities.

[0009] Furthermore, the step of pre-treating the glass includes: selecting a glass substrate; ultrasonically cleaning the glass substrate with deionized water, acetone, and ethanol in sequence, with each cleaning time being 15-30 minutes to remove impurities on the glass surface; blowing dry with high-purity nitrogen; and keeping warm for a preset time.

[0010] Furthermore, after pre-treating the glass and before introducing the mixed gas into the reaction chamber, the preparation method further includes: ion cleaning the glass substrate.

[0011] Furthermore, the step of ion cleaning the glass substrate includes: placing the pretreated glass substrate on a sample stage of a reaction chamber of a coating deposition device; evacuating the reaction chamber to a vacuum of 1.0×10 -3 pa, when heated to 50℃~100℃, the surface of the glass substrate is ion cleaned with argon gas by hot wire arc discharge plasma etching process, the etching bias voltage is ≤100V, and the ionization power is 1000W to remove surface impurities.

[0012] In order to achieve the above-mentioned purpose, one aspect of the present application provides a diamond-like protective film obtained by the above-mentioned preparation method, wherein the diamond-like protective film contains Si—H functional groups.

[0013] Furthermore, the thickness of the diamond-like carbon protective film is within 500 nm.

[0014] The last aspect of the present application provides a glass, comprising: a glass substrate; a diamond-like protective film, disposed on the surface of the glass substrate, and the diamond-like protective film is the above-mentioned diamond-like protective film.

[0015] Applying the technical solution of the present application, the preparation of a diamond-like protective film on the glass surface has at least the following three advantages: First, the hydrophobicity is significantly enhanced: a specific ratio of argon and acetylene is used as the reaction gas, and silane coupling is introduced. From the analysis of chemical principles and material properties, this formula and process can accurately control the structure and composition of the film layer at the molecular level. Acetylene and argon ions are ionized and reacted in the plasma atmosphere to form a diamond-like structure, which gives the film layer the basic characteristics of high hardness and good chemical stability, and the addition of silane coupling agents, through chemical bonding or physical mixing, ingeniously changes the surface energy and microstructure of the film layer. Due to the regulating effect of the silane coupling agent on the surface energy, the hydrophobicity of the film layer is significantly improved, and the contact angle is increased, so that the glass surface is not easily infiltrated and adhered by water stains, oil stains, etc., and the cleanliness and transparency of the glass are maintained. Second, maintain high transparency: because the entire deposition process is carried out under precisely controlled pressure, temperature and time conditions, a uniform and dense film layer can be formed. This uniformity and density further ensures that the transparency of the film layer is not affected, and visible light can pass through smoothly, so that the optical properties of the glass can be maintained, and no obvious haze or light scattering will be generated due to the presence of the protective film, which expands the application potential of glass in optical instruments and other fields that have strict requirements on transparency. Third, environmental friendliness: the present invention avoids the use of fluorine-containing compounds as hydrophobic group introduction agents, thereby reducing potential pollution to the environment, and meets the requirements of green manufacturing and sustainable development. By selecting more environmentally friendly materials and optimizing the process flow, the film layer prepared by the present invention not only improves the performance of the glass, but also enhances the green attributes of the product, which is beneficial to the application in the fields of environmental protection and food safety.

[0016] In addition to the above-described objects, features and advantages, the present invention has other objects, features and advantages. The present invention will be further described in detail with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the accompanying drawings:

[0018] Figure 1 A schematic structural diagram of an embodiment of glass according to the present invention is shown.

[0019] The above drawings include the following reference numerals:

[0020] 10. Glass substrate; 20. Diamond-like carbon protective film. DETAILED DESCRIPTION

[0021] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0022] In order to enable those skilled in the art to better understand the scheme of the present invention, the technical scheme in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0023] It should be noted that the terms "first", "second", etc. in the specification and claims of the present invention and the above-mentioned drawings are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. It should be understood that the terms used in this way can be interchanged where appropriate, so as to describe the embodiments of the present invention described herein. In addition, the terms "including" and "having" and any variations thereof are intended to cover non-exclusive inclusions, for example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to those steps or units that are clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0024] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present application. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, it indicates the presence of features, steps, operations, devices, components and / or combinations thereof.

[0025] One aspect of the present application provides a preparation method for preparing a diamond-like protective film on a glass surface, comprising: introducing a mixed gas of silane, acetylene and argon with a flow ratio of 10:5:1-20:10:1 into a reaction chamber; adjusting the pressure in the reaction chamber to 0.1-10Pa; setting the power of the pulsed ionization power supply to 100-2000W; setting the plasma auxiliary voltage to 10-1000V; and depositing a diamond-like protective film having Si-H functional groups on the glass surface under the conditions of a deposition temperature of 50-200°C and a deposition time of 10-120min.

[0026] Applying the technical solution of the present application, the preparation of a diamond-like protective film on the glass surface has at least the following three advantages: First, the hydrophobicity is significantly enhanced: a specific ratio of argon and acetylene is used as the reaction gas, and silane coupling is introduced. From the analysis of chemical principles and material properties, this formula and process can accurately control the structure and composition of the film layer at the molecular level. Acetylene and argon ions are ionized and reacted in the plasma atmosphere to form a diamond-like structure, which gives the film layer the basic characteristics of high hardness and good chemical stability, and the addition of silane coupling agents, through chemical bonding or physical mixing, ingeniously changes the surface energy and microstructure of the film layer. Due to the regulating effect of the silane coupling agent on the surface energy, the hydrophobicity of the film layer is significantly improved, and the contact angle is increased, so that the glass surface is not easily infiltrated and adhered by water stains, oil stains, etc., and the cleanliness and transparency of the glass are maintained. Second, maintain high transparency: because the entire deposition process is carried out under precisely controlled pressure, temperature and time conditions, a uniform and dense film layer can be formed. This uniformity and density further ensures that the transparency of the film layer is not affected, and visible light can pass through smoothly, so that the optical properties of the glass can be maintained, and no obvious haze or light scattering will be generated due to the presence of the protective film, which expands the application potential of glass in optical instruments and other fields that have strict requirements on transparency. Third, environmental friendliness: the present invention avoids the use of fluorine-containing compounds as hydrophobic group introduction agents, thereby reducing potential pollution to the environment, and meets the requirements of green manufacturing and sustainable development. By selecting more environmentally friendly materials and optimizing the process flow, the film layer prepared by the present invention not only improves the performance of the glass, but also enhances the green attributes of the product, which is beneficial to the application in the fields of environmental protection and food safety.

[0027] It should be noted that the use of silane gas combined with appropriate deposition process parameters can successfully introduce Si-H functional groups into the middle of the diamond-like coating, reduce the surface energy and improve the hydrophobicity.

[0028] Further, the silane is one of monosilane, hexamethylsilane, dimethylsilane and monomethylsilane. Specifically, the preferred order of the use of silane is hexamethylsilane>dimethylsilane>monomethylsilane>monosilane, wherein monosilane has the highest silicon content and the smallest molecule, hexamethylsilane has the smallest silicon content but the largest molecular weight, monosilane is easy to provide Si, but H is easily ionized, and Si-H functional groups cannot be effectively introduced, and hydrophobicity is poor, while those with large molecular weight retain more Si-H and have good hydrophobicity.

[0029] Furthermore, before the mixed gas is introduced into the reaction chamber, the preparation method further comprises: pre-treating the glass to remove impurities.

[0030] Furthermore, the step of pre-treating the glass includes: selecting a glass substrate; ultrasonically cleaning the glass substrate with deionized water, acetone, and ethanol in sequence, with each cleaning time being 15-30 minutes to remove impurities on the glass surface; blowing dry with high-purity nitrogen; and keeping warm for a preset time. First, in the pre-treatment stage of the glass substrate, oil, dust and other impurities on the glass surface can be effectively removed through ultrasonic cleaning with acetone, ethanol and deionized water and subsequent drying treatment. The pure glass surface provides a uniform and interference-free foundation for subsequent film formation, which is conducive to the formation of a high-quality protective film, thereby ensuring the integrity and stability of the film layer, and indirectly improving the consistency and reliability of the overall performance of the protective film.

[0031] Furthermore, after the glass substrate is pretreated and before the mixed gas is introduced into the reaction chamber, the preparation method further includes: ion cleaning the glass substrate. Ion cleaning is a surface treatment technology that uses ion bombardment or active particles to act on the surface of the material to remove surface pollutants, oxides, organic residues and other impurities. Its main effects include: 1. Surface cleaning: Ion cleaning can effectively remove pollutants such as particles, grease, dust and other pollutants on the surface of the material, providing a clean substrate for subsequent deposition, coating, bonding and other processes. This is because the ion beam can penetrate the tiny pores on the surface and remove impurities attached to these difficult-to-reach areas, thereby achieving a more thorough cleaning effect. 2. Surface activation: During the ion cleaning process, high-energy ions or plasma can break the chemical bonds of the molecules on the surface of the material, generating a large number of free radicals and active groups, which makes the surface more "activated". The activated surface is easier to participate in subsequent chemical reactions, such as chemical bonding with the deposited material, thereby enhancing the adhesion between the new material layer and the substrate and improving the stability of the film layer. 3. Changes in surface microstructure: Ion beam bombardment can also change the microstructure of the material surface, such as removing the surface oxide layer, changing the surface roughness, etc. For some applications that require a specific surface state, such as photolithography in semiconductor manufacturing, pretreatment before thin film deposition, etc., ion cleaning can accurately control the surface state to ensure the smooth progress of subsequent processes. 4. Improve wettability and adhesion: The surface activation effect of ion cleaning can improve the wettability of the material surface and reduce the contact angle of the liquid on the surface, or conversely, in applications that require enhanced hydrophobicity, the target surface performance can be achieved by controlling the cleaning conditions. In addition, the activated surface can enhance the adhesion with subsequent added materials, which is crucial to improving the fit and service life of coatings, films, etc.

[0032] Furthermore, the step of ion cleaning the glass substrate includes: placing the pretreated glass substrate on a sample stage of a reaction chamber of a coating deposition device; evacuating the reaction chamber to a vacuum of 1.0×10 -3pa, when heated to 50℃~100℃, the surface of the glass substrate is ion cleaned with argon gas by hot wire arc discharge plasma etching process, the etching bias is ≤100V, and the ionization power is 1000W to remove surface impurities. This deep cleaning method can effectively improve the bonding strength between the film layer and the substrate, reduce defects in the film layer, and is suitable for industrial applications requiring high reliability and long life. The above steps are specifically the plasma activation link, in which argon gas is introduced and processed at a specific power and time. Because the plasma produces active groups on the glass surface, the presence of active groups is like an "anchor point", which greatly enhances the adhesion of the subsequent diamond-like film to the glass surface. This enhanced adhesion makes the protective film not easy to fall off or peel off during the use of the glass. Whether it is facing daily slight friction, vibration or temperature changes, it can fit the glass tightly, so that the glass is blessed with the performance of the protective film for a long time, such as continuous scratch resistance and anti-pollution, thereby extending the effective protection time of the glass and improving the service life and performance stability of the glass.

[0033] Another aspect of the present application provides a diamond-like protective film obtained by the above preparation method, wherein the diamond-like protective film contains Si-H functional groups. This film layer not only has excellent mechanical properties, but also can maintain good hydrophobicity and light transmittance.

[0034] Furthermore, the thickness of the diamond-like carbon protective film is within 500nm. By controlling the thickness of the film layer, the impact on the transparency of the glass can be reduced while ensuring the protective effect, which is suitable for occasions with strict requirements on light transmittance.

[0035] Another aspect of the present application provides a glass, comprising: a glass substrate; a diamond-like protective film, disposed on the surface of the glass substrate, the diamond-like protective film being the above-mentioned diamond-like protective film. The glass not only has high hardness and wear resistance, but also maintains good light transmittance, chemical stability and hydrophobicity.

[0036] The following is a detailed description of the specific method for preparing the diamond-like protective film of the present application:

[0037] Selecting a glass substrate;

[0038] Deionized water, acetone, and ethanol were used to ultrasonically clean the glass substrate in sequence, and each cleaning time was 15

[0039] –30min to remove impurities on the glass surface;

[0040] Blow dry with high-purity nitrogen;

[0041] Preset insulation time;

[0042] Placing the pretreated glass substrate on a sample stage of a reaction chamber of a coating deposition device;

[0043] The reaction chamber was vacuumed to 1.0×10 -3 pa, when heated to 50° C. to 100° C., ion cleaning is performed on the surface of the glass substrate using argon gas by a hot wire arc discharge plasma etching process, with an etching bias voltage of ≤100V and an ionization power of 1000W to remove surface impurities;

[0044] A mixed gas of silane, acetylene and argon with a flow ratio of 10:5:1-20:10:1 is introduced into the reaction chamber;

[0045] Adjust the pressure in the reaction chamber to 0.1-10Pa;

[0046] Set the pulse ionization power supply to 100-2000W;

[0047] Set the plasma auxiliary voltage to 10-1000V;

[0048] A diamond-like protective film having Si-H functional groups is deposited on the glass surface under the conditions of a deposition temperature of 50-200° C. and a deposition time of 10-120 min.

[0049] In this application, the specific implementation details of the method for preparing the diamond-like carbon protective film are elaborated in detail to prove the feasibility and superiority of the technical solution. Below, the preparation method of this protective film will be deeply analyzed and expanded according to the above parameter range to provide more examples and show the changes in the structure and performance of the protective film under different conditions.

[0050] Example 1

[0051] In this embodiment, the coating preparation method follows the following steps:

[0052] Selecting a glass substrate;

[0053] The glass substrate is ultrasonically cleaned with deionized water, acetone, and ethanol in sequence, with each cleaning time being 20 minutes, to remove impurities on the glass surface;

[0054] Blow dry with high-purity nitrogen;

[0055] Preset insulation time;

[0056] Placing the pretreated glass substrate on a sample stage of a reaction chamber of a coating deposition device;

[0057] The reaction chamber was vacuumed to 1.0×10 -3 pa, when heated to 80° C., ion cleaning is performed on the surface of the glass substrate using argon gas by a hot wire arc discharge plasma etching process, with an etching bias voltage of ≤100V and an ionization power of 1000W to remove surface impurities;

[0058] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 10:5:1 is introduced into the reaction chamber;

[0059] Adjust the pressure in the reaction chamber to 0.1 Pa;

[0060] Set the pulse ionization power supply to 100W;

[0061] Set the plasma auxiliary voltage to 100V;

[0062] Under the conditions of deposition temperature of 100°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0063] The prepared transparent hydrophobic diamond-like protective film was tested for water contact angle by an optical contact angle meter, and for visible light transmittance by a spectrophotometer. According to the test, the water contact angle of the diamond-like protective film of this embodiment was 95°, and the transmittance in the visible light range was 89%.

[0064] It should be noted that the experimental parameters of the glass pretreatment and ion cleaning steps in the subsequent examples remain unchanged. In order to illustrate the differences between the examples, only the steps after ion cleaning are listed.

[0065] Example 2

[0066] In this example, after ion cleaning, the coating preparation method follows the following steps:

[0067] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 10:5:1 is introduced into the reaction chamber;

[0068] Adjust the pressure in the reaction chamber to 0.1 Pa;

[0069] Set the pulse ionization power supply to 1000W;

[0070] Set the plasma auxiliary voltage to 500V;

[0071] Under the conditions of deposition temperature of 100°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0072] After testing, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 99°, and the transmittance in the visible light range is 89%.

[0073] Example 3

[0074] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0075] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 10:5:1 is introduced into the reaction chamber;

[0076] Adjust the pressure in the reaction chamber to 0.1 Pa;

[0077] Set the pulse ionization power supply to 2000W;

[0078] Set the plasma auxiliary voltage to 1000V;

[0079] Under the conditions of deposition temperature of 100°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0080] After testing, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 97°, and the transmittance in the visible light range is 89%.

[0081] Example 4

[0082] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0083] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 20:10:1 is introduced into the reaction chamber;

[0084] Adjust the pressure in the reaction chamber to 10 Pa;

[0085] Set the pulse ionization power supply to 100W;

[0086] Set the plasma auxiliary voltage to 100V;

[0087] Under the conditions of deposition temperature of 100°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0088] After testing, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 96°, and the transmittance in the visible light range is 90%.

[0089] Example 5

[0090] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0091] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 20:10:1 is introduced into the reaction chamber;

[0092] Adjust the pressure in the reaction chamber to 10 Pa;

[0093] Set the pulse ionization power supply to 1000W;

[0094] Set the plasma auxiliary voltage to 500V;

[0095] Under the conditions of deposition temperature of 100°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0096] According to the test, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 100°, and the light transmittance in the visible light range is 90%.

[0097] Example 6

[0098] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0099] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 20:10:1 is introduced into the reaction chamber;

[0100] Adjust the pressure in the reaction chamber to 10 Pa;

[0101] Set the pulse ionization power supply to 2000W;

[0102] Set the plasma auxiliary voltage to 1000V;

[0103] Under the conditions of deposition temperature of 100°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0104] After testing, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 99°, and the transmittance in the visible light range is 90%.

[0105] Example 7

[0106] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0107] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 10:10:1 was introduced into the reaction chamber;

[0108] Adjust the pressure in the reaction chamber to 1 Pa;

[0109] Set the pulse ionization power supply to 100W;

[0110] Set the plasma auxiliary voltage to 100V;

[0111] Under the conditions of deposition temperature of 100°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0112] After testing, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 96°, and the transmittance in the visible light range is 90%.

[0113] Example 8

[0114] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0115] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 10:10:1 was introduced into the reaction chamber;

[0116] Adjust the pressure in the reaction chamber to 1 Pa;

[0117] Set the pulse ionization power supply to 1000W;

[0118] Set the plasma auxiliary voltage to 500V;

[0119] Under the conditions of deposition temperature of 100°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0120] After testing, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 102°, and the transmittance in the visible light range is 91%.

[0121] Example 9

[0122] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0123] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 10:10:1 was introduced into the reaction chamber;

[0124] Adjust the pressure in the reaction chamber to 1 Pa;

[0125] Set the pulse ionization power supply to 2000W;

[0126] Set the plasma auxiliary voltage to 1000V;

[0127] Under the conditions of deposition temperature of 100°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0128] After testing, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 98°, and the transmittance in the visible light range is 90%.

[0129] Example 10

[0130] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0131] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 10:10:1 was introduced into the reaction chamber;

[0132] Adjust the pressure in the reaction chamber to 1 Pa;

[0133] Set the pulse ionization power supply to 1000W;

[0134] Set the plasma auxiliary voltage to 500V;

[0135] Under the conditions of deposition temperature of 100° C. and deposition time of 60 min, a diamond-like carbon protective film having Si—H functional groups is deposited on the glass surface.

[0136] According to the test, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 100°, and the light transmittance in the visible light range is 91%.

[0137] Embodiment 11

[0138] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0139] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 10:10:1 was introduced into the reaction chamber;

[0140] Adjust the pressure in the reaction chamber to 1 Pa;

[0141] Set the pulse ionization power supply to 1000W;

[0142] Set the plasma auxiliary voltage to 500V;

[0143] Under the conditions of deposition temperature of 100°C and deposition time of 10 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0144] After testing, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 94°, and the transmittance in the visible light range is 92%.

[0145] Example 12

[0146] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0147] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 10:10:1 was introduced into the reaction chamber;

[0148] Adjust the pressure in the reaction chamber to 1 Pa;

[0149] Set the pulse ionization power supply to 2000W;

[0150] Set the plasma auxiliary voltage to 1000V;

[0151] Under the conditions of deposition temperature of 50°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups was deposited on the glass surface.

[0152] After testing, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 93°, and the transmittance in the visible light range is 89%.

[0153] Embodiment 13

[0154] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0155] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 10:10:1 was introduced into the reaction chamber;

[0156] Adjust the pressure in the reaction chamber to 1 Pa;

[0157] Set the pulse ionization power supply to 2000W;

[0158] Set the plasma auxiliary voltage to 1000V;

[0159] Under the conditions of deposition temperature of 150° C. and deposition time of 120 min, a diamond-like carbon protective film having Si—H functional groups is deposited on the glass surface.

[0160] According to the test, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 98°, and the light transmittance in the visible light range is 90%.

[0161] Embodiment 14

[0162] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0163] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 10:10:1 was introduced into the reaction chamber;

[0164] Adjust the pressure in the reaction chamber to 1 Pa;

[0165] Set the pulse ionization power supply to 2000W;

[0166] Set the plasma auxiliary voltage to 1000V;

[0167] Under the conditions of deposition temperature of 200°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0168] After testing, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 96°, and the transmittance in the visible light range is 90%.

[0169] Embodiment 15

[0170] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0171] A mixed gas of dimethylsilane, acetylene and argon with a flow ratio of 10:10:1 was introduced into the reaction chamber;

[0172] Adjust the pressure in the reaction chamber to 1 Pa;

[0173] Set the pulse ionization power supply to 2000W;

[0174] Set the plasma auxiliary voltage to 1000V;

[0175] Under the conditions of deposition temperature of 200°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0176] After testing, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 95°, and the transmittance in the visible light range is 91%.

[0177] Example 16

[0178] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0179] A mixed gas of monomethylsilane, acetylene and argon with a flow ratio of 10:10:1 was introduced into the reaction chamber;

[0180] Adjust the pressure in the reaction chamber to 1 Pa;

[0181] Set the pulse ionization power supply to 2000W;

[0182] Set the plasma auxiliary voltage to 1000V;

[0183] Under the conditions of deposition temperature of 200°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0184] After testing, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 93°, and the transmittance in the visible light range is 91%.

[0185] Embodiment 17

[0186] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0187] A mixed gas of monosilane, acetylene and argon with a flow ratio of 10:10:1 was introduced into the reaction chamber;

[0188] Adjust the pressure in the reaction chamber to 1 Pa;

[0189] Set the pulse ionization power supply to 2000W;

[0190] Set the plasma auxiliary voltage to 1000V;

[0191] Under the conditions of deposition temperature of 200°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0192] After testing, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 92°, and the transmittance in the visible light range is 88%.

[0193] In summary, the water contact angle of the protective film prepared by the preparation method of this embodiment is ≥93°, the hardness is significantly improved compared with the untreated glass, and the light transmittance is maintained at more than 88% in the visible light range.

[0194] Comparative Example 1

[0195] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0196] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 5:5:1 is introduced into the reaction chamber;

[0197] Adjust the pressure in the reaction chamber to 0.08 Pa;

[0198] Set the pulse ionization power supply to 100W;

[0199] Set the plasma auxiliary voltage to 100V;

[0200] Under the conditions of deposition temperature of 100°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0201] After testing, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 40°, and the transmittance in the visible light range is 92%.

[0202] Comparative Example 2

[0203] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0204] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 20:20:1 was introduced into the reaction chamber;

[0205] Adjust the pressure in the reaction chamber to 12 Pa;

[0206] Set the pulse ionization power supply to 2000W;

[0207] Set the plasma auxiliary voltage to 1000V;

[0208] Under the conditions of deposition temperature of 100°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0209] According to the test, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 80°, and the light transmittance in the visible light range is 70%.

[0210] Comparative Example 3

[0211] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0212] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 10:10:1 was introduced into the reaction chamber;

[0213] Adjust the pressure in the reaction chamber to 1 Pa;

[0214] Set the pulse ionization power supply to 3000W;

[0215] Set the plasma auxiliary voltage to 1000V;

[0216] Under the conditions of deposition temperature of 100°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0217] After testing, the prepared transparent hydrophobic diamond-like carbon protective film has a water contact angle of 70° and a light transmittance of 75% in the visible light range.

[0218] Comparative Example 4

[0219] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0220] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 10:10:1 was introduced into the reaction chamber;

[0221] Adjust the pressure in the reaction chamber to 1 Pa;

[0222] Set the pulse ionization power supply to 2000W;

[0223] Set the plasma auxiliary voltage to 1200V;

[0224] Under the conditions of deposition temperature of 100°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0225] After testing, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 85°, and the transmittance in the visible light range is 76%.

[0226] Comparative Example 5

[0227] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0228] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 10:10:1 was introduced into the reaction chamber;

[0229] Adjust the pressure in the reaction chamber to 1 Pa;

[0230] Set the pulse ionization power supply to 2000W;

[0231] Set the plasma auxiliary voltage to 1000V;

[0232] Under the conditions of deposition temperature of 100°C and deposition time of 150 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0233] According to the test, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 95°, and the light transmittance in the visible light range is 85%.

[0234] Comparative Example 6

[0235] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0236] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 10:10:1 was introduced into the reaction chamber;

[0237] Adjust the pressure in the reaction chamber to 1 Pa;

[0238] Set the pulse ionization power supply to 2000W;

[0239] Set the plasma auxiliary voltage to 1000V;

[0240] Under the conditions of deposition temperature of 100° C. and deposition time of 5 min, a diamond-like carbon protective film having Si—H functional groups is deposited on the glass surface.

[0241] After testing, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 85°, and the transmittance in the visible light range is 92%.

[0242] Comparative Example 7

[0243] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0244] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 10:10:1 was introduced into the reaction chamber;

[0245] Adjust the pressure in the reaction chamber to 1 Pa;

[0246] Set the pulse ionization power supply to 2000W;

[0247] Set the plasma auxiliary voltage to 1000V;

[0248] Under the conditions of deposition temperature of 40°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0249] After testing, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 85°, and the transmittance in the visible light range is 88%.

[0250] Comparative Example 8

[0251] In this embodiment, after ion cleaning, the method for preparing the protective film follows the following steps:

[0252] A mixed gas of hexamethylsilane, acetylene and argon with a flow ratio of 10:10:1 was introduced into the reaction chamber;

[0253] Adjust the pressure in the reaction chamber to 1 Pa;

[0254] Set the pulse ionization power supply to 2000W;

[0255] Set the plasma auxiliary voltage to 1000V;

[0256] Under the conditions of deposition temperature of 250°C and deposition time of 120 min, a diamond-like carbon protective film having Si-H functional groups is deposited on the glass surface.

[0257] After testing, the water contact angle of the prepared transparent hydrophobic diamond-like carbon protective film is 88°, and the transmittance in the visible light range is 85%.

[0258] In addition, the present application also provides a diamond-like protective film, which is obtained by the above-mentioned preparation method. According to an embodiment of the diamond-like protective film of the present application, the diamond-like protective film contains Si—H functional groups.

[0259] Furthermore, the thickness of the diamond-like carbon protective film is within 500 nm. The above structure can ensure that the light transmittance of the diamond-like carbon protective film is not affected.

[0260] Finally, if Figure 1 As shown, the present application also provides a glass, and the glass according to the embodiment of the present application includes a glass substrate 10 and a diamond-like protective film 20. The diamond-like protective film 20 is disposed on the surface of the glass substrate 10, and the diamond-like protective film 20 is the above-mentioned diamond-like protective film. Since the above-mentioned diamond-like protective film has the advantages of good hydrophobicity, good light transmittance, and wear resistance, the glass having the same also has the above-mentioned advantages.

[0261] Unless otherwise specifically stated, the relative arrangement of the parts and steps described in these embodiments, numerical expressions and numerical values ​​do not limit the scope of the present invention. At the same time, it should be understood that, for ease of description, the sizes of the various parts shown in the accompanying drawings are not drawn according to the actual proportional relationship. The technology, method and equipment known to ordinary technicians in the relevant field may not be discussed in detail, but in appropriate cases, the technology, method and equipment should be regarded as a part of the authorization specification. In all examples shown and discussed here, any specific value should be interpreted as being merely exemplary, rather than as a limitation. Therefore, other examples of exemplary embodiments may have different values. It should be noted that similar reference numerals and letters represent similar items in the following drawings, so once a certain item is defined in an accompanying drawing, it does not need to be further discussed in subsequent drawings.

[0262] For ease of description, spatially relative terms such as "above", "above", "on the upper surface of", "above", etc. may be used here to describe the spatial positional relationship between a device or feature and other devices or features as shown in the figure. It should be understood that spatially relative terms are intended to include different orientations of the device in use or operation in addition to the orientation described in the figure. For example, if the device in the accompanying drawings is inverted, the device described as "above other devices or structures" or "above other devices or structures" will be positioned as "below other devices or structures" or "below other devices or structures". Thus, the exemplary term "above" can include both "above" and "below". The device can also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatially relative descriptions used here are interpreted accordingly.

[0263] In the description of the present invention, it is necessary to understand that the directions or positional relationships indicated by directional words such as "front, back, up, down, left, right", "lateral, vertical, perpendicular, horizontal" and "top, bottom" are usually based on the directions or positional relationships shown in the drawings. They are only for the convenience of describing the present invention and simplifying the description. Unless otherwise specified, these directional words do not indicate or imply that the devices or elements referred to must have a specific direction or be constructed and operated in a specific direction. Therefore, they cannot be understood as limiting the scope of protection of the present invention. The directional words "inside and outside" refer to the inside and outside relative to the contours of each component itself.

[0264] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a diamond-like protective film on a glass surface, characterized in that: include: A mixed gas of silane, acetylene and argon with a flow ratio of 10:5:1-20:10:1 is introduced into the reaction chamber; Adjust the pressure in the reaction chamber to 0.1-10Pa; Set the pulse ionization power supply to 100-2000W; Set the plasma auxiliary voltage to 10-1000V; A diamond-like protective film having Si-H functional groups is deposited on the glass surface under the conditions of a deposition temperature of 50-200° C. and a deposition time of 10-120 min.

2. The preparation method according to claim 1, characterized in that: The silane is one of monosilane, hexamethylsilane, dimethylsilane and monomethylsilane.

3. The preparation method according to claim 1, characterized in that: Before introducing the mixed gas into the reaction chamber, the preparation method further comprises: The glass is pre-treated to remove impurities.

4. The preparation method according to claim 3, characterized in that: The step of pre-treating the glass comprises: Selecting a glass substrate; The glass substrate is ultrasonically cleaned with deionized water, acetone, and ethanol in sequence, with each cleaning time being 15-30 minutes to remove impurities on the glass surface; Blow dry with high-purity nitrogen; Preset keep warm time.

5. The preparation method according to claim 3, characterized in that: After pre-treating the glass and before introducing the mixed gas into the reaction chamber, the preparation method further includes: The glass substrate is ion cleaned.

6. The preparation method according to claim 5, characterized in that: The step of ion cleaning the glass substrate comprises: Placing the pretreated glass substrate on a sample stage of a reaction chamber of a coating deposition device; The reaction chamber was vacuumed to 1.0×10 -3 pa, when heated to 50°C to 100°C, the surface of the glass substrate is ion cleaned with argon gas using a hot wire arc discharge plasma etching process, with an etching bias voltage of ≤100V and an ionization power of 1000W to remove surface impurities.

7. A diamond-like protective film, characterized in that: The diamond-like carbon protective film is obtained by the preparation method according to any one of claims 1 to 6, wherein the diamond-like carbon protective film contains Si-H functional groups.

8. The diamond-like carbon protective film according to claim 7, characterized in that: The thickness of the diamond-like carbon protective film is within 500 nm.

9. A glass comprising: A glass substrate (10); A diamond-like protective film (20) is arranged on the surface of the glass substrate (10), characterized in that the diamond-like protective film (20) is the diamond-like protective film according to claim 7 or 8.

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