Preparation method of high-durability transparent hydrophobic glass

Abstract

The invention discloses a preparation method of high-durability transparent hydrophobic glass, and aims to solve the problems that when the roughness of a super-hydrophobic coating is greater than 100nm, the transparency of the super-hydrophobic coating is poor, and the stability of the super-hydrophobic coating is poor. The preparation method comprises the following steps: 1, spin-coating photoresist on the surface of a pretreated glass substrate; 2, carrying out photoetching exposure treatment on the glass substrate coated with the photoresist; 3, rotary spraying of a developing solution; 4, hardening the glass substrate; 5, performing ion etching on the surface of the glass substrate to form a micropore array structure; 6, ultrasonic water washing; and 7, evaporating a PDMS film on the surface of the glass substrate by adopting an electron beam evaporation coating process. According to the preparation method, a micron-sized microporous structure is etched by adopting a reactive ion etching technology, and a uniform and compact film layer is prepared by adopting an electron beam evaporation coating technology, so that the friction resistance of the hydrophobic film layer is remarkably improved. The surface contact angle of the transparent super-hydrophobic glass is larger than 140 degrees, and the visible light transmittance of 300-800 nm is larger than 89%.

Description

Technical Field

[0001] The invention belongs to the technical field of transparent hydrophobic material preparation, and particularly relates to a method for preparing highly durable transparent hydrophobic glass. Background Art

[0002] The static contact angle of the super-hydrophobic surface is greater than 150° and the rolling angle is less than 10°. It has excellent hydrophobic and self-cleaning properties and is widely used in scenarios such as corrosion protection, pollution prevention, anti-icing, anti-oxidation, anti-fogging, and moisture prevention. When the super-hydrophobic surface is applied to the glass curtain wall of a building, when raindrops fall on the glass, they can carry away the surface dust, giving the glass a self-cleaning function, reducing the cost of manual cleaning and keeping the building facade clean and tidy. Applying the super-hydrophobic surface to solar panels can effectively prevent dust adhesion and improve power generation efficiency. Applying the super-hydrophobic surface to the windshield of a car can effectively reduce the interference of rainwater on the driver.

[0003] Transparent substrates such as sapphire, glass, organic glass (PMMA), polyvinyl chloride (PVC), polyethylene terephthalate (PET) and other materials have high transmittance, high strength and high chemical stability, and are widely used in optical windows. However, they are easily contaminated during use, which affects optical transmittance. Combining high transmittance and superhydrophobicity can make optical windows have both high transmittance and excellent hydrophobic properties, which has broad application prospects. For example, applying superhydrophobic surfaces to cameras in mines or tunnels can reduce dust accumulation on optical lenses, avoid the impact of pollution on lens imaging, and reduce maintenance costs. Applying superhydrophobic surfaces to optical windows of marine vessels can resist seawater corrosion and reduce the attachment of marine organisms, thereby increasing service life.

[0004] Super-hydrophobic surfaces have micro-nano structures and low surface energy components. When liquid contacts the material surface, the low surface energy components reduce the intrinsic contact angle, and the rough structure captures the air layer to reduce the contact area, effectively improving the wetting performance of the optical window. However, a major bottleneck limiting the development of super-hydrophobic coatings on optical windows is the incompatibility between the roughness of the structure and the transparency of the surface: when the roughness of the super-hydrophobic coating is greater than 100nm, the hydrophobicity is effectively improved, but the wavelength of visible light is 380-780nm, and light scattering is prone to occur under this roughness range, and it is impossible to meet the requirements of transparency. In addition, traditional super-hydrophobic coatings mostly use organic coating technologies such as fluorosilane, mainly prepared by spraying, dipping, sol-gel, laminating, laser etching, etc. When the material is exposed to a high pressure, corrosive environment, it is prone to wear and degradation, the micro-nano structure fails, and the stability is poor. Super-hydrophobicity is mainly determined by the micro-nano structure and chemical composition of the material surface, and the improvement of hydrophobicity depends on the precise control of the microstructure. However, simply increasing the roughness in a disordered manner cannot guarantee a significant improvement in hydrophobicity. Therefore, it is necessary to prepare a highly durable transparent hydrophobic glass by designing a specific surface roughness morphology and optimizing the micro-geometric features to enhance the hydrophobicity, and at the same time using evaporation coating technology to improve the friction resistance of the film layer. Summary of the Invention

[0005] The purpose of the present invention is to solve the technical problems of poor transparency and poor stability of the super-hydrophobic coating when the roughness of the super-hydrophobic coating is greater than 100 nm, and to provide a method for preparing a highly durable transparent hydrophobic glass.

[0006] The preparation method of the highly durable transparent hydrophobic glass of the present invention is achieved by the following steps:

[0007] 1. Cleaning and baking the glass substrate in sequence, and then pre-treating the surface with a tackifier (HMDS) to obtain a pre-treated glass substrate, and then spin-coating a photoresist on the surface of the pre-treated glass substrate to obtain a glass substrate coated with the photoresist;

[0008] 2. performing a photolithographic exposure process on the glass substrate coated with the photoresist according to the microhole array structure to obtain a photolithographic glass substrate;

[0009] 3. Spinning a developer onto the surface of the photolithographic glass substrate to dissolve the photoresist in the exposed portion, thereby obtaining a developed glass substrate;

[0010] 4. Heating the developed glass substrate to 100-110° C. and baking the substrate to obtain a hardened glass substrate;

[0011] 5. Placing the hardened glass substrate into a chamber, evacuating the chamber, and introducing argon (Ar) and boron trichloride (BCl3) with the argon flow rate controlled at 8-15 sccm and the boron trichloride flow rate controlled at 40-50 sccm to perform ion etching to form a micropore array structure on the surface of the glass substrate. The micropores are circular holes with a diameter of 2-30 μm, a spacing of 5 μm between the edges of the holes, and a depth of 2 μm, thereby obtaining a glass substrate with a micropore array.

[0012] 6. ultrasonically washing the glass substrate with the micropore array and drying it to obtain a cleaned glass substrate;

[0013] 7. Using electron beam evaporation coating technology, a PDMS film (organic silicone polydimethylsiloxane film) is evaporated on the surface of the glass substrate cleaned in step 6 to obtain a highly durable transparent hydrophobic glass.

[0014] This invention aims to provide a method for preparing highly durable, transparent, hydrophobic glass, primarily for applications such as mine / tunnel / underwater cameras, cameras, glass curtain walls, solar panels, automotive windshields, and rearview mirrors. The method first designs a regular micron-scale array pattern on the glass surface based on the Wenzel and Cassie-Baxter equations. By varying the microstructure's dimensional parameters, the hydrophobic properties and optical transmittance are adjusted. Reactive ion etching (RIE) is then used to etch the micron-scale structure onto the glass surface. Electron beam evaporation (EBE) is then used to uniformly deposit a non-polar PMDS thin film onto the microstructure, creating a secondary micro-nanocomposite structure. EBE ensures that the film particles are evenly coated on the substrate surface, forming a uniform and dense film layer, significantly improving the friction resistance of the hydrophobic film. During the EBE process, high-energy ions impinge on the substrate surface, promoting the formation of strong physical and chemical bonds between the film and substrate, significantly enhancing adhesion.

[0015] The present invention prepares a transparent hydrophobic glass surface with a visible light transmittance of greater than 88% in the range of 300-800 nm and a hydrophobic angle greater than 140°. Under the action of a 100-g weight, a 5-cm push along a ruler in the horizontal direction is defined as one cycle. After 20 cycles, the surface hydrophobic angle is still greater than 130°.

[0016] The method for preparing the highly durable transparent hydrophobic glass of the present invention has the following beneficial effects:

[0017] ① Using the Wenzel and Cassie-Baxter equations, a regular micron-scale micropore array structure was designed. Reactive ion etching (RIE) was used to create the micron-scale micropore structure, achieving a high etching rate. Electron beam evaporation (EBE) was used to create a uniform and dense film layer, significantly improving the friction resistance of the hydrophobic film. The flexible and controllable fabrication process ensures both visible light transmittance and hydrophobic properties.

[0018] ② The prepared transparent hydrophobic surface has excellent self-cleaning properties, with a surface contact angle greater than 140°, making it difficult for water droplets to adhere, and can quickly roll off and carry away pollutants (such as dust and microorganisms).

[0019] ③ The prepared transparent hydrophobic surface has excellent visible light transmittance, with a visible light transmittance of more than 89% from 300 to 800 nm. It is suitable for scenarios such as optical lenses and solar panels that need to be kept clean for a long time.

[0020] ④ The prepared transparent hydrophobic surface has high wear resistance. Under the action of a 100g weight, pushing 5cm horizontally along the ruler is defined as one cycle. After 20 cycles, the surface hydrophobic angle is still greater than 130°, enhancing the surface's scratch resistance, solving the current pain point of transparent hydrophobic surfaces being non-wear-resistant, and significantly improving the service life of transparent hydrophobic surfaces. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a schematic diagram of a three-dimensional model of a regular microporous structure designed based on theoretical calculations and simulations in the present invention;

[0022] Figure 2 This is a scanning electron microscope image of a microwell array processed by reactive ion etching technology in the present invention;

[0023] Figure 3 This is the EDS (energy dispersive X-ray spectroscopy) composition analysis diagram of the PDMS hydrophobic film layer on the transparent hydrophobic glass surface prepared by the present invention;

[0024] Figure 4 (a) The transmittance of a transparent hydrophobic glass prepared in Example 1 in the 300-800 nm band and (b) the static contact angle test graph of a water droplet;

[0025] Figure 5 (a) The transmittance of a transparent hydrophobic glass prepared in Example 2 in the 300-800 nm wavelength range and (b) the static contact angle test graph of a water droplet;

[0026] Figure 6 (a) The transmittance of a transparent hydrophobic glass prepared in Example 3 in the visible light band of 300-800 nm and (b) the static contact angle test graph of a water droplet. DETAILED DESCRIPTION

[0027] Specific embodiment 1: The preparation method of the highly durable transparent hydrophobic glass of this embodiment is implemented according to the following steps:

[0028] 1. Cleaning and baking the glass substrate in sequence, and then pre-treating the surface with a tackifier (HMDS) to obtain a pre-treated glass substrate, and then spin-coating a photoresist on the surface of the pre-treated glass substrate to obtain a glass substrate coated with the photoresist;

[0029] 2. performing a photolithographic exposure process on the glass substrate coated with the photoresist according to the microhole array structure to obtain a photolithographic glass substrate;

[0030] 3. Spinning a developer onto the surface of the photolithographic glass substrate to dissolve the photoresist in the exposed portion, thereby obtaining a developed glass substrate;

[0031] 4. Heating the developed glass substrate to 100-110° C. and baking the substrate to obtain a hardened glass substrate;

[0032] 5. Placing the hardened glass substrate into a chamber, evacuating the chamber, and introducing argon (Ar) and boron trichloride (BCl3) with the argon flow rate controlled at 8-15 sccm and the boron trichloride flow rate controlled at 40-50 sccm to perform ion etching to form a micropore array structure on the surface of the glass substrate. The micropores are circular holes with a diameter of 2-30 μm, a spacing of 5 μm between the edges of the holes, and a depth of 2 μm, thereby obtaining a glass substrate with a micropore array.

[0033] 6. ultrasonically washing the glass substrate with the micropore array and drying it to obtain a cleaned glass substrate;

[0034] 7. Using electron beam evaporation coating technology, a PDMS film (organic silicone polydimethylsiloxane film) is evaporated on the surface of the glass substrate cleaned in step 6 to obtain a highly durable transparent hydrophobic glass.

[0035] Specific embodiment 2: This embodiment differs from specific embodiment 1 in that the glass substrate is cleaned using the RCA method in step 1. The cleaning process is as follows:

[0036] S1, SPM cleaning:

[0037] use The mixed solution is used to clean the glass substrate at a temperature of 120-150° C., and then rinsed with hot water to obtain an SPM-cleaned glass substrate;

[0038] S2, APM cleaning:

[0039] use The mixed solution is used to clean the glass substrate after SPM cleaning at a temperature of 75-85° C., and then rinsed with hot water to obtain the glass substrate after APM cleaning;

[0040] S3, HPM cleaning:

[0041] use The mixed solution is used to clean the glass substrate after APM cleaning at a temperature of 65-85° C. to obtain a glass substrate after HPM cleaning;

[0042] S4, DHF cleaning:

[0043] The glass substrate after HPM cleaning was cleaned using diluted hydrofluoric acid with a mass concentration of 5% at a temperature of 20-25°C;

[0044] S5. Rinse:

[0045] The glass substrate is rinsed with flowing deionized water (DIW) and then dried to complete the cleaning of the glass substrate.

[0046] Specific embodiment three: The difference between this embodiment and specific embodiment one or two is that in step one, the glass substrate is baked at 100° C. for 10 minutes.

[0047] Specific embodiment 4: This embodiment differs from any one of specific embodiments 1 to 3 in that in step 1, the adhesion promoter is coated on the surface of the glass substrate and cured at 120°C.

[0048] Specific embodiment 5: This embodiment differs from specific embodiments 1 to 4 in that the coating thickness of the photoresist in step 1 is 1-4 μm.

[0049] Specific embodiment 6: This embodiment differs from any one of specific embodiments 1 to 5 in that the baking treatment time in step 4 is 3 to 4 minutes.

[0050] Specific embodiment seven: This embodiment differs from specific embodiments one to five in that in step five, the flow rate of argon gas is controlled to be 10 sccm, the flow rate of boron trichloride is controlled to be 45 sccm for ion etching, and the microwave power is set to 100-500W.

[0051] Specific embodiment eight: The difference between this embodiment and any one of specific embodiments one to seven is that in step six, the glass substrate with the micropore array is cleaned seven times. The first and second cleanings are both ultrasonically cleaned in a cleaning tank with isopropyl alcohol for 5 minutes each, and the ultrasonic power is 900w; the third cleaning is rinsed with deionized water in a spray tank for 5 minutes; the fourth, fifth and sixth cleanings are all ultrasonically cleaned with deionized water for 5 minutes each, and the ultrasonic power is 900w; the seventh cleaning is cleaned in a slow pulling tank with deionized water for 5 minutes, and the pulling speed is 5mm / s.

[0052] Specific embodiment 9: This embodiment differs from any one of specific embodiments 1 to 8 in that the drying temperature in step 6 is 50°.

[0053] Specific embodiment ten: This embodiment differs from specific embodiments one to nine in that the thickness of the evaporated PDMS film in step seven is 6-20 nm.

[0054] Example 1: The preparation method of the highly durable transparent hydrophobic glass of this embodiment is carried out according to the following steps:

[0055] 1. The glass substrate is cleaned and baked (100°C) in sequence using the RCA method. The process of cleaning the glass substrate using the RCA method is as follows:

[0056] S1, SPM cleaning:

[0057] use Mixed solution ( The volume ratio of raw materials is 7:3. The mass percentage is 70%, The glass substrate was cleaned at 120°C for 10 minutes to remove heavy organic matter and some metals by strong oxidation, and then rinsed with 80°C hot water to obtain a glass substrate cleaned by SPM;

[0058] S2, APM cleaning:

[0059] use ( The volume ratio of the raw materials is 1:2:5. The mass percentage is 28%, The mass percentage of the mixed solution is 30%), the glass substrate after SPM cleaning is cleaned at 80°C for 10 minutes to remove particles, organic residues and complexed heavy metal impurities, and then rinsed with 80°C hot water to obtain a glass substrate after APM cleaning;

[0060] S3, HPM cleaning:

[0061] use ( The volume ratio is 1:2:50, and the mass percentage of HCl in the raw material is 8%. The mass percentage of the mixed solution is 2%), and the glass substrate after APM cleaning is cleaned at 70°C for 15 minutes to remove alkali metals (sodium, potassium) and metal ions such as iron and magnesium, thereby obtaining a glass substrate after HPM cleaning;

[0062] S4, DHF cleaning:

[0063] The glass substrates after HPM cleaning were cleaned with 5% diluted hydrofluoric acid at 25°C for 10 seconds to dissolve the surface oxide layer and remove metal hydroxides such as Al / Fe / Zn / Ni.

[0064] S5. Rinse:

[0065] Rinse the glass substrate with flowing deionized water (DIW) for 20 minutes and dry it with hot nitrogen to complete the cleaning of the glass substrate;

[0066] Then, the surface was pretreated with a tackifier (HMDS) for 10 minutes and heated to 120°C to obtain a pretreated glass substrate. Then, AZ4620 photoresist was spin-coated (1500 rpm) on the surface of the pretreated glass substrate to evenly spread the AZ4620 photoresist to obtain a glass substrate coated with photoresist. The thickness of the photoresist spin-coated was 1.5 μm.

[0067] Second, using a laser direct writing device and a single-point light source, the photolithography accuracy can reach 300nm, and the glass substrate coated with photoresist is photolithographically processed according to the micro-hole array structure to obtain a photolithographic glass substrate;

[0068] 3. Spin-spraying AZ400K developer onto the surface of the photolithographic glass substrate to dissolve the photoresist in the exposed portion, and then rinsing with ultrapure water for 20 minutes to remove the residual developer to obtain a developed glass substrate;

[0069] Fourth, the developed glass substrate is heated to 100° C. and baked for 3 minutes to further volatilize the residual solvent in the developed photoresist. The baking process makes the photoresist more closely bonded to the substrate surface, preventing the photoresist from falling off during the subsequent dry etching process, and obtaining a hardened glass substrate;

[0070] 5. Place the hardened glass substrate into the chamber and evacuate to 2×10 -4 Pa, introduce argon (Ar) and boron trichloride (BCl3), control the flow rate of argon to 10sccm, and the flow rate of boron trichloride to 45sccm for ion etching, and form a micropore array structure on the surface of the glass substrate. The micropores are circular holes with a diameter of 20μm, a distance between the edges of the circular holes is 5μm, and a depth of the circular holes is 2μm, thereby obtaining a glass substrate with a micropore array;

[0071] 6. The glass substrate with the micropore array was cleaned seven times. The first and second cleanings were both ultrasonically cleaned in a cleaning tank with isopropyl alcohol for 5 minutes each, with an ultrasonic power of 900W, to quickly remove large particles of impurities; the third cleaning was rinsed in a spray tank with deionized water for 5 minutes to further remove impurities with slightly stronger adhesion and residual cleaning agent on the surface; the fourth, fifth and sixth cleanings were all ultrasonically cleaned with deionized water for 5 minutes each, with an ultrasonic power of 900W to ensure that there were no residual impurities; the seventh cleaning was rinsed in a slow pulling tank with deionized water for 5 minutes, with a pulling speed of 5mm / s, and then dried at 50° for 5 minutes to obtain the cleaned glass substrate;

[0072] 7. Electron beam evaporation coating process was used to evaporate PDMS thin film on the glass substrate surface after cleaning in step 6. A mechanical pump and diffusion pump exhaust system was used to extract the gas in the vacuum chamber and reduce the chamber pressure to 1.2×10 -3 Pa starts heating. The PDMS evaporation source is heated to 100°C, the material vaporizes, the baffle is opened, and a PDMS film with a thickness of about 8.5 nm is formed on the surface of the substrate, resulting in a highly durable transparent hydrophobic glass.

[0073] The key factors in constructing a super-hydrophobic surface are low surface energy and micro-nanostructures. The constructed micro-nanostructure effectively reduces the solid-liquid contact area by storing air, thereby achieving super-hydrophobicity. However, when light enters the surface, the micro-nanostructure will introduce light scattering and multiple reflection interfaces. According to Mie scattering theory, when the size of the microstructure is close to the wavelength of visible light (380-780nm), Mie scattering resonance will occur, the scattering loss will be significantly enhanced, and the surface transparency will be reduced; according to Fresnel reflection, it can be seen that the multi-layer micro-nano interface causes the incident light to undergo multiple reflections, resulting in transmittance attenuation. Therefore, the micropore array in the glass substrate designed by the present invention has the advantages of high visible light transmittance, low scattering loss, significantly enhanced transparency, simple preparation process, and low cost compared to existing nanoscale array structures, such as nano-cone (column) array structures.

[0074] Furthermore, under the same external load conditions, the nanoscale microstructure's reduced effective load-bearing area leads to stress concentration. Its high specific surface area makes the interface susceptible to crack initiation under extreme conditions, ultimately causing structural failure. Therefore, compared to existing nanoscale conical-pillar array structures, the micropore array in the glass substrate designed by this invention connects the areas outside the micropore structure into a single integrated whole, resulting in high structural stability and friction resistance.

[0075] In addition, the low surface energy modification layer that imparts surface hydrophobicity is commonly used in Czochralski coating, and this Czochralski uniformity is poor, chemical stability is poor, and substrate adhesion is weak, very easy friction damage failure, drying process may produce bubbles or cracks, easy physical property degradation under extreme environment, cause surface loss of hydrophobicity, this is the main reason affecting the widespread use of super-hydrophobic materials. The present invention adopts electron beam evaporation coating process to deposit in a vacuum environment, and impurity gas is extremely low, and film purity is significantly higher than Czochralski coating, and film thickness is accurately controllable. Simultaneously, evaporation coating forms physical / chemical bonding with substrate during deposition, and adhesion is significantly enhanced.

[0076] The highly durable transparent hydrophobic glass obtained in this example has a transmittance greater than 89% in the 300-800 nm band and a static hydrophobic angle greater than 140°. Under the action of a 100 g weight, a horizontal pressure of 5 cm along a ruler is defined as one cycle. After 20 cycles, the surface hydrophobic angle is still greater than 130°.

[0077] Example 2: The difference between this example and Example 1 is that in step five, a micropore array structure is formed on the surface of the glass substrate. The micropores are circular holes with a diameter of 15 μm, a distance between the edges of the circular holes of 5 μm, and a depth of 2 μm.

[0078] The highly durable transparent hydrophobic glass obtained in this example has a transmittance greater than 89% in the 300-800 nm band and a static hydrophobic angle greater than 141°. Under the action of a 100 g weight, a horizontal pressure of 5 cm along a ruler is defined as one cycle. After 20 cycles, the surface hydrophobic angle is still greater than 130°.

[0079] Example 3: The difference between this example and Example 1 is that in step five, a micropore array structure is formed on the surface of the glass substrate. The micropores are circular holes with a diameter of 10 μm, a distance between the edges of the circular holes of 5 μm, and a depth of 2 μm.

[0080] The highly durable transparent hydrophobic glass obtained in this example has a transmittance greater than 89% in the 300-800 nm band and a static hydrophobic angle greater than 142°. Under the action of a 100 g weight, a horizontal pressure of 5 cm along a ruler is defined as one cycle. After 20 cycles, the surface hydrophobic angle is still greater than 130°.

Claims

1. A method for preparing highly durable transparent hydrophobic glass, characterized in that The preparation method of the highly durable transparent hydrophobic glass is achieved by the following steps:

1. Cleaning and baking the glass substrate in sequence, then pre-treating the surface with a tackifier to obtain a pre-treated glass substrate, and then spin-coating a photoresist on the surface of the pre-treated glass substrate to obtain a glass substrate coated with the photoresist; 2. performing a photolithographic exposure process on the glass substrate coated with the photoresist according to the microhole array structure to obtain a photolithographic glass substrate; 3. Spinning a developer onto the surface of the photolithographic glass substrate to dissolve the photoresist in the exposed portion, thereby obtaining a developed glass substrate; 4. Heating the developed glass substrate to 100-110° C. and baking the substrate to obtain a hardened glass substrate; 5. Placing the hardened glass substrate into a chamber, evacuating the chamber, introducing argon and boron trichloride, controlling the argon flow rate to 8-15 sccm and the boron trichloride flow rate to 40-50 sccm, and performing ion etching to form a micropore array structure on the surface of the glass substrate. The micropores are circular holes with a diameter of 2-30 μm, a spacing of 5 μm between the edges of the holes, and a depth of 2 μm, thereby obtaining a glass substrate with a micropore array; 6. ultrasonically washing the glass substrate with the micropore array and drying it to obtain a cleaned glass substrate; 7. Using electron beam evaporation coating technology, a PDMS film is evaporated on the surface of the glass substrate cleaned in step 6 to obtain a highly durable transparent hydrophobic glass.

2. The method for preparing the highly durable transparent hydrophobic glass according to claim 1, wherein In step 1, the glass substrate is cleaned using the RCA method. The cleaning process is as follows: S1, SPM cleaning: use The mixed solution is used to clean the glass substrate at a temperature of 120-150° C., and then rinsed with hot water to obtain an SPM-cleaned glass substrate; S2, APM cleaning: use The mixed solution is used to clean the glass substrate after SPM cleaning at a temperature of 75-85° C., and then rinsed with hot water to obtain the glass substrate after APM cleaning; S3, HPM cleaning: use The mixed solution is used to clean the glass substrate after APM cleaning at a temperature of 65-85° C. to obtain a glass substrate after HPM cleaning; S4, DHF cleaning: The glass substrate after HPM cleaning was cleaned using diluted hydrofluoric acid with a mass concentration of 5% at a temperature of 20-25°C; S5. Rinse: The glass substrate is rinsed with flowing deionized water and then dried to complete the cleaning of the glass substrate.

3. The method for preparing the highly durable transparent hydrophobic glass according to claim 1, wherein In step 1, the glass substrate is baked at 100° C. for 10 minutes.

4. The method for preparing the highly durable transparent hydrophobic glass according to claim 1, wherein In step 1, the adhesion promoter is coated on the surface of the glass substrate and cured at 120°C.

5. The method for preparing the highly durable transparent hydrophobic glass according to claim 1, wherein The coating thickness of the photoresist in step 1 is 1-4 μm.

6. The method for preparing the highly durable transparent hydrophobic glass according to claim 1, wherein The baking time in step 4 is 3 to 4 minutes.

7. The method for preparing the highly durable transparent hydrophobic glass according to claim 1, characterized in that In step 5, the flow rate of argon gas is controlled to be 10 sccm, the flow rate of boron trichloride is controlled to be 45 sccm for ion etching, and the microwave power is set to 100~500W.

8. The method for preparing the highly durable transparent hydrophobic glass according to claim 1, wherein In step six, the glass substrate with the micropore array is cleaned seven times. The first and second cleanings are both ultrasonically cleaned in a cleaning tank with isopropyl alcohol for 5 minutes each, and the ultrasonic power is 900w; the third cleaning is rinsed with deionized water in a spray tank for 5 minutes; the fourth, fifth and sixth cleanings are all ultrasonically cleaned with deionized water for 5 minutes each, and the ultrasonic power is 900w; the seventh cleaning is cleaned in a slow pulling tank with deionized water for 5 minutes, and the pulling speed is 5mm / s.

9. The method for preparing the highly durable transparent hydrophobic glass according to claim 1, wherein The drying temperature in step 6 is 50°.

10. The method for preparing a highly durable transparent hydrophobic glass according to claim 1, wherein The thickness of the evaporated PDMS film in step seven is 6-20 nm.

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