CN117430343A - Corrosion-resistant ultraviolet-resistant SiO 2 Nanometer antireflection film and preparation method thereof - Google Patents
Corrosion-resistant ultraviolet-resistant SiO 2 Nanometer antireflection film and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229910004298 SiO 2 Inorganic materials 0.000 title claims abstract description 23
- 238000005260 corrosion Methods 0.000 title claims abstract description 23
- 230000007797 corrosion Effects 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 20
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 230000005855 radiation Effects 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims abstract description 5
- 238000004528 spin coating Methods 0.000 claims abstract description 4
- 230000002378 acidificating effect Effects 0.000 claims abstract description 3
- 238000009501 film coating Methods 0.000 claims abstract 2
- 239000007888 film coating Substances 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims abstract 2
- 239000011521 glass Substances 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 238000002834 transmittance Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 9
- 230000001070 adhesive effect Effects 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 239000002120 nanofilm Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 230000006750 UV protection Effects 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims 1
- 230000002238 attenuated effect Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- 238000010345 tape casting Methods 0.000 claims 1
- 238000007790 scraping Methods 0.000 abstract description 3
- 108010025899 gelatin film Proteins 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000007171 acid catalysis Methods 0.000 description 3
- 238000005815 base catalysis Methods 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/213—SiO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/73—Anti-reflective coatings with specific characteristics
- C03C2217/732—Anti-reflective coatings with specific characteristics made of a single layer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/112—Deposition methods from solutions or suspensions by spraying
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/114—Deposition methods from solutions or suspensions by brushing, pouring or doctorblading
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
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- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention belongs to the field of antireflection films, and discloses a corrosion-resistant ultraviolet radiation-resistant SiO 2 The nanometer antireflection film and the preparation method thereof solve the problems of poor ultraviolet radiation resistance and the like caused by the capillary absorption of the mesoporous film on water vapor. The preparation method of the film mainly comprises the steps of adopting isobutyl triethoxysilane (IBTS) in the process of preparing the film, wherein the preparation process comprises sol preparation, film coating, drying, heat treatment and the like; the preparation method comprises the following steps of hydrolyzing silicate organic matters, oxysilane and deionized water according to a certain molar ratio in an acidic environment, adding an organic pore-forming agent after refluxing, and dissolving to obtain sol liquid; the obtained sol is coated on the surface of an object by using the processes of spin coating, lifting or film scraping and the like, and the SiO can be obtained after drying 2 The gel film is subjected to heat treatment at 100-400 ℃ to obtain the nano antireflection film. The film and the preparation method thereofThe preparation process is simple, the cost is low, the preparation method is environment-friendly, and the preparation method is suitable for industrial production and popularization.
Description
Technical Field
The invention belongs to the technical field of optical antireflection film materials and preparation thereof, and in particular relates to a high-performance corrosion-resistant ultraviolet radiation-resistant SiO (silicon dioxide) 2 A nanometer antireflection film and a preparation method thereof.
Background
The anti-reflection film is widely applied to a glass cover plate of a solar cell, so that the reflection loss of sunlight is effectively reduced, and the photoelectric conversion efficiency is improved. The common materials of the antireflection film are SiO 2 、TiO 2 、MgF 2 Etc. Wherein, siO is prepared by a sol-gel method 2 The porous antireflection film can better match the cover glass because the refractive index can be adjusted by the porosityRefractive index matching, high antireflection is achieved. The sol-gel method for preparing an antireflection film is classified into a base catalysis method and an acid catalysis method.
SiO prepared by base catalysis method on glass substrate 2 The nano film has the advantages of higher porosity and good antireflection effect, but has lower adhesive force, surface hardness and the like, and is difficult to adapt to the severe working environment of the photovoltaic glass cover plate. Patent application CN105399340A discloses a method for modifying SiO by using trimethylchlorosilane 2 The method for preparing the antireflection film synthesizes SiO under the condition of alkali catalysis 2 Sol, an antireflection film was prepared. The same kind of technology is also granted patent CN108761581B, patent CN110564187A, CN106477909A, CN104230178A, etc. SiO produced by this base catalysis 2 The antireflection film is made of solid SiO 2 Nanoparticles are loosely packed and there are a large number of open pores between particles [ WANG Y, NIE L, LIU J.Inorganic Chemistry,2020,5 (53) 10220-10227.]The surface of the particles contains abundant hydroxyl groups [ inert leaves, liu Shiquan, chengxin, chinese powder technology, 2006, (03): 35-39.]. The surface of such a polar porous structure is extremely prone to adsorb polar contaminants in the environment, resulting in a decrease in the optical performance of the antireflection film. More importantly, the mechanical properties of the film are generally poor, the hardness is lower than 2H, the film can be damaged by slightly wiping the finger, and the film is difficult to popularize as an antireflection film on the surface of a glass cover plate of a solar cell.
Acid catalyzed preparation of SiO on glass substrates 2 Nanoparticle antireflection films generally have lower porosity, higher adhesion and surface hardness. The disadvantage is that the single-layer acid-catalyzed antireflection film has a higher refractive index, which is n with silicate glass such as photovoltaic glass 0 (1.42-1.55) is too small away from the ideal refractive indexThe antireflection effect is very limited. Preparation of SiO in micro-nano particles under acid catalysis condition 2 The molecules are chain-shaped, and exposed polar hydroxyl groups on the molecules can form silica bonds with the surface of glass after the film is prepared, so that the film has good adhesive force, and the film has high hardness by regulating the components and the proportion of the catalyst. Shen (Shen)Similar results are reported in patent CN105776883a and CN102617045A, but neither relates to film adhesion nor hardness characterization, furthermore the dense film material does not reduce too much the refractive index, acid catalyzed SiO 2 The anti-reflection effect of the film is not ideal.
The mesoporous antireflection film is formed by orderly small holes on the surface of the acid catalytic film, which obviously reduces the refractive index of the film layer and improves the acid catalytic SiO 2 Antireflection effect of the film. One of the preparation methods is that a surfactant template is introduced, pores are formed through evaporation induction, and the template agent is removed through high-temperature calcination after film formation, thus obtaining mesoporous SiO 2 A film. The film has lower refractive index and better mechanical property. Application 202010264897 discloses a mesoporous SiO 2 The preparation method of the film comprises the steps of dispersing a pore-forming agent into acid catalytic sol, and sealing and aging to obtain mesoporous acid catalytic sol; and drawing the sol into a film and performing heat treatment to obtain the mesoporous antireflection film. Ye et al adopts Tetraethoxysilane (TEOS) as a precursor and hexadecyl trimethyl ammonium bromide (CTAB) as a template to prepare an antireflection film with the weighted average transmittance up to 98.7%; the film also has excellent mechanical abrasion resistance and can withstand 20 times of repeated rubbing of the paper towel. [ Ye L, zhang S, wang Q, et al RSC Advances,2014,4 (67): 35818]. Xu and the like take TEOS as a precursor and a nonionic triblock copolymer surfactant (F127) as a template agent to prepare the stain-resistant SiO with good optical performance on a quartz glass substrate 2 The mesoporous antireflection film can improve the visible light transmittance of the quartz plate by 5.3 percent, and has stain resistance by performing surface treatment by FAS-17 to reduce pores. [ Sun J, zhang Q, ding R, et al physical Chemistry Chemical Physics,2014, 16 (31): 16684-16693]。
However, if the surface aperture of the mesoporous film is too large, the film can absorb water vapor in the air, seriously reduce the transmittance of the antireflection film, damage the structure of the antireflection film, and possibly further corrode the substrate, thereby greatly shortening the service life of the antireflection film. Furthermore, siO is prepared by sol-gel method 2 In the process, a large amount of organic siloxane and organic modifier are used to prepare mesoporous SiO 2 The antireflection contains at least organic matters which cannot be removed cleanly at high temperature. When the diameter of the surface pores of the antireflection film exceeds 500nm, ultraviolet rays can be incident into the film (application patent: 202111125468. X), organic matters are aged and damaged, and the light transmittance of the antireflection film is reduced.
In conclusion, the film system structure of the acid-catalyzed mesoporous antireflection film is relatively simple, and the refractive index can be changed by adjusting the pore rate. Has higher light transmission performance, high adhesive force and high hardness. However, the problems of poor capillary adsorption of water vapor, poor ultraviolet radiation resistance and the like of the mesoporous film need to be properly solved, so that the requirement of long-term and high-efficiency operation of the solar cell under a field severe environment can be met.
Disclosure of Invention
The invention aims at acid catalysis mesoporous SiO 2 The nano particle antireflection film has the advantages of acid corrosion resistance, ultraviolet radiation resistance and good adhesion to organic matters in the film. The film is characterized in that the film is mainly composed of SiO 2 Nanoparticles are composed, uniform and fine pores are formed among the nanoparticles, and the pore diameter of the nanoparticles is about 10nm to 50nm; the glass is also characterized in that the glass is attached to the surface of the photovoltaic glass, the light transmittance of the glass at 380-1100nm can be improved by 4-6 percent, the pencil hardness reaches the highest level 9H (GB/T1727-92), and the adhesive force reaches the highest level 0 (GB/T1727-1992); after 100 hours of irradiation with 250W ultraviolet lamp, the transmittance is only reduced by 0.45 percent, but the hardness and the adhesive force are unchanged. After 100H of 0.5mol/L hydrochloric acid solution soaking, the hardness was reduced to 9H, the adhesion was reduced to 1 grade, but the transmittance was increased by 1 percentage point.
The invention has the beneficial effects that the adhesive force, the surface hardness, the ultraviolet irradiation resistance and the acid corrosion resistance of the film are obviously improved on the premise of ensuring the obvious antireflection effect of the film.
The invention is realized by adopting the following technical scheme:
(1) Fully hydrolyzing silicate organic matters, isobutyl triethoxysilane (IBTS) and water in ethanol under an acidic condition prepared from hydrochloric acid according to a certain proportion, adding a pore-forming agent after refluxing, and fully dissolving the pore-forming agent to obtain sol colloid;
the mass ratio of the pore-forming agent to the sol is 1:20-1:50, the volume ratio of silicate matters to the organic solvent is 1:10-1:20, the volume ratio of silicate matters to IBTS is 1:0.1-1:1, the volume ratio of silicate matters to water is 1:0.1-1:0.5, and the reaction temperature is 25-100 ℃;
(2) Uniformly coating the sol colloid obtained in the step (1) on the surface of glass by adopting a dipping and pulling method, a spin coating method, a film scraping method and the like, and drying to obtain SiO 2 Calcining the gel film in a muffle furnace to remove the pore-forming agent to obtain porous SiO 2 A film;
the pulling speed is 100-800 mu m/s, the pulling times are 1-3 times, the drying temperature is 80 ℃, and the calcining temperature is 100-500 ℃; the thickness of the porous film is about 80nm to 500nm.
Preferably, the corrosion resistant siloxane in step (1) is isobutyltriethoxysilane.
Preferably, the silicate substance in the step (1) is tetramethyl silicate, tetraethyl silicate, n-propyl silicate, tetrabutyl silicate, etc.; the corrosion resistant siloxane is isobutyl triethoxysilane.
Preferably, the organic porogen in step (1) is one or more of polyethylene glycol monomethyl ether (mPEG) 350, mPEG750, mPEG1000, mPEG1900 or another molecular weight mPEG.
Preferably, the acid used for regulating the pH in the step (1) is one or more of hydrochloric acid, acetic acid and nitric acid;
preferably, the solvent in step (1) is ethanol, methanol, propanol, ethylene glycol, or the like.
Preferably, the water in step (1) is deionized water.
The invention effectively increases the preparation of SiO by sol-gel method 2 The film has ultraviolet resistance and acid corrosion resistance, and is convenient for outdoor use.
Detailed Description
The invention is further illustrated by the following examples, which are intended to be illustrative, not limiting, and not limiting in any way.
Embodiment one:
a corrosion-resistant ultraviolet-resistant antireflection nano film and a preparation method thereof comprise the following steps: tetraethyl orthosilicate, isobutyl triethoxysilane and deionized water are subjected to cohydrolysis in absolute ethyl alcohol for 2 hours according to the volume ratio of 1:1:0.3, the pH value of the solution is adjusted to 5 by hydrochloric acid, and the solution is refluxed for 2 hours to obtain stable modified nano SiO 2 Colloidal solution. And adding a certain amount of mPEG into the sol to obtain the solution for preparing the anti-reflection coating. The solution is coated on a photovoltaic white glass sheet at a speed of 500 mu m/min by using a dipping and pulling method, and after the film material is dried, the film material is heated for 1h at 400 ℃ to obtain the antireflection film.
Embodiment two:
a corrosion-resistant ultraviolet-resistant antireflection nano film and a preparation method thereof comprise the following steps: tetrapropyl orthosilicate, isobutyl triethoxysilane and deionized water are subjected to cohydrolysis in absolute ethyl alcohol for 2 hours according to the mol ratio of 1:1:0.3, the pH value of the solution is adjusted to 3 by utilizing hydrochloric acid, and the solution is refluxed for 2 hours to obtain stable modified nano SiO 2 Colloidal solution. And adding quantitative mPEG into the solution to obtain the solution for preparing the anti-reflection coating. The solution is coated on a photovoltaic white glass sheet at a speed of 400 mu m/min by using a dipping and pulling method, and after a film material is dried, the film material is heated for 1h at 400 ℃ to obtain the antireflection film.
Embodiment III:
a corrosion-resistant ultraviolet-resistant antireflection nano film and a preparation method thereof comprise the following steps: tetrabutyl orthosilicate, isobutyl triethoxysilane and deionized water are subjected to cohydrolysis in absolute ethyl alcohol for 2h according to the mol ratio of 1:1:0.3, the pH value of the solution is regulated and 5 is regulated by hydrochloric acid, and the solution is refluxed for 2h to obtain stable modified nano SiO 2 Colloidal solution. A solution for preparing the anti-reflection coating is obtained. The solution is coated on a photovoltaic white glass sheet at a speed of 200 mu m/min by using a dipping and pulling method, and is heated for 1h at 400 ℃ to obtain the antireflection film.
Embodiment four:
a corrosion-resistant ultraviolet-resistant antireflection nano film and a preparation method thereof comprise the following steps: tetraethyl orthosilicate, isobutyl triethoxysilane and deionized water are subjected to cohydrolysis in absolute ethyl alcohol for 2 hours according to the volume ratio of 1:1:0.3, the pH value of the solution is adjusted to 5 by hydrochloric acid, and the solution is refluxed for 2 hours to obtain stable modified nano SiO 2 Colloidal solution. And adding a certain amount of mPEG into the sol to obtain the solution for preparing the anti-reflection coating. The solution is coated on a photovoltaic white glass sheet by a film scraping method, and after a film material is dried, the film material is heated for 1h at 400 ℃ to obtain the antireflection film.
Fifth embodiment:
a corrosion-resistant ultraviolet-resistant antireflection nano film and a preparation method thereof comprise the following steps: tetraethyl orthosilicate, isobutyl triethoxysilane and deionized water are subjected to cohydrolysis in absolute ethyl alcohol for 2 hours according to the volume ratio of 1:1:0.3, the pH value of the solution is adjusted to 5 by hydrochloric acid, and the solution is refluxed for 2 hours to obtain stable modified nano SiO 2 Colloidal solution. And adding a certain amount of mPEG into the sol to obtain the solution for preparing the anti-reflection coating. The solution is coated on a photovoltaic white glass sheet at a speed of 800rpm by using a spin coating method, and after a film material is dried, the film material is heated at 400 ℃ for 1 hour, so that the antireflection film can be obtained.
Drawings
FIG. 1 is a schematic diagram of selected SiO of the present invention 2 The magnification is 40000 times, which proves that the surface of the film has uniform pores, which is beneficial to reducing the refractive index of the film.
Fig. 2 is a graph showing the transmittance ratio of the ultra-white glass coated with the anti-reflective film selected by the present invention compared with that of the uncoated glass, and it can be seen that the layer has good properties.
FIG. 3 is a graph showing the film material of the selected antireflection film coated glass of the present invention after 100 hours of ultraviolet irradiation by a grippa tester and tearing using a 3M tape. It can be seen that the adhesive tape is torn and pulled without obvious falling off.
FIG. 4 is a photograph of a pencil hardness score mark of 9H using a pencil after 100 hours of ultraviolet irradiation of the selected antireflection film-coated glass according to the present invention, and it can be seen that sufficient hardness is achieved.
FIG. 5 is a film material of the selected antireflection film coated glass of the present invention after 100h of 0.5mol/L hydrochloric acid solution immersion in a hundred blade adhesion tester scratch and tearing with a 3M tape. It can be seen that the adhesive tape is torn and pulled without obvious falling off.
FIG. 6 is a photograph of a pencil hardness tester scratch after immersing the selected glass coated with an antireflection film of the present invention in a hydrochloric acid solution of 0.5mol/L for 100 hours, using a pencil of 9H, it can be seen that sufficient hardness is achieved.
Claims (8)
1. Corrosion-resistant ultraviolet radiation-resistant SiO 2 The nanometer antireflection film and the preparation method thereof, wherein the film is attached on transparent substrates such as glass and the like, and is characterized in that: the film is mainly composed of SiO 2 Nanoparticle composition, siO 2 Pores are uniformly distributed among the particles; when the light-absorbing agent is coated on the surface of the light Fu Bai glass, the light transmittance of the glass within the range of 380-1100nm can be improved by 4-6 percentage points; the hardness of the pencil reaches more than 9H (GB/T1727-92) and the adhesive force reaches more than 0 (GB/T1727-1992); after the ultraviolet lamp with the power of 250W irradiates for 100 hours, the light transmittance is reduced by 0.45 percent, and the hardness and the adhesive force are not attenuated; after 0.5mol/L hydrochloric acid solution is soaked for 100 hours, the hardness is reduced to 8H, the adhesive force is reduced to 1 level, but the light transmittance is improved by 1.0 percent; the preparation method is characterized in that: in the sol preparation process, isobutyl triethoxysilane (IBTS) with excellent corrosion resistance and ultraviolet resistance is adopted as a co-hydrolysis reactant, and the sol preparation process comprises sol preparation, film coating, drying, heat treatment and the like.
2. The anti-corrosion ultraviolet-resistant antireflection film and the preparation method thereof as claimed in claim 1, wherein: the porous nano SiO 2 The particle size of the film is about 20-300 nm, the thickness of the nano film is 80-800 nm, and the porous nano SiO 2 The pore diameter of the film is about 20 nm.
3. The anti-corrosion ultraviolet-resistant antireflection film and the preparation method thereof as claimed in claim 1, wherein: in the sol-gel process, silicate organic matters, IBTS, organic macromolecular pore-forming agents and deionized water are hydrolyzed in an acidic environment according to a certain molar ratio, and sol liquid is obtained after reflux.
4. The anti-corrosion ultraviolet-resistant antireflection film and the preparation method thereof as claimed in claim 1, wherein: the organic pore-forming agent is one or more of polyethylene glycol monomethyl ether 350, polyethylene glycol monomethyl ether 750, polyethylene glycol monomethyl ether 1000 and polyethylene glycol monomethyl ether 1900.
5. The anti-corrosion ultraviolet-resistant antireflection film and the preparation method thereof as claimed in claim 1, wherein: the acid used for regulating the pH is one or more of hydrochloric acid, acetic acid and nitric acid; the solvent is one or more of ethanol, methanol and propanol.
6. The anti-corrosion ultraviolet-resistant antireflection film and the preparation method thereof as claimed in claim 1, wherein: the mass ratio of the pore-forming agent to the sol is 1:20-1:50, the volume ratio of silicate matters to the organic solvent is 1:10-20, the volume ratio of silicate organic matters to IBTS is 1:0.1-1:1, and the volume ratio of silicate organic matters to water is 1:0.1-1:0.5.
7. The anti-corrosion ultraviolet-resistant antireflection film and the preparation method thereof as claimed in claim 1, wherein: the reaction temperature is 25-100 ℃, the reaction time is 1-10 h, the reflux temperature is 50-100 ℃, and the reflux time is 1-12 h. The aging time is 0-48 h, and the heat treatment temperature of the film is 100-550 ℃.
8. The corrosion-resistant ultraviolet-resistant antireflection film and the preparation method thereof as claimed in claims 1 to 7, characterized in that: methods for applying the sol to the transparent substrate include, but are not limited to, a pulling method, a spin coating method, a doctor blading method, a spraying method, and the like.
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