Preparation method of rare earth element modified SiO2 film with high radiation resistance, high mechanical property and high antireflection

Abstract

The invention discloses a preparation method of a rare earth modified SiO2 film with high radiation resistance, high mechanical property and high antireflection. Polyethylene glycol is used as a pore-foaming agent, tetraethyl silicate and methyltriethoxysilane are used as precursors, absolute ethyl alcohol is used as a solvent, nitric acid is used as a catalyst, and rare earth elements are used as an anti-radiation agent. The prepared SiO2 sol is coated on glass, the sol is dried into gel, and the porous nano-film is obtained through heat treatment. The spectrum average transmittance (transmittance of coated glass) of the film at 400-1100 nm is 93.1%, and is improved by 4.57% compared with that of glass; the surface hardness of the film reaches the highest level 9H of a pencil method, and the adhesive force also reaches the highest level 0 of an adhesive tape method. After 5000 equivalent solar hours are irradiated by ultraviolet rays, the average transmittance of the film is 92.25% and is only reduced by 0.85%. The high-radiation-resistance, high-mechanical-property and high-antireflection film is simple in preparation process and suitable for industrial popularization.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of antireflection film materials, and particularly relates to a preparation method of a high-anti-radiation high-mechanical-property high-antireflection SiO2 film modified by a rare earth element. BACKGROUND

[0002] Solar cells convert solar energy into electrical energy through the photovoltaic effect, and are one of the most important green energy sources today. Solar cells generally work outdoors or in the wild and need to be protected by a glass cover plate. The refractive index of the glass cover plate is about 1.52, and the refractive index of air is about 1. The difference between the two causes about 8% of the sunlight to be lost due to light reflection of the glass cover plate. Therefore, an antireflection film needs to be coated on the surface of the glass to improve the transmittance of the glass cover plate.

[0003] SiO2 porous antireflection films prepared by the sol-gel method have controllable refractive index and excellent optical performance

Ceramics International, 2024, 50(4): 7029-7038

Journal of Sol-Gel Science and Technology, 2010, 53(2): 322-327

Surface & Coatings Technology, 2011, 206(6): 1490-1494

Renewable & Sustainable Energy Reviews, 2016, 59: 1307-1316

Journal of Coatings Technology and Research, 2019, 16(2): 615-622

[0004] The ultraviolet band (250-400 nm) of the solar spectrum also severely damages the residual organic matter on the antireflection film prepared by the sol-gel method, leading to destruction of the film structure and degradation of the antireflection performance, and even having the opposite effect of reducing the transmittance of the glass cover plate

Npj Materials Degradation, 2024, 8(1): 12

[0005] Meanwhile, as the outermost layer of photovoltaic modules, in addition to the need for good anti-reflective, anti-radiation characteristics, it also needs to withstand mechanical wear and tear from the outside world, such as bumps during handling, washing of surface dust, etc. If the mechanical strength of the anti-reflective film is insufficient, the film and film base bonding force is weak, which leads to film damage, cracking, peeling and other problems during use, thereby shortening the service life or reducing the anti-reflective effect, which all require the film to have good mechanical properties.

[0006] Chinese patent CN 108424722 A discloses a preparation method of a hardening anti-reflective optical coating solution for flexible display devices. Organic siloxane is synthesized with organic amine to form bridged silsesquioxane, and surfactant, silane, acid, etc. are added to obtain the final coating solution. The film prepared by the pull-up method has a maximum transmittance of 99.69%, and the transmittance only decreases by 0.1% after being rubbed by CS-10F rubbing head for 25 times, which has good wear resistance, but does not involve the study of anti-radiation performance. Chinese patent CN 110922625 A discloses a preparation method of PDMS super-hydrophobic surface using surface focusing heat effect. First, PDMS with periodic regular hemispherical protrusions on the surface is prepared, and the protrusions are scanned by infrared to obtain a hydrophobic surface. The contact angle of the PDMS super-hydrophobic surface is 155.9° before UV irradiation, and the contact angle of the surface is 156.7° after irradiation for 72 hours under a 200 mW / cm 2 UV lamp with a wavelength of 365 nm, which has good anti-radiation performance, but does not involve the study of optical and mechanical properties. Chinese patent CN 113444430 A discloses a preparation method of a stain-resistant coating and a stain-resistant and anti-UV radiation coating. The isocyanate in the hexamethylene diisocyanate trimer reacts with the amino group in the amino-terminated polydimethylsiloxane to covalently graft the low-surface-energy polydimethylsiloxane onto the hexamethylene diisocyanate trimer. The maximum transmittance of the cured coating is 98.8%, and the pencil hardness is 8H, but no anti-UV radiation data is provided. Chinese patent CN 114108317 A discloses a preparation method of surface-grafted PBO fibers. 4,4-hexafluoroisopropyl phthalic anhydride (6FDA) is grafted onto PBO fibers containing amino groups on the surface, and the fibers are irradiated by 800 W / m 2The initial PBO fiber strength retention rate was 49.1% after 100h of UV irradiation, and the grafted PBO fiber strength retention rate was 75.4%. Chinese patent CN 115872629 A discloses a high-performance mesoporous antireflection nanofilm and a preparation method thereof. In the sol-gel process, polyethylene glycol monomethyl ether substances are used as pore-forming agents. The film attached to the surface of photovoltaic glass can increase the transmittance by 4-6 percentage points in the range of 380-1100nm, the pencil hardness is above 9H, and the adhesion reaches 0 level or above, but it does not involve the characterization of the anti-radiation performance of the film. Chinese patent CN 117430343 A discloses a corrosion-resistant and anti-ultraviolet SiO2 nanometer antireflection film and a preparation method thereof. Isobutyl triethoxysilane is added to the silica sol, and the prepared film has a transmittance increase of 4-6 percentage points in the range of 380-1100nm, a pencil hardness of up to 9H above (GB / T1727-92), and an adhesion of up to 0 level (GB / T 1727-1992): After 100h of 250W ultraviolet lamp irradiation, the transmittance decreases by 0.45 percentage points, the hardness and adhesion remain unchanged, but the results of longer irradiation are not known.

[0007] An et al.

Colloids and Surfaces a-Physicochemical and Engineering Aspects, 2021, 625

ACS Applied Materials & Interfaces, 2022:8

Journal of Sol-Gel Science and Technology, 2023, 106(2):381-392

Progress in Organic Coatings, 2023, 174: 8

ACS Applied Materials & Interfaces, 2023, 15(14): 18300-18310

[0008] In summary, the preparation process of SiO2 thin film is relatively simple, and the refractive index can be changed by adjusting the porosity. However, in order to meet the requirements of solar cells to work continuously and efficiently in harsh outdoor environments, the antireflection thin film must have high optical performance, high radiation resistance, and high mechanical properties. SUMMARY

[0009] The purpose of the present application is to provide a preparation method of a rare earth modified high radiation resistant high mechanical property high antireflection SiO2 thin film to overcome the shortcomings of the prior art. The antireflection thin film prepared by the method of the present application has high transmittance, high radiation resistance, and high mechanical properties. The average transmittance (transmittance of coated glass) in the wavelength range of 400-1100 nm reaches 93.1%, which is 4.57 percentage points higher than that of the glass substrate. The thin film has high hardness, reaching the highest level of 9H by pencil method; has high adhesion, reaching the highest level of 0 by adhesive tape method. After 5000 equivalent solar hours (ESHs) of ultraviolet irradiation, the average transmittance of the thin film is 92.25%, which decreases by only 0.85 percentage points, and has a pencil hardness of 8H and an adhesive tape adhesion of 0. The preparation process of the technical scheme of the present application is simple, low in cost, suitable for large-area coating, good in stability, and easy to industrialize and popularize.

[0010] To achieve the above purpose, the technical scheme of the present application is as follows:

[0011] The application discloses a preparation method of a rare earth modified high-anti-radiation high-mechanical-property high-anti-reflection SiO2 film, and is characterized by the following steps: preparing the anti-reflection film by using tetraethyl orthosilicate, methyl triethoxysilane, nitric acid, water, a porogen and an anti-radiation agent by adopting a sol-gel method, wherein the mass ratio of the anti-radiation agent to the sol is 1:10-1:200, the mass ratio of the porogen to the sol is 1:10-1:100, and the volume ratio of the tetraethyl orthosilicate, the methyl triethoxysilane, anhydrous ethanol, deionized water and concentrated nitric acid is 1:(0.1-6.0):10:0.3:(0.1-1.0). The anti-reflection film is prepared by using mPEG as the porogen and nitrate of a rare earth as the anti-radiation agent, and the transmittance, the anti-radiation performance, the surface hardness and the adhesion of the anti-reflection film can be adjusted by adjusting the content of the nitrate of the rare earth.

[0012] The application discloses a preparation method of a rare earth modified high-anti-radiation high-mechanical-property high-anti-reflection SiO2 film, and is characterized by the following steps:

[0013] (1) raw material preparation: the mass ratio of the porogen to the sol in the anti-reflection film raw material is 1:10-1:100, the mass ratio of the anti-radiation agent to the sol is 1:10-1:200, and the volume ratio of the tetraethyl orthosilicate, the methyl triethoxysilane, anhydrous ethanol, deionized water and concentrated nitric acid is 1:(0.1-6.0):10:0.3:(0.1-1.0).

[0014] (2) preparation of a sol: according to the stoichiometric ratio of a target product, the concentrated nitric acid, the water and the anhydrous ethanol are first poured into a pre-cleaned beaker, and then stirred at a speed of 1-3000 r / min for 0.1-25 h by using a magnetic stirrer; then the tetraethyl orthosilicate, the methyl triethoxysilane, mPEG and the nitrate of a rare earth element are added into the above solution, and the solution is moved into a conical flask and aged in a water bath at 25-100 DEG C for 0.1-25 h and for 0.1-10 days, so as to obtain the required sol.

[0015] (3) preparation of an anti-reflection film: a film layer is coated on a clean glass, the coated glass substrate is dried in an oven at 25-200 DEG C for 0.1-25 h, and then moved into a muffle furnace and annealed at 200-600 DEG C for 0.1-25 h, so as to obtain the rare earth modified high-anti-radiation high-mechanical-property high-anti-reflection SiO2 film.

[0016] The present application is to improve the transmittance, radiation resistance, surface hardness and adhesion of acid catalyzed SiO2 film, and the nitrate of rare earth is added as a radiation resistance agent. The nitrate of rare earth generates gas and rare earth oxide after heat treatment, improves the porosity of the film and the uniformity of the porosity, thereby improving the antireflection performance of the film; and the generated rare earth oxide is uniformly distributed on the surface of the film, which significantly improves the reflection of light in the ultraviolet wavelength range, improves the reflection of the SiO2 antireflection film to the ultraviolet part, and thereby improves the radiation resistance of the film. The SiO2 film with high radiation resistance, high mechanical properties and high antireflection is prepared by sol-gel method, which is simple in process and low in cost. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 The transmittance of the ultrawhite glass coated with the antireflection film of the present application and the ultrawhite glass without the antireflection film, and the transmittance after irradiation of 5000 ESHs by a 250W ultraviolet lamp (ultraviolet energy density 15mW / cm 2 ) can be seen from the comparison spectrum diagram of the transmittance that the film has good antireflection effect, maintains high transmittance after irradiation of 5000 ESHs, and still has good antireflection performance.

[0018] Figure 2 The scanning electron microscope picture of the ultrawhite glass coated with the antireflection film of the present application, with a magnification of 50K, the film has good porosity, and the generated rare earth oxide on the surface of the film is uniformly distributed.

[0019] Figure 3 The average transmittance of the ultrawhite glass coated with the antireflection film of the present application changes with the irradiation time during the ultraviolet irradiation of 5000 ESHs, and the linear fitting curve thereof.

[0020] Figure 4 The scanning electron microscope picture (SEM) of the surface of the high radiation resistance, high mechanical property and high antireflection SiO2 film prepared by the present application before and after 5000 ESHs ultraviolet irradiation, after testing the adhesion by the adhesive tape method; the adhesion of the film is tested according to the standard "GB / T 33049-2016". It can be seen that before irradiation, the edge of the scratch is not obviously peeled off after being torn by the adhesive tape, the adhesion is above 0 level, and after irradiation, the edge of the scratch is obviously, but no peeling occurs, and the adhesion still remains above 0 level.

[0021] Figure 5The scanning electron microscope (SEM) of the surface of the high-anti-radiation high-mechanical-property high-anti-reflection SiO2 film in the application after the pencil test before and after 5000 ESHs ultraviolet irradiation; the surface hardness of the film is tested according to the standard “GB / T 6739-2006”, and the pencil used in the figure is 9H and 8H, so it can be seen that no pencil marks are left before irradiation, the hardness of the film reaches 9H, the 9H pencil leaves a slight scratch after irradiation, and the 8H pencil does not leave a scratch, and the hardness is above 8H. DETAILED DESCRIPTION

[0022] A rare earth modified high-anti-radiation high-mechanical-property high-anti-reflection SiO2 film and a preparation method thereof, the mass ratio of the porogen to the sol in the SiO2 anti-reflection film is 1:10-1:100, the mass ratio of the anti-radiation agent to the sol is 1:10-1:200, and the volume ratio of tetraethyl orthosilicate, methyl triethoxysilane, anhydrous ethanol, deionized water, concentrated nitric acid is 1:(0.1-6.0):10:0.3:(0.1-1.0), and the film is prepared by a sol-gel method.

[0023] A rare earth modified high-anti-radiation high-mechanical-property high-anti-reflection SiO2 film and a preparation method thereof, including the following steps:

[0024] The SiO2 anti-reflection film is prepared by a sol-gel method using anhydrous ethanol, tetraethyl orthosilicate, methyl triethoxysilane, concentrated nitric acid, deionized water, mPEG and a rare earth nitrate.

[0025] The application will be further described in detail in combination with examples:

[0026] Example 1:

[0027] In order to compare the modification effect of rare earth elements, an acid-catalyzed SiO2 film without adding rare earth is first prepared, and the preparation method includes the following steps:

[0028] (1) Raw material preparation: the anti-reflection film raw materials are anhydrous ethanol, tetraethyl orthosilicate, methyl triethoxysilane, deionized water, concentrated nitric acid, and the volume ratio of each component is 10:1:1:0.3:0.3, and the mass ratio of the porogen to the sol is 1:50.

[0029] (2) Preparation of sol: the chemicals are accurately measured according to the stoichiometric ratio of the target product, the concentrated nitric acid, water and anhydrous ethanol are first poured into a pre-cleaned beaker, and stirred at a speed of 1500 r / min for 2 h on a magnetic stirrer, then the tetraethyl orthosilicate, methyl triethoxysilane and mPEG are added to the above solution while stirring, and then moved into a conical flask in a water bath at 60℃ for 2 h, and then cooled to room temperature and aged for 3 days to obtain an acid-catalyzed sol.

[0030] (3) Preparation of the anti-reflective film: coating the film layer on the cleaned glass, putting the coated glass substrate into the oven at 80℃ for drying for 1 h, then moving into the muffle furnace, annealing at 400℃ for 1 h, to obtain the anti-reflective SiO2 film.

[0031] Example Two:

[0032] The preparation method of the rare earth modified high radiation resistance high mechanical property high anti-reflective SiO2 film comprises the following steps:

[0033] (1) Preparation of raw materials: the anti-reflective film raw materials are anhydrous ethanol, tetraethyl orthosilicate, methyl triethoxysilane, deionized water and concentrated nitric acid, and the volume ratio of each component is 10:1:1:0.3:0.3, the mass ratio of the pore former to the sol is 1:50, and the mass ratio of lanthanum nitrate to the sol is 1:150.

[0034] (2) Preparation of the sol: according to the stoichiometric ratio of the target product, accurately measure the amount, first pour the concentrated nitric acid, water and anhydrous ethanol into a pre-cleaned beaker, place it on a magnetic stirrer, stir at a speed of 1500 r / min for 2 h, then add tetraethyl orthosilicate, methyl triethoxysilane, mPEG and lanthanum nitrate to the above solution while stirring, move into a conical flask, water bath at 60℃ for 2 h, cool to room temperature, then age for 3 days, to obtain the modified acid catalytic sol.

[0035] (3) Preparation of the anti-reflective film: coating the film layer on the cleaned glass, putting the coated glass substrate into the oven at 80℃ for drying for 1 h, then moving into the muffle furnace, annealing at 400℃ for 1 h, to obtain the rare earth modified high radiation resistance high mechanical property high anti-reflective SiO2 film.

[0036] Example Three:

[0037] The preparation method of the rare earth modified high radiation resistance high mechanical property high anti-reflective SiO2 film comprises the following steps:

[0038] (1) Preparation of raw materials: the anti-reflective film raw materials are anhydrous ethanol, tetraethyl orthosilicate, methyl triethoxysilane, deionized water and concentrated nitric acid, and the volume ratio of each component is 10:1:1:0.3:0.3, the mass ratio of the pore former to the sol is 1:70, and the mass ratio of lanthanum nitrate to the sol is 1:150.

[0039] (2) Preparation of the sol: according to the stoichiometric ratio of the target product, accurately measure the amount, first pour the concentrated nitric acid, water and anhydrous ethanol into a pre-cleaned beaker, place it on a magnetic stirrer, stir at a speed of 1500 r / min for 2 h, then add tetraethyl orthosilicate, methyl triethoxysilane, mPEG and lanthanum nitrate to the above solution while stirring, move into a conical flask, water bath at 60℃ for 2 h, cool to room temperature, then age for 3 days, to obtain the modified acid catalytic sol.

[0040] (3) Preparation of the anti-reflective film: coating the film layer on the cleaned glass, placing the coated glass substrate into an oven at 80°C for drying for 1 h, then moving into a muffle furnace, annealing at 400°C for 1 h, to obtain the rare earth modified high radiation resistance high mechanical property high anti-reflective SiO2 film.

[0041] Example Four:

[0042] The preparation method of the rare earth modified high radiation resistance high mechanical property high anti-reflective SiO2 film comprises the following steps:

[0043] (1) Preparation of raw materials: the anti-reflective film raw materials are anhydrous ethanol, tetraethyl orthosilicate, methyl triethoxysilane, deionized water and concentrated nitric acid, and the volume ratio of each component is 10:1:1:0.3:0.3, the mass ratio of the porogen to the sol is 1:50, and the mass ratio of lanthanum nitrate to the sol is 1:120.

[0044] (2) Preparation of the sol: accurately measuring the stoichiometric ratio of the target product, first pouring the concentrated nitric acid, water and anhydrous ethanol into a pre-cleaned beaker, placing it on a magnetic stirrer, stirring at a speed of 1500 r / min for 2 h, then adding tetraethyl orthosilicate, methyl triethoxysilane, mPEG and lanthanum nitrate to the above solution while stirring, moving into a conical flask, and placing it in a water bath at 60°C for 2 h, cooling to room temperature and aging for 3 days to obtain the modified acid catalytic sol.

[0045] (3) Preparation of the anti-reflective film: coating the film layer on the cleaned glass, placing the coated glass substrate into an oven at 80°C for drying for 1 h, then moving into a muffle furnace, annealing at 400°C for 1 h, to obtain the rare earth modified high radiation resistance high mechanical property high anti-reflective SiO2 film.

[0046] Example Five:

[0047] The preparation method of the rare earth modified high radiation resistance high mechanical property high anti-reflective SiO2 film comprises the following steps:

[0048] (1) Preparation of raw materials: the anti-reflective film raw materials are anhydrous ethanol, tetraethyl orthosilicate, methyl triethoxysilane, deionized water and concentrated nitric acid, and the volume ratio of each component is 10:1:1:0.3:0.3, the mass ratio of the porogen to the sol is 1:50, and the mass ratio of lanthanum nitrate to the sol is 1:120.

[0049] (2) Preparation of sol: The concentrated nitric acid, water and anhydrous ethanol were accurately measured according to the stoichiometric ratio of the target product, first poured into a previously cleaned beaker, placed on a magnetic stirrer, stirred at a speed of 1500 r / min for 2 h, then tetraethyl orthosilicate, methyl triethoxysilane, mPEG and lanthanum nitrate were added to the above solution while stirring, moved into a conical flask, water bathed at 60℃ for 2 h, cooled to room temperature and aged for 3 days to obtain the modified acid catalytic sol.

[0050] (3) Preparation of antireflection film: The film layer was coated on the cleaned glass, the coated glass substrate was placed in an oven at 80℃ for 1 h, then moved into a muffle furnace, annealed at 400℃ for 1 h to obtain the rare earth modified high radiation resistance, high mechanical property and high antireflection SiO2 film.

[0051] Example Six:

[0052] The preparation method of the rare earth modified high radiation resistance, high mechanical property and high antireflection SiO2 film comprises the following steps:

[0053] (1) Raw material preparation: The antireflection film raw materials are anhydrous ethanol, tetraethyl orthosilicate, methyl triethoxysilane, deionized water and concentrated nitric acid, and the volume ratio of each component is 10:1:2:0.3:0.3, the mass ratio of the pore former to the sol is 1:50, and the mass ratio of lanthanum nitrate to the sol is 1:120.

[0054] (2) Preparation of sol: The concentrated nitric acid, water and anhydrous ethanol were accurately measured according to the stoichiometric ratio of the target product, first poured into a previously cleaned beaker, placed on a magnetic stirrer, stirred at a speed of 1500 r / min for 2 h, then tetraethyl orthosilicate, methyl triethoxysilane, mPEG and lanthanum nitrate were added to the above solution while stirring, moved into a conical flask, water bathed at 60℃ for 2 h, cooled to room temperature and aged for 3 days to obtain the modified acid catalytic sol.

[0055] (3) Preparation of antireflection film: The film layer was coated on the cleaned glass, the coated glass substrate was placed in an oven at 80℃ for 1 h, then moved into a muffle furnace, annealed at 400℃ for 1 h to obtain the rare earth modified high radiation resistance, high mechanical property and high antireflection SiO2 film.

[0056] Example Seven:

[0057] The preparation method of the rare earth modified high radiation resistance, high mechanical property and high antireflection SiO2 film comprises the following steps:

[0058] (1) Raw material preparation: the raw material of the anti-reflective film is anhydrous ethanol, tetraethyl orthosilicate, methyl triethoxysilane, deionized water and concentrated nitric acid, the volume ratio of each component is 10:1:1:0.3:0.5, the mass ratio of the porogen to the sol is 1:50, and the mass ratio of lanthanum nitrate to the sol is 1:120.

[0059] (2) Preparation of the sol: according to the stoichiometric ratio of the target product, accurately measure the components, first pour the concentrated nitric acid, water and anhydrous ethanol into a pre-cleaned beaker, place it on a magnetic stirrer, stir at a speed of 1500 r / min for 2 h, then add tetraethyl orthosilicate, methyl triethoxysilane, mPEG and lanthanum nitrate to the above solution while stirring, move it into a conical flask, water bath at 60℃ for 2 h, cool to room temperature and then age for 3 days to obtain the modified acid catalytic sol.

[0060] (3) Preparation of the anti-reflective film: coat the film layer on a clean glass, place the coated glass substrate into an oven at 80℃ for drying for 1 h, then move it into a muffle furnace, anneal at 400℃ for 2 h to obtain the rare earth modified high radiation resistance, high mechanical property and high anti-reflective SiO2 film.

[0061] Example Eight:

[0062] The preparation method of the rare earth modified high radiation resistance, high mechanical property and high anti-reflective SiO2 film comprises the following steps:

[0063] (1) Raw material preparation: the raw material of the anti-reflective film is anhydrous ethanol, tetraethyl orthosilicate, methyl triethoxysilane, deionized water and concentrated nitric acid, the volume ratio of each component is 10:1:1:0.3:0.1, the mass ratio of the porogen to the sol is 1:50, and the mass ratio of lanthanum nitrate to the sol is 1:120.

[0064] (2) Preparation of the sol: according to the stoichiometric ratio of the target product, accurately measure the components, first pour the concentrated nitric acid, water and anhydrous ethanol into a pre-cleaned beaker, place it on a magnetic stirrer, stir at a speed of 1500 r / min for 2 h, then add tetraethyl orthosilicate, methyl triethoxysilane, mPEG and lanthanum nitrate to the above solution while stirring, move it into a conical flask, water bath at 60℃ for 2 h, cool to room temperature and then age for 3 days to obtain the modified acid catalytic sol.

[0065] (3) Preparation of the anti-reflective film: coat the film layer on a clean glass, place the coated glass substrate into an oven at 80℃ for drying for 1 h, then move it into a muffle furnace, anneal at 400℃ for 2 h to obtain the rare earth modified high radiation resistance, high mechanical property and high anti-reflective SiO2 film.

[0066] Example Nine:

[0067] The preparation method of the rare earth modified high radiation resistance high mechanical property high reflection reducing SiO2 film comprises the following steps:

[0068] (1) Raw material preparation: the raw material of the reflection reducing film is anhydrous ethanol, tetraethyl orthosilicate, methyl triethoxysilane, deionized water and concentrated nitric acid, the volume ratio of each component is 10:1:1:0.3:0.6, the mass ratio of the pore former to the sol is 1:50, and the mass ratio of lanthanum nitrate to the sol is 1:120.

[0069] (2) Preparation of the sol: according to the stoichiometric ratio of the target product, accurately measure the components, first pour the concentrated nitric acid, water and anhydrous ethanol into a pre-cleaned beaker, place it on a magnetic stirrer, stir at a speed of 1500 r / min for 2 h, then add tetraethyl orthosilicate, methyl triethoxysilane, mPEG and lanthanum nitrate to the above solution while stirring, move it into a conical flask, water bath at 60℃ for 2 h, cool to room temperature, then age for 3 days to obtain the modified acid catalytic sol.

[0070] (3) Preparation of the reflection reducing film: coat the film layer on the clean glass, put the coated glass substrate into an 80℃ oven to dry for 1 h, then move it into a muffle furnace, anneal at 400℃ for 1 h to obtain the rare earth modified high radiation resistance high mechanical property high reflection reducing SiO2 film.

[0071] Example ten:

[0072] The preparation method of the rare earth modified high radiation resistance high mechanical property high reflection reducing SiO2 film comprises the following steps:

[0073] (1) Raw material preparation: the raw material of the reflection reducing film is anhydrous ethanol, tetraethyl orthosilicate, methyl triethoxysilane, deionized water and concentrated nitric acid, the volume ratio of each component is 10:1:1:0.3:0.3, the mass ratio of the pore former to the sol is 1:50, and the mass ratio of lanthanum nitrate to the sol is 1:120.

[0074] (2) Preparation of the sol: according to the stoichiometric ratio of the target product, accurately measure the components, first pour the concentrated nitric acid, water and anhydrous ethanol into a pre-cleaned beaker, place it on a magnetic stirrer, stir at a speed of 1500 r / min for 2 h, then add tetraethyl orthosilicate, methyl triethoxysilane, mPEG and lanthanum nitrate to the above solution while stirring, move it into a conical flask, water bath at 60℃ for 2 h, cool to room temperature, then age for 3 days to obtain the modified acid catalytic sol.

[0075] (3) Preparation of the reflection reducing film: coat the film layer on the clean glass, put the coated glass substrate into an 80℃ oven to dry for 1 h, then move it into a muffle furnace, anneal at 400℃ for 1 h to obtain the rare earth modified high radiation resistance high mechanical property high reflection reducing SiO2 film.

[0076] Example Eleven

[0077] The preparation method of the rare earth modified high radiation resistance high mechanical property high reflection reducing SiO2 film comprises the following steps:

[0078] (1) Raw material preparation: the raw material of the reflection reducing film is anhydrous ethanol, tetraethyl orthosilicate, methyl triethoxysilane, deionized water and concentrated nitric acid, the volume ratio of each component is 10:1:1:0.3:0.3, the mass ratio of the pore former to the sol is 1:50, and the mass ratio of lanthanum nitrate to the sol is 1:120.

[0079] (2) Preparation of the sol: according to the stoichiometric ratio of the target product, accurately measure the amount of concentrated nitric acid, water and anhydrous ethanol, pour them into a pre-cleaned beaker, place it on a magnetic stirrer, stir at a speed of 1500 r / min for 2 h, then add tetraethyl orthosilicate, methyl triethoxysilane, mPEG and lanthanum nitrate to the above solution while stirring, move it into a conical flask, water bath at 60℃ for 2 h, cool to room temperature, then age for 4 days to obtain the modified acid catalytic sol.

[0080] (3) Preparation of the reflection reducing film: coat the film on a clean glass, place the coated glass substrate in an 80℃ oven to dry for 1 h, then move it into a muffle furnace, anneal at 400℃ for 1 h to obtain the rare earth modified high radiation resistance high mechanical property high reflection reducing SiO2 film.

[0081] Example Twelve

[0082] The preparation method of the rare earth modified high radiation resistance high mechanical property high reflection reducing SiO2 film comprises the following steps:

[0083] (1) Raw material preparation: the raw material of the reflection reducing film is anhydrous ethanol, tetraethyl orthosilicate, methyl triethoxysilane, deionized water and concentrated nitric acid, the volume ratio of each component is 10:1:1:0.3:0.3, the mass ratio of the pore former to the sol is 1:50, and the mass ratio of lanthanum nitrate to the sol is 1:120.

[0084] (2) Preparation of the sol: according to the stoichiometric ratio of the target product, accurately measure the amount of concentrated nitric acid, water and anhydrous ethanol, pour them into a pre-cleaned beaker, place it on a magnetic stirrer, stir at a speed of 1500 r / min for 2 h, then add tetraethyl orthosilicate, methyl triethoxysilane, mPEG and lanthanum nitrate to the above solution while stirring, move it into a conical flask, water bath at 60℃ for 2 h, cool to room temperature, then age for 3 days to obtain the modified acid catalytic sol.

[0085] (3) Preparation of the anti-reflective film: coating the film layer on the cleaned glass, putting the coated glass substrate into the oven at 80 DEG C for drying 1h, then moving into the muffle furnace, annealing at 300 DEG C for 2h, to obtain the rare earth modified high anti-radiation high mechanical property high anti-reflective SiO2 film.

[0086] Example XIII:

[0087] The preparation method of the rare earth modified high anti-radiation high mechanical property high anti-reflective SiO2 film comprises the following steps:

[0088] (1) Raw material preparation: the anti-reflective film raw material is anhydrous ethanol, tetraethyl orthosilicate, methyl triethoxysilane, deionized water and concentrated nitric acid, the volume ratio of each component is 10:1:1:0.3:0.3, the mass ratio of the pore former to the sol is 1:50, and the mass ratio of lanthanum nitrate to the sol is 1:120.

[0089] (2) Preparation of the sol: according to the stoichiometric ratio of the target product, accurately measure the concentrated nitric acid, water and anhydrous ethanol, pour them into a pre-cleaned beaker, place it on a magnetic stirrer, stir at a speed of 1500r / min for 2h, then add tetraethyl orthosilicate, methyl triethoxysilane, mPEG and lanthanum nitrate to the above solution while stirring, move into a conical flask, water bath at 60 DEG C for 2h, cool to room temperature, then age for 3 days, to obtain the modified acid catalytic sol.

[0090] (3) Preparation of the anti-reflective film: coating the film layer on the cleaned glass, putting the coated glass substrate into the oven at 80 DEG C for drying 1h, then moving into the muffle furnace, annealing at 500 DEG C for 0.5h, to obtain the rare earth modified high anti-radiation high mechanical property high anti-reflective SiO2 film.

[0091] The above only describes the preferred embodiments of the present application and should not be used to limit the present application, and any modification, equivalent replacement and improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. A method for preparing a high radiation resistance high mechanical property high anti-reflective SiO2 thin film modified by rare earth elements, characterized in that, The porous nanometer film is prepared by using polyethylene glycol (mPEG) as a porogen, tetraethyl orthosilicate (TEOS) and methyl triethoxysilane (MTES) as precursors, nitric acid as a catalyst, and nitrate of rare earth element (lanthanum nitrate, yttrium nitrate, europium nitrate, cerium nitrate, etc.) as an anti-radiation agent. The anhydrous ethanol, TEOS, MTES, deionized water, nitric acid and rare earth substance are sequentially added into a previously cleaned beaker, and then stirred at room temperature for a period of time, and then refluxed in a water bath. After being cooled to room temperature, the required sol is obtained by aging. The sol is coated on glass, and the sol is dried to become a gel, and then the organic matter in the gel is volatilized and the rare earth salt substance is decomposed to generate gas, so as to increase the porosity, form nano-pores, and finally form the porous nanometer film.

2. The method for preparing a high radiation resistance, high mechanical property, high anti-reflective Si02 thin film modified by rare earth elements according to claim 1, characterized in that, The mass ratio of the anti-radiation agent to the sol is 1:10-1:200, the mass ratio of mPEG to the sol is 1:10-1:100, and the volume ratio of tetraethyl orthosilicate, methyl triethoxysilane, anhydrous ethanol, deionized water and concentrated nitric acid is 1:(0.1-6.0):10:0.3:(0.1-1.0).

3. The method for preparing a rare-earth modified SiO2 thin film with high radiation resistance, high mechanical properties, and high anti-reflection properties according to claim 1, characterized in that, The tetraethyl orthosilicate, methyl triethoxysilane, anhydrous ethanol, deionized water, concentrated nitric acid, mPEG and nitrate of rare earth element are sequentially added into a previously cleaned beaker according to the ratio of claim 2, and then stirred at room temperature at a speed of 1-3000 r / min for 0.1-25 h. The obtained mixture is moved into a conical flask and aged in a water bath at 25-100 ℃ for 0.1-25 h, and then aged for 0.1-10 days to obtain the required sol.

4. The method of claim 1, wherein the method of preparing a high radiation resistance, high mechanical property, and high anti-reflective SiO2 thin film modified by a rare earth element is characterized by, The sol is coated on glass, and then dried at 25-200 ℃ for 0.1-25 h, and then heat-treated at 200-600 ℃ for 0.1-25 h.

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