SiO2 anti-reflection film based on water-phase solution high-permeability induced closed holes and preparation method and application of SiO2 anti-reflection film
Preparing a closed-pore SiO2 anti-reflection film through aqueous solution solves the contradiction between weather resistance and mechanical properties of photovoltaic glass anti-reflection film, achieves a balance of high transmittance and mechanical stability, and avoids safety hazards and environmental pollution of traditional organic solvents.
Patent Information
- Application Number
- CN202510423620.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-07
- Publication Date
- 2025-07-08
AI Technical Summary
The existing photovoltaic glass anti-reflective films have contradictions in weather resistance and mechanical properties, and traditional alcohol organic coating solutions have safety hazards and environmental pollution problems.
A closed-porous SiO2 anti-reflection film was prepared by aqueous solution. By impregnation and pulling method combined with chemical corrosion, ZnS nanoparticle film and acid SiO2 sol film were formed on the glass substrate to form an internal pore structure. The template was removed by using the inorganic properties of ZnS nanoparticles to prepare an anti-reflection film with high permeability, mechanical stability and weather resistance.
The balance between high transmittance and mechanical stability is achieved, the wear resistance and chemical stability of the film layer are improved, and the safety hazards and environmental pollution of organic solvents are avoided, thereby reducing the coating cost.
Smart Images
Figure CN120271245A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of nanomaterials, and relates to a highly transparent and airtight pore SiO2 antireflection film based on an aqueous solution, a preparation method and an application thereof. Background Art
[0002] Photovoltaic modules face complex environments such as dust, rain, and temperature changes outdoors. This requires that the antireflection film of photovoltaic glass not only has good antireflection properties but also can remain stable in complex environments, while meeting high-performance standards such as light transmittance, mechanical properties, and weather resistance. However, in practice, the transmittance of the film layer is often restricted by mechanical properties and weather resistance. To match the refractive index of photovoltaic glass, the antireflection film needs to have a low refractive index, which usually requires introducing a pore structure into the material, but this will weaken the mechanical properties and weather resistance of the film layer. In addition, the commonly used alcohol-based organic coating solutions for preparing antireflection films not only easily volatilize and pollute the environment but also pose safety hazards due to their low flash points. Therefore, when developing antireflection films, it is necessary to balance light transmittance and stability by reasonably designing the film layer structure, and at the same time optimize the coating solution formula to make it safer and more environmentally friendly.
[0003] SiO2 is the most commonly used antireflection film material at present, and its intrinsic refractive index is 1.46. The SiO2 antireflection films used in the photovoltaic industry have gone through the development process of solid particle films, mesoporous films, and hollow particle films. Compared with traditional nano-solid silica particle films, the new mesoporous silica films perform better in terms of weather resistance and mechanical strength. However, the pores of the mesoporous film are connected to the outside world, and it is easy to adsorb water vapor and particulate matter through capillary action, resulting in a change in the refractive index of the film layer and a decline in optical properties (Journal of Non-Crystalline Solids 606 (2023) 122198). The antireflection film based on hollow SiO2 nanoparticles achieves high transmittance with a low refractive index, and has a closed pore structure inside and a smooth and continuous surface, which is superior to traditional open pore structure antireflection films in terms of wear resistance, stain resistance, and moisture resistance. However, the preparation of hollow SiO2 nanoparticles is difficult and the yield is low (Ceramics International 49 (2023) 6805–6810). This evolution shows that the closed pore structure can not only regulate the refractive index to improve light transmittance but also prevent the film layer from communicating with the outside world and enhance the structural stability. In terms of coating solutions, the commonly used alcohol-based organic solvent coating solutions at present, during the drying process, a large amount of solvent evaporates rapidly, which easily causes the film to shrink violently and crack. Moreover, organic solvents have low flash points, pose safety hazards, and the volatile VOCs will pollute the environment. In addition, these solvents are expensive and difficult to recycle, increasing the coating cost. Therefore, developing safe and environmentally friendly coating solutions such as aqueous solutions has become an important direction for optimizing the coating solution formula. Summary of the Invention
[0004] One of the objectives of the present invention is to provide a preparation method of a highly transmissive and sealed pore SiO2 antireflection film based on an aqueous solution. This preparation method is based on an aqueous solution, uses an aqueous solvent with a high flash point, less volatile VOC emissions, and is safer and more environmentally friendly as the coating solution, and combines the dip-coating method. First, a ZnS nanoparticle film is deposited on a glass substrate, and then an acidic SiO2 sol is dip-coated. The prepared film has the advantages of high transmissivity, mechanical stability, and weather resistance, etc.
[0005] To achieve the above objective, the present invention adopts the following technical solutions: A preparation method of a highly transmissive and sealed pore SiO2 antireflection film based on an aqueous solution, comprising the following steps:
[0006] S1. Take monodisperse ZnS nanoparticles with a particle size of 60 - 90 nm, disperse them in a mixed solution of 10 - 30 ml of anhydrous ethanol (EtOH) and deionized water (H2O), and use it as coating solution 1 for standby.
[0007] S2. Use tetraethyl orthosilicate (TEOS) as the silicon source, nitric acid (HNO3) as the catalyst, and anhydrous ethanol (EtOH) as the solvent, and prepare an acidic SiO2 sol through hydrolysis and polymerization reaction. After aging the acidic SiO2 sol at room temperature, dilute it and use it as coating solution 2 for standby.
[0008] S3. Pretreat the glass substrate to obtain a clean and dry surface. Use the dip-coating method for coating. First, immerse the glass substrate in coating solution 1, then take it out and dry it, then immerse it in coating solution 2, take it out and dry it, and then anneal it at 650 - 750 °C for 2 - 3 min to obtain a double-coated glass substrate.
[0009] S4. Through the chemical etching method, remove the ZnS particle template inside the film layer of the double-coated glass substrate, and prepare a highly transmissive and sealed pore SiO2 antireflection film based on an aqueous solution on the glass substrate.
[0010] As a further improvement of the preparation method of the highly transmissive and sealed pore SiO2 antireflection film based on an aqueous solution:
[0011] Preferably, the highly transmissive and sealed pore SiO2 antireflection film based on an aqueous solution includes a dense film layer and a porous film layer from top to bottom in structure. The total thickness of the film layer of this SiO2 antireflection film is 80 - 130 nm, the thickness of the dense film layer is 10 - 80 nm, the thickness of the porous film layer is 30 - 120 nm, and the size of the pores inside the porous film layer is 30 - 60 nm.
[0012] Preferably, the preparation method of the ZnS nanoparticles in step S1 is as follows: Dissolve thiourea CH4N2S and zinc acetate Zn(AC)2 in 25 ml of deionized water, with the dissolution concentrations being 0.114 - 0.152 g / ml and 0.0088 g / ml in sequence. After fully stirring, add polyvinylpyrrolidone PVP, and the addition concentration of PVP in deionized water is 0.03 g / ml. Continue stirring until homogeneous to obtain a mixed solution;
[0013] Transfer the mixed solution to a polytetrafluoroethylene inner liner, seal the reaction kettle, keep it warm at 120 - 150 °C for 4 - 6 h. After the reaction ends, use deionized water and absolute ethanol to remove the residual reaction solution by centrifugal cleaning method to obtain monodisperse ZnS nanoparticles with a particle size of 60 - 90 nm.
[0014] Preferably, the preparation method of the acidic SiO2 sol in step S2 is as follows: Add 15 ml of tetraethyl orthosilicate TEOS and 28 ml of absolute ethanol EtOH to a conical flask, and stir at room temperature for 15 - 20 min to obtain solution A;
[0015] Then mix 4 ml of deionized water and 0.091 - 0.106 ml of nitric acid and magnetically stir at room temperature for 15 - 20 min to obtain solution B;
[0016] Slowly drop solution B into solution A to obtain a reaction precursor solution, where the molar ratio of TEOS, EtOH in solution A to deionized water, nitric acid in solution B is 1:7:4:(0.03 - 0.035). Keep the reaction precursor solution warm in a 60 °C water bath for 3 h to obtain an acidic SiO2 sol.
[0017] Preferably, in the mixed solution of step S1, the mixing volume ratio of absolute ethanol EtOH to deionized water H2O is 1:(5 - 10).
[0018] Preferably, in step S2, the acidic SiO2 sol is aged at room temperature for 3 - 5 days and then diluted 1 - 5 times with deionized water for use as coating solution 2; in step S4, the double - coated glass substrate is immersed in a 0.5 - 1 mol / L hydrochloric acid solution for 1 - 3 h to remove the ZnS particle template inside the film layer.
[0019] Preferably, the specific steps for pre - treating the glass substrate in step S3 are as follows: Put the glass substrate cut to an appropriate size into a NaOH solution and perform ultrasonic cleaning for 10 - 15 min; after cleaning, first rinse the substrate with tap water, then immerse it in deionized water and continue ultrasonic cleaning for 10 - 15 min, gently wipe it with a lint - free cloth, then immerse it in absolute ethanol for soaking treatment, and finally take it out and dry it to obtain a clean glass substrate for use.
[0020] Preferably, in step S3, the glass substrate is first immersed in the coating solution 1 for 20 - 30 s, then taken out at a pulling speed of 50 - 150 mm / min at room temperature, and placed in an oven at 60 - 80 °C for drying to obtain a glass substrate with a single coating; then the glass substrate with a single coating is immersed in the coating solution 2, taken out at a pulling speed of 25 - 200 mm / min after 2 - 3 min, and placed in an oven at 60 - 80 °C for drying.
[0021] The second object of the present invention is to provide a high - transmittance and closed - pore SiO2 antireflection film based on an aqueous solution prepared by the above - mentioned preparation method of a high - transmittance and closed - pore SiO2 antireflection film based on an aqueous solution.
[0022] The third object of the present invention is to provide an application of the above - mentioned high - transmittance and closed - pore SiO2 antireflection film based on an aqueous solution on photovoltaic glass.
[0023] The beneficial effects of the present invention compared with the prior art are as follows:
[0024] (1) The present invention provides a preparation method of a dense SiO2 antireflection film with an internal hole structure. By using the sol - gel combined with acid etching method, an antireflection film structure is orderly constructed on a clean glass substrate. First, ZnS nanoparticles prepared by the hydrothermal method are used to deposit a continuous and uniform ZnS nanoparticle film by virtue of their characteristics of uniform particle size and good aqueous phase dispersibility. Subsequently, an acidic SiO2 sol is pulled on this particle film, not only forming a uniform and dense acidic SiO2 film on the surface, but also part of the sol penetrating into the gaps between ZnS particles, enhancing the adhesion of the film to the substrate. Then, the obtained film layer is annealed at 700 °C for 2.5 min. By virtue of the characteristics of ZnS nanoparticles as inorganic substances, etching with HCl solution can completely remove ZnS to form a closed - hole structure. At this time, the dense SiO2 structure on the top layer significantly improves the wear resistance of the antireflection film, which can not only effectively resist daily friction loss, but also block the intrusion of external chemical substances, protect the underlying structure, and greatly improve the chemical stability and service life. It is worth mentioning that the present invention uses an aqueous solution as the coating solution, which not only has rich resources and low pollution, but also helps the coating materials to be uniformly dispersed, realizing precise control of the film thickness and refractive index.
[0025] In summary, with a safe and environmentally friendly aqueous coating solution formulation, the present invention successfully prepares a closed - pore dense SiO2 antireflection film with an internal hole structure, high transmittance, mechanical stability and weather resistance on a glass substrate by a low - cost and easy - to - operate process.
[0026] (2) The present invention focuses on antireflection film technology and introduces a closed-cell dense SiO2 antireflection film, which breaks through traditional limitations and demonstrates significant advantages in multiple dimensions. In terms of performance, this antireflection film not only has an extremely high visible light transmittance with a peak of 99.7%, but also has excellent mechanical durability. Compared with traditional mesoporous SiO2 antireflection coatings, its closed-cell structure endows the film with better stain resistance and moisture resistance. The main body of the film is a continuous and dense SiO2 film, with strong adhesion between the bottom and the substrate, and the top dense layer effectively protects the internal pore structure, significantly improving the hardness and wear resistance of the film. In terms of the preparation process, the present invention uses acidic SiO2 sols with different concentrations as refractive index regulators and controls the film thickness by different pulling speeds, greatly improving the flexibility of comprehensive performance regulation. Treating the coating at a glass tempering temperature of 700°C can complete the tempering of the glass while curing the acidic SiO2 sol, reducing the operation process, and there are no problems of organic matter pollution and pore collapse during the annealing process. In addition, the coating solution is mainly aqueous. Compared with organic solvent coating solutions, it has a higher flash point and less VOC volatilization, which is safe and environmentally friendly. This coating solution has a wide range of applications and is expected to be extended to more similar coating materials. The closed-cell dense SiO2 antireflection film of the present invention is simple to prepare and has wide applicability, showing broad application prospects in many fields such as solar cells, displays, optical lenses, and buildings. Description of the Drawings
[0027] Figure 1 is a schematic structural diagram of the high-transmission and closed-cell SiO2 antireflection film based on an aqueous solution prepared by the present invention.
[0028] Figure 2 is an SEM image of the high-transmission and closed-cell SiO2 antireflection film based on an aqueous solution prepared in Example 1, (a) surface view of the film layer, (b) cross-sectional view of the film layer.
[0029] Figure 3 is the transmittance test of bare glass and glass coated with the high-transmission and closed-cell SiO2 antireflection film based on an aqueous solution prepared in Example 1. Detailed Description of the Embodiments
[0030] In order to make the objectives, technical solutions, and advantages of the present invention clearer, the following further elaborates on the present invention in conjunction with embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.
[0031] Preparation Example 1
[0032] This preparation example provides a method for preparing ZnS nanoparticles, which specifically includes the following steps:
[0033] Dissolve 2.85 g of thiourea (CH4N2S) and 0.22 g of zinc acetate (Zn(AC)2) in 25 ml of deionized water. After stirring well, add 0.75 g of polyvinylpyrrolidone (PVP), and continue stirring until homogeneous. Transfer the mixed solution to a polytetrafluoroethylene liner, seal the reaction kettle, and keep it at 140 °C for 5 h. After the reaction, use deionized water and absolute ethanol to remove the residual reaction solution by centrifugal washing to obtain monodisperse ZnS nanoparticles. After testing, the particle size is 90 nm.
[0034] Preparation Example 2
[0035] This preparation example provides a method for preparing ZnS nanoparticles, which specifically includes the following steps: Dissolve 3.25 g of thiourea (CH4N2S) and 0.22 g of zinc acetate (Zn(AC)2) in 25 ml of deionized water. After stirring well, add 0.75 g of polyvinylpyrrolidone (PVP), and continue stirring until homogeneous. Transfer the mixed solution to a polytetrafluoroethylene liner, seal the reaction kettle, and keep it at 140 °C for 5 h. After the reaction, use deionized water and absolute ethanol to remove the residual reaction solution by centrifugal washing to obtain monodisperse ZnS nanoparticles. After testing, the particle size is 80 nm.
[0036] Preparation Example 3
[0037] This preparation example provides a method for preparing ZnS nanoparticles, which specifically includes the following steps: Dissolve 3.80 g of thiourea (CH4N2S) and 0.22 g of zinc acetate (Zn(AC)2) in 25 ml of deionized water. After stirring well, add 0.75 g of polyvinylpyrrolidone (PVP), and continue stirring until homogeneous. Transfer the mixed solution to a polytetrafluoroethylene liner, seal the reaction kettle, and keep it at 140 °C for 5 h. After the reaction, use deionized water and absolute ethanol to remove the residual reaction solution by centrifugal washing to obtain monodisperse ZnS nanoparticles. After testing, the particle size is 60 nm.
[0038] Preparation Example 4
[0039] This preparation example provides a method for preparing acidic SiO2 sol, which specifically includes the following steps:
[0040] Add 15 ml of tetraethyl orthosilicate (TEOS) and 28 ml of absolute ethanol (EtOH) to a conical flask, and stir at room temperature for 20 min to obtain solution A;
[0041] Then mix 4 ml of H2O and 0.106 ml of nitric acid (HNO3) and stir magnetically at room temperature for 20 min to obtain solution B;
[0042] Subsequently, solution B was slowly dropped into solution A to obtain a reaction precursor solution, where the molar ratio of TEOS, EtOH in solution A to deionized water, nitric acid in solution B was 1:7:4:0.035. The precursor solution was kept at 60 °C in a water bath for 3 h. After the reaction ended, an acidic SiO2 sol was obtained and aged at room temperature for 5 days.
[0043] Preparation Example 5
[0044] This preparation example provides a method for preparing an acidic SiO2 sol, which specifically includes the following steps:
[0045] Add 15 ml of tetraethyl orthosilicate (TEOS) and 28 ml of absolute ethanol (EtOH) into a conical flask, and stir at room temperature for 20 min to obtain solution A;
[0046] Then mix 4 ml of H2O and 0.098 ml of nitric acid (HNO3) and stir magnetically at room temperature for 20 min to obtain solution B;
[0047] Subsequently, solution B was slowly dropped into solution A to obtain a reaction precursor solution, where the molar ratio of TEOS, EtOH in solution A to deionized water, nitric acid in solution B was 1:7:4:0.032. The precursor solution was kept at 60 °C in a water bath for 3 h. After the reaction ended, an acidic SiO2 sol was obtained and aged at room temperature for 5 days.
[0048] Preparation Example 6
[0049] This preparation example provides a method for preparing an acidic SiO2 sol, which specifically includes the following steps:
[0050] Add 15 ml of tetraethyl orthosilicate (TEOS) and 28 ml of absolute ethanol (EtOH) into a conical flask, and stir at room temperature for 20 min to obtain solution A;
[0051] Then mix 4 ml of H2O and 0.091 ml of nitric acid (HNO3) and stir magnetically at room temperature for 20 min to obtain solution B;
[0052] Subsequently, solution B was slowly dropped into solution A to obtain a reaction precursor solution, where the molar ratio of TEOS, EtOH in solution A to deionized water, nitric acid in solution B was 1:7:4:0.03. The precursor solution was kept at 60 °C in a water bath for 3 h. After the reaction ended, an acidic SiO2 sol was obtained and aged at room temperature for 5 days.
[0053] Preparation Example 7
[0054] This preparation example provides a method for pre-treating a glass substrate, which specifically includes the following steps:
[0055] Place the glass substrate cut to the appropriate size into the NaOH solution and perform ultrasonic cleaning for 15 minutes. After cleaning, first rinse the substrate thoroughly with tap water, then immerse it in deionized water and continue ultrasonic cleaning for 10 minutes. Gently wipe it with a lint-free cloth, then soak it in anhydrous ethanol, and finally take it out and dry it to obtain a clean glass substrate ready for use.
[0056] Example 1
[0057] This example provides a method for preparing a high-transmission closed-pore SiO2 antireflection film based on an aqueous solution, which specifically includes the following steps:
[0058] S1. Take the monodisperse ZnS nanoparticles prepared in Preparation Example 1 and disperse them in a mixed solution of 20 ml of anhydrous ethanol (EtOH) and deionized water (H2O) with a volume ratio of EtOH:H2O = 1:9 as Coating Solution 1 for standby.
[0059] S2. Age the acidic SiO2 sol prepared in Preparation Example 4 at room temperature for 5 days and then dilute it 3 times as Coating Solution 2 for standby.
[0060] S3. Take the glass substrate pretreated in Preparation Example 7, first immerse it in Coating Solution 1 for 30 s, then lift it out at a lifting speed of 100 mm / min at room temperature and place it in an oven at 60 °C for drying. Then immerse it in Coating Solution 2, lift it out at a lifting speed of 100 mm / min after 3 min, place it in an oven at 80 °C for drying and then anneal it at 700 °C for 2.5 min to obtain a double-coated glass substrate.
[0061] S4. Immerse the double-coated glass substrate in a 1 mol / L hydrochloric acid solution for 2 h to remove the ZnS particle template inside the film layer, and obtain a closed-pore SiO2 antireflection film with a dense outer layer and an internal pore structure.
[0062] After testing, the thickness of the prepared film layer is 80 nm, the pore size is 60 nm, and the thickness of the top dense film layer is 20 nm. The highest transmittance in the visible light range can reach 99.7%.
[0063] Example 2
[0064] This example provides a method for preparing a high-transmission closed-pore SiO2 antireflection film based on an aqueous solution, which specifically includes the following steps:
[0065] S1. Take the monodisperse ZnS nanoparticles prepared in Preparation Example 2 and disperse them in a mixed solution of 20 ml of anhydrous ethanol (EtOH) and deionized water (H2O) with a volume ratio of EtOH:H2O = 1:9 as Coating Solution 1 for standby.
[0066] S2. The acidic SiO2 sol prepared in Preparation Example 5 was aged at room temperature for 5 days and then diluted 3 times to be used as Coating Solution 2 for later use.
[0067] S3. Take the glass substrate pretreated in Preparation Example 7, first immerse it in Coating Solution 1 for 30 s, then lift it out at a lifting speed of 100 mm / min at room temperature, and place it in an oven at 60 °C for drying; then immerse it in Coating Solution 2, lift it out at a lifting speed of 150 mm / min after 3 min, place it in an oven at 80 °C for drying and then anneal it at 700 °C for 2.5 min to obtain a double-coated glass substrate.
[0068] S4. Immerse the double-coated glass substrate in a 1 mol / L hydrochloric acid solution for 2 h to remove the ZnS particle template inside the film layer, and obtain a closed-pore SiO2 antireflection film with an internal pore structure and an external dense layer.
[0069] After testing, the thickness of the prepared film layer is 100 nm, the pore size is 42 nm, and the thickness of the top dense film layer is 58 nm; the highest transmittance in the visible light range can reach 98.2%.
[0070] Example 3
[0071] This example provides a preparation method of a high-transmittance and closed-pore SiO2 antireflection film based on an aqueous solution, which specifically includes the following steps:
[0072] S1. Take the monodisperse ZnS nanoparticles prepared in Preparation Example 3, disperse them in a mixed solution of 20 ml of anhydrous ethanol (EtOH) and deionized water (H2O) with a volume ratio of EtOH:H2O = 1:9 to be used as Coating Solution 1 for later use.
[0073] S2. The acidic SiO2 sol prepared in Preparation Example 6 was aged at room temperature for 5 days and then diluted 3 times to be used as Coating Solution 2 for later use.
[0074] S3. Take the glass substrate pretreated in Preparation Example 7, first immerse it in Coating Solution 1 for 30 s, then lift it out at a lifting speed of 100 mm / min at room temperature, and place it in an oven at 60 °C for drying; then immerse it in Coating Solution 2, lift it out at a lifting speed of 200 mm / min after 3 min, place it in an oven at 80 °C for drying and then anneal it at 700 °C for 2.5 min to obtain a double-coated glass substrate.
[0075] S4. Immerse the double-coated glass substrate in a 1 mol / L hydrochloric acid solution for 3 h to remove the ZnS particle template inside the film layer, and obtain a closed-pore SiO2 antireflection film with an internal pore structure and an external dense layer.
[0076] After testing, the thickness of the prepared film layer is 110 nm, the pore size is 30 nm, and the thickness of the top dense film layer is 80 nm; the highest transmittance in the visible light range can reach 97.6%.
[0077] Figure 1 It is a schematic diagram of the structure of the hermetically sealed pore SiO2 antireflection film with an internal pore structure prepared by the present invention. The structure of the film layer is as shown in Figure 1 the figure, which is composed of upper and lower layers. The bottom pore film layer is obtained after removing ZnS particles, and its thickness is determined by the thickness of the ZnS particle layer, mainly depending on the size of ZnS particles and the concentration of Coating Solution 1; the top dense film layer is composed of acidic SiO2 sol, and its thickness is determined by the concentration of Coating Solution 2 and the pulling speed.
[0078] Figure 2 It is an SEM image of the highly transmissive hermetically sealed pore SiO2 antireflection film based on an aqueous solution prepared in Example 1 of the present invention, where (a) is the surface view of the film layer and (b) is the cross-sectional view of the film layer. It can be seen from Figure 2 the figure that the surface of the prepared film layer is flat and dense, with an overall thickness of 80 nm, where the pore size of the bottom layer is 60 nm and the thickness of the top dense film is 20 nm.
[0079] Figure 3 It is a transmittance test of bare glass and glass coated with the SiO2 antireflection film with an external dense and internal pore structure prepared in Example 1. It can be seen from the comparison in Figure 3 the figure that the transmittance of the coated glass is significantly improved in the visible light region, with the average transmittance increased by nearly 8%, and the highest transmittance can reach 99.7%.
[0080] Those skilled in the art should understand that the above are only several specific embodiments of the present invention, rather than all embodiments. It should be noted that many variations and improvements can be made for those of ordinary skill in the art. All variations or improvements that do not exceed the scope of the claims shall be regarded as the protection scope of the present invention.
Claims
1. A preparation method of a high-transmission and airtight pore SiO2 antireflection film based on an aqueous solution, characterized in that, The steps include: S1, taking monodisperse ZnS nanoparticles with a particle size of 60-90 nm, dispersing them in a mixed solution of 10-30 ml of anhydrous ethanol EtOH and deionized water H2O, and using it as a coating solution 1; S2, using tetraethyl orthosilicate TEOS as a silicon source, nitric acid HNO3 as a catalyst, and anhydrous ethanol EtOH as a solvent, a hydrolysis polymerization reaction is performed to prepare an acidic SiO2 sol, and the acidic SiO2 sol is aged at room temperature and then diluted to be used as a coating solution 2; S3, pre-treating the glass substrate to obtain a clean and dry surface, using the immersion-pulling method to coat the glass substrate, first immersing the glass substrate in coating solution 1, then pulling it out and drying it, then immersing it in coating solution 2, then pulling it out and drying it, and then annealing it at 650-750° C. for 2-3 minutes to obtain a double-coated glass substrate; S4. The ZnS particle template inside the double-coated glass substrate film layer is removed by chemical etching, and a high-transmittance, dense, closed-pore SiO2 anti-reflection film based on an aqueous solution is prepared on the glass substrate.
2. The preparation method of the anti-reflection film with highly permeable closed pores SiO2 based on an aqueous solution according to claim 1, characterized in that, The SiO2 anti-reflection film structure includes a dense film layer and a porous film layer from top to bottom. The total film thickness of the SiO2 anti-reflection film is 80-130nm, the thickness of the dense film layer is 10-80nm, the thickness of the porous film layer is 30-120nm, and the size of the holes inside the porous film layer is 30-60nm.
3. The preparation method of the anti-reflection film based on water-phase solution with high-permeability closed-pore SiO2 according to claim 1, characterized in that, The preparation method of the ZnS nanoparticles in step S1 is as follows: dissolve thiourea CH4N2S and zinc acetate Zn(AC)2 in 25 ml of deionized water, the dissolved concentrations are 0.114-0.152 g / ml and 0.0088 g / ml respectively, and add polyvinyl pyrrolidone PVP after sufficient stirring, the added concentration of PVP in deionized water is 0.03 g / ml, and continue stirring until uniform to obtain a mixed solution; The mixed solution was transferred to a polytetrafluoroethylene liner, the reactor was sealed, and the temperature was kept at 120-150°C for 4-6 hours. After the reaction was completed, the residual reaction solution was removed by centrifugal washing with deionized water and anhydrous ethanol to obtain monodisperse ZnS nanoparticles with a particle size of 60-90 nm.
4. The preparation method of the anti-reflection film based on high-permeability closed-pore SiO2 in an aqueous solution according to claim 1, characterized in that, The preparation method of the acidic SiO2 sol in step S2 is as follows: add 15 ml of tetraethyl orthosilicate TEOS and 28 ml of anhydrous ethanol EtOH into a conical flask, stir at room temperature for 15 to 20 minutes, and obtain solution A; Then, 4 ml of deionized water and 0.091-0.106 ml of nitric acid were mixed and magnetically stirred at room temperature for 15-20 min to obtain solution B; Solution B was slowly dripped into solution A to obtain a reaction precursor solution, wherein the molar ratio of TEOS and EtOH in solution A to deionized water and nitric acid in solution B was 1:7:4:(0.03-0.035), and the reaction precursor solution was kept in a 60° C. water bath for 3 h to obtain an acidic SiO2 sol.
5. The preparation method of the anti-reflection film with high-transmission and closed pores SiO2 based on aqueous solution according to claim 1 or 3, characterized in that, In the mixed solution of step S1, the mixing volume ratio of anhydrous ethanol EtOH and deionized water H2O is 1:(5-10).
6. The preparation method of the high-transmittance hermetic pore SiO2 antireflection film based on an aqueous solution according to claim 1 or 4, characterized in that, In step S2, the acidic SiO2 sol is aged at room temperature for 3 to 5 days and then diluted 1 to 5 times with deionized water to be used as coating solution 2; in step S4, the double-coated glass substrate is immersed in a 0.5 to 1 mol / L hydrochloric acid solution for 1 to 3 h to remove the ZnS particle template inside the film layer.
7. The preparation method of the anti-reflection film of high-permeability closed-pore SiO2 based on an aqueous solution according to claim 1, wherein, The specific steps for the pretreatment of the glass substrate in step S3 are as follows: The glass substrate cut to an appropriate size is placed in a NaOH solution and ultrasonically cleaned for 10 to 15 min; after the cleaning is completed, the substrate is first rinsed thoroughly with tap water, then immersed in deionized water and ultrasonically cleaned for another 10 to 15 min, gently wiped with a lint-free cloth, then immersed in absolute ethanol for soaking treatment, and finally taken out and dried to obtain a clean glass substrate for use.
8. The preparation method of the anti-reflection film with high-transmission and closed pores SiO2 based on aqueous solution according to claim 1 or 4, characterized in that, In step S3, the glass substrate is first immersed in coating solution 1 for 20 to 30 s, then withdrawn at a withdrawal speed of 50 to 150 mm / min at room temperature, and placed in an oven at 60 to 80 °C for drying to obtain a single-coated glass substrate; then the single-coated glass substrate is immersed in coating solution 2, and after 2 to 3 min, it is withdrawn at a withdrawal speed of 25 to 200 mm / min and placed in an oven at 60 to 80 °C for drying.
9. A high-transmission and hermetic pore SiO2 antireflection film based on an aqueous solution prepared by the preparation method of the high-transmission and hermetic pore SiO2 antireflection film based on an aqueous solution according to any one of claims 1-8.
10. An application of the high-transmission and hermetic pore SiO2 antireflection film based on an aqueous solution according to claim 9 on photovoltaic glass.