CN117285258A - Anti-reflection film and preparation method thereof - Google Patents
Anti-reflection film and preparation method thereof Download PDFInfo
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- CN117285258A CN117285258A CN202311120656.2A CN202311120656A CN117285258A CN 117285258 A CN117285258 A CN 117285258A CN 202311120656 A CN202311120656 A CN 202311120656A CN 117285258 A CN117285258 A CN 117285258A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000003756 stirring Methods 0.000 claims abstract description 47
- 239000002243 precursor Substances 0.000 claims abstract description 42
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 26
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 230000032683 aging Effects 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000010992 reflux Methods 0.000 claims abstract description 12
- 239000004246 zinc acetate Substances 0.000 claims abstract description 12
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000007789 sealing Methods 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 7
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000137 annealing Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 9
- 238000004140 cleaning Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 238000003483 aging Methods 0.000 abstract 1
- 238000005815 base catalysis Methods 0.000 abstract 1
- 238000007654 immersion Methods 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 19
- 238000007598 dipping method Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000002390 rotary evaporation Methods 0.000 description 5
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- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 235000009161 Espostoa lanata Nutrition 0.000 description 1
- 240000001624 Espostoa lanata Species 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
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- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 230000001699 photocatalysis Effects 0.000 description 1
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- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
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- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection 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
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/23—Mixtures
-
- 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
Abstract
The invention discloses an antireflection film and a preparation method thereof, wherein the preparation method comprises the following steps: adding 3- (2, 3-glycidoxy) propyl trimethoxy silane and hexamethyldisilazane into methanol, and reacting to obtain modified organic silicon; uniformly mixing tetramethoxysilane and modified organic silicon to obtain a mixed solution, and reacting under the condition of base catalysis to obtain modified SiO 2 Precursor sol; adding diethanolamine into isopropanol, then adding zinc acetate, and stirring for reaction to obtain ZnO precursor sol; adding ZnO precursor sol into modified SiO 2 Regulating pH in precursor sol, sealing, ageing, heating and refluxing to obtain modified SiO 2 -ZnO composite sol; modified SiO 2 Preparing the ZnO composite sol on a transparent substrate by an immersion pulling method to obtain the antireflection film; the antireflection film can improve the transmittance of solar rays and the photoelectric conversion efficiency, and has the effects of dirt resistance, hydrophobicity and self-cleaning.
Description
Technical Field
The invention relates to the technical field of antireflection films, in particular to an antireflection film and a preparation method thereof.
Background
The antireflection film is mainly used for reducing redundant reflected light on the surface of a lens or an optical element, so that the light transmittance of the element is improved, and therefore, the antireflection film is also called an antireflection film. The anti-reflection film is widely applied to the fields of display panels, solar cells, optical lenses, building glass and the like. There are many types of antireflection films available to meet the demands of the fields of optics, energy, and the like. However, with technological progress and social development, the requirements of people on the anti-reflection film performance are higher and higher, and not only excellent optical performance but also excellent hydrophobicity, friction resistance, self-cleaning performance and the like are required; in addition, there is a need for an antireflection film that can have an antireflection effect in a specific wavelength region. Therefore, the research of high-performance multifunctional antireflection films is a very potential problem in the present and future, both from the viewpoint of the huge yield of the antireflection films and from the viewpoint of wide use.
The research of the anti-reflection film depends on the preparation process, and the high-quality anti-reflection film is beneficial to the development of the performance research and application of the anti-reflection film. With the development of social progress and scientific technology, more and more preparation processes are applied to the research of the antireflection film. According to its working principle, it is mainly classified into physical vapor deposition (PhysicalVaporDeposition, PVD), chemical vapor deposition (Chemical VaporDeposition, CVD) and Sol-Gel (Sol-Gel).
Sol-Gel (Sol-Gel) is a method in which a substance such as a metal compound (inorganic salt or metal alkoxide) which is easily hydrolyzed in a solvent is reacted with water to form a Sol through hydrolysis and polycondensation, the Sol is coated on a substrate to form a liquid film, and finally the liquid film is converted into an amorphous or crystalline film by heat treatment or the like. Wherein, the viscosity, water quantity and coating process parameters (pulling speed, dipping speed and time) of the sol affect the thickness and structure of the single-layer film. The sol-gel method has been used for preparing various films since the 80 s of the 20 th century, and has a series of advantages of low cost, simple operation, quantitative doping, controllable thickness and the like, so that the method is widely applied to the preparation of the anti-reflection film. The film prepared by the sol-gel method is not only suitable for large-area production, but also can be directly used without any subsequent treatment.
Chinese patent document CN202110681570.1 discloses an antireflection film for GaAs solar cell based on magnetron sputtering, and a preparation method and application thereof. The antireflection film comprises a ZnO layer and SiO 2 A layer of ZnO and SiO 2 Layer crossingStacking instead of the ZnO layer and SiO 2 The optical thickness of each layer is 0.1-0.25 times of the reference wavelength of the corresponding material of each layer; the refractive index of the ZnO layer is 1.9-2.1, and the SiO 2 The refractive index of the layer is 1.4-1.6. The anti-reflection film prepared by the invention has better matching performance with solar spectrum in a wide spectrum range (the optimal average reflectivity is as low as 7.05 percent in a range of 300-1400 nm), and the anti-reflection effect is improved compared with that of a conventional anti-reflection film system.
The existing anti-reflection film is placed outdoors in actual use, is easy to suffer from wind and sun exposure and adsorbs moisture and dust in the air, so that the anti-reflection performance is reduced after a period of use.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide the antireflection film and the preparation method thereof, wherein the antireflection film prepared by the preparation method can reduce directional reflection of glass, increase internal reflection effect, promote the antireflection film to effectively absorb solar energy, improve the transmittance of solar rays, furthest improve photoelectric conversion efficiency, and the light transmittance of the photovoltaic glass subjected to double-sided treatment can reach 94.2% -96.8%, is not easy to absorb water and dust and has self-cleaning property.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the antireflection film comprises the following steps:
(1) Adding 3- (2, 3-epoxypropoxy) propyl trimethoxy silane and hexamethyldisilazane into methanol, and continuously introducing N 2 Stirring for reaction to obtain modified organic silicon;
(2) Uniformly mixing tetramethoxysilane and modified organic silicon to obtain a mixed solution, then adding methanol, ammonia water and deionized water, and uniformly stirring to obtain modified SiO 2 Precursor sol;
(3) Adding diethanolamine into isopropanol, stirring and mixing uniformly, then adding zinc acetate, and stirring and reacting until the solution is completely clear to obtain ZnO precursor sol;
(4) Adding the ZnO precursor sol obtained in the step (3) into the modified SiO obtained in the step (2) 2 In the precursor sol, stirring uniformly, regulatingSol pH, sealing aging, heating reflux to obtain modified SiO 2 -ZnO composite sol;
(5) Modified SiO 2 The ZnO composite sol is used for preparing a double-sided modified coating on a transparent substrate by a dip-and-pull method, and then annealing treatment is carried out, namely, an antireflection film is obtained on the transparent substrate.
Preferably, in the step (1), the molar ratio of 3- (2, 3-glycidoxy) propyl trimethoxysilane to hexamethyldisilazane is 1:1.
preferably, in the step (1), the stirring reaction condition is that stirring is carried out for 18-24 hours at 40-60 ℃.
Preferably, in the step (2), the molar ratio of tetramethoxysilane to modified organosilicon is 10:0.1 to 0.4; the volume ratio of the mixed solution to the methanol to the ammonia water to the deionized water is 1: 5-10: 0.2 to 0.5:0.1; stirring for 4-6 h at 40-60 ℃.
Preferably, in the step (3), the mol ratio of diethanolamine to zinc acetate is 1:1.
preferably, in the step (3), the stirring reaction condition is 50-70 ℃ and the stirring reaction is carried out for 2-4 hours.
Preferably, in step (4), the SiO is modified 2 SiO in ZnO composite sol 2 The mol ratio of ZnO to ZnO is 4-8: 1.
preferably, in the step (4), the pH of the sol is regulated to 7.5-9.5, the aging condition is aging for 5-10 days at 25-35 ℃, and the heating reflux time is 8-12 h.
Preferably, in the step (5), the temperature is 15-35 ℃, the humidity is 20-40%, the pulling speed is 800-2000 mu m/s, the annealing temperature is 200-500 ℃, and the annealing time is 1-2 h.
The invention also discloses an antireflection film prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention provides an antireflection film, which is prepared by synthesizing modified organic silicon from 3- (2, 3-glycidoxy) propyl trimethoxy silane and hexamethyldisilazane through a ring opening addition reaction, and then taking the modified organic silicon and tetramethoxy silane together as the materialsSilicon source monomer, alcohol solvent, alkali catalyst and deionized water are added, and under the condition of alkali catalysis, a sol-gel method is utilized to prepare modified SiO 2 Precursor sol; then zinc acetate is used as a precursor to prepare ZnO precursor sol, and modified SiO is prepared 2 The precursor sol and the ZnO precursor sol are mixed to prepare the modified SiO 2 -ZnO composite sol; finally, modified SiO 2 The ZnO composite sol is formed into a film on a transparent substrate by a dipping and pulling method, and is cured at high temperature to obtain an antireflection film, wherein the antireflection film can reduce directional reflection of glass, increase internal reflection effect, promote the glass to effectively absorb solar energy, improve solar ray transmittance, furthest improve photoelectric conversion efficiency, and the photovoltaic glass subjected to double-sided treatment has light transmittance of 94.2% -96.8%, is not easy to absorb water and dust and has self-cleaning property.
2) The invention synthesizes and uses modified organic silicon, introduces a nitrogen-silicon bond into 3- (2, 3-glycidoxy) propyl trimethoxy silane to obtain modified organic silicon through the reaction of-NH-in hexamethyldisilazane and epoxy group in 3- (2, 3-glycidoxy) propyl trimethoxy silane, and simultaneously the modified organic silicon also contains silicon hydroxyl, and the modified organic silicon and tetramethoxy silane can provide a large number of crosslinking sites for the dehydration condensation reaction of sol precursors; the introduction of the nitrogen-silicon bond in the modified organic silicon can endow the anti-reflection film with excellent anti-fouling, hydrophobic and self-cleaning properties, and can effectively improve the weather resistance.
3) The invention provides a modified SiO 2 The ZnO composite sol can form an antireflection film after dipping and pulling, znO has high transmittance in a wide spectrum range, is a wide forbidden band semiconductor material, has a photocatalysis effect, can degrade organic matters, can take away impurities after being washed by rain, and can be used with modified SiO 2 The functions of decontamination and self-cleaning are cooperatively achieved; whereas ZnO has relatively weak chemical stability, and will modify SiO 2 After being compounded with ZnO, the composite material can effectively increase the physical and chemical stability of the film, thereby improving the mechanical strength and weather resistance of the film.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples. Of course, the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Unless otherwise specified, both chemical reagents and materials in the present invention are purchased through a market route or synthesized from raw materials purchased through a market route.
The photovoltaic glass sizes were 12mm by 44mm by 3mm and were purchased from Jiangxi Anyuan photovoltaic glass Limited company.
The invention will be further illustrated by the following examples.
Example 1
The preparation method of the antireflection film comprises the following steps:
(1) 1mol of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane and 1mol of hexamethyldisilazane are added to 500mL of methanol at 60℃N 2 Stirring and reacting for 24 hours in the atmosphere, and removing unreacted substances by rotary evaporation after the reaction is finished to obtain modified organic silicon;
(2) Uniformly mixing 10mol of tetramethoxysilane and 0.4mol of modified organic silicon to obtain a mixed solution, adding 1000mL of methanol, 50mL of 25wt% ammonia water and 10mL of deionized water into 100mL of the mixed solution, and stirring at 60 ℃ for 6h to obtain modified SiO 2 Precursor sol;
(3) Adding 1mol of diethanolamine into 500mL of isopropanol, stirring and mixing uniformly, then adding 1mol of zinc acetate, and stirring and reacting for 4 hours at 70 ℃ until the solution is completely clarified to obtain ZnO precursor sol;
(4) Adding the ZnO precursor sol obtained in the step (3) into the modified SiO obtained in the step (2) 2 Stirring the precursor sol for 4 hours at normal temperature, adjusting the pH of the sol to 8, sealing and aging for 8 days at 35 ℃, and then heating and refluxing for 10 hours to obtain modified SiO 2 ZnO composite sol (modified SiO) 2 The molar ratio of ZnO to ZnO is 8: 1) The method comprises the steps of carrying out a first treatment on the surface of the
(5) Modified SiO at 25deg.C and humidity of 30% 2 The ZnO composite sol is used for preparing a double-sided modified coating on the photovoltaic glass by a dipping and pulling method, the pulling speed is 1000 mu m/s, and then annealing treatment is carried out at 400 ℃ for 1.5 hours, so that the antireflection film is obtained on the photovoltaic glass.
Example 2
The preparation method of the antireflection film comprises the following steps:
(1) 1mol of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane and 1mol of hexamethyldisilazane are added to 500mL of methanol at 40℃and N 2 Stirring and reacting for 18h in the atmosphere, and removing unreacted substances by rotary evaporation after the reaction is finished to obtain modified organic silicon;
(2) Uniformly mixing 10mol of tetramethoxysilane and 0.1mol of modified organic silicon to obtain a mixed solution, adding 500mL of methanol, 20mL of 25wt% ammonia water and 10mL of deionized water into 100mL of the mixed solution, and stirring for 4h at 40 ℃ to obtain modified SiO 2 Precursor sol;
(3) Adding 1mol of diethanolamine into 500mL of isopropanol, stirring and mixing uniformly, then adding 1mol of zinc acetate, and stirring and reacting at 50 ℃ for 2 hours until the solution is completely clarified to obtain ZnO precursor sol;
(4) Adding the ZnO precursor sol obtained in the step (3) into the modified SiO obtained in the step (2) 2 Stirring the precursor sol for 2 hours at normal temperature, adjusting the pH of the sol to 8, sealing and aging for 8 days at 25 ℃, and then heating and refluxing for 10 hours to obtain modified SiO 2 ZnO composite sol (modified SiO) 2 The molar ratio of ZnO to ZnO is 4: 1) The method comprises the steps of carrying out a first treatment on the surface of the
(5) Modified SiO at 25deg.C and humidity of 30% 2 The ZnO composite sol is used for preparing a double-sided modified coating on the photovoltaic glass by a dipping and pulling method, the pulling speed is 1000 mu m/s, and then annealing treatment is carried out at 400 ℃ for 1.5 hours, so that the antireflection film is obtained on the photovoltaic glass.
Example 3
The preparation method of the antireflection film comprises the following steps:
(1) 1mol of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane and 1mol of hexamethyldisilazane are added to 500mL of methanol at 45℃and N 2 Stirring and reacting for 20 hours in the atmosphere, and removing unreacted substances by rotary evaporation after the reaction is finished to obtain modified organic silicon;
(2) Uniformly mixing 10mol of tetramethoxysilane and 0.2mol of modified organic silicon to obtain a mixed solution, and then adding 600mL of methanol, 30mL of 25wt% ammonia water and 10mL of deionized water into 100mL of the mixed solutionStirring the sub-water at 45 ℃ for 5 hours to obtain modified SiO 2 Precursor sol;
(3) Adding 1mol of diethanolamine into 500mL of isopropanol, stirring and mixing uniformly, then adding 1mol of zinc acetate, and stirring and reacting for 3 hours at 55 ℃ until the solution is completely clarified to obtain ZnO precursor sol;
(4) Adding the ZnO precursor sol obtained in the step (3) into the modified SiO obtained in the step (2) 2 Stirring the precursor sol for 3 hours at normal temperature, adjusting the pH of the sol to 8, sealing and aging for 8 days at 30 ℃, and then heating and refluxing for 10 hours to obtain modified SiO 2 ZnO composite sol (modified SiO) 2 The molar ratio of ZnO to ZnO is 5: 1) The method comprises the steps of carrying out a first treatment on the surface of the
(5) Modified SiO at 25deg.C and humidity of 30% 2 The ZnO composite sol is used for preparing a double-sided modified coating on the photovoltaic glass by a dipping and pulling method, the pulling speed is 1000 mu m/s, and then annealing treatment is carried out at 400 ℃ for 1.5 hours, so that the antireflection film is obtained on the photovoltaic glass.
Example 4
The preparation method of the antireflection film comprises the following steps:
(1) 1mol of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane and 1mol of hexamethyldisilazane are added to 500mL of methanol at 50℃N 2 Stirring and reacting for 22 hours in the atmosphere, and removing unreacted substances by rotary evaporation after the reaction is finished to obtain modified organic silicon;
(2) Uniformly mixing 10mol of tetramethoxysilane and 0.3mol of modified organic silicon to obtain a mixed solution, adding 800mL of methanol, 40mL of 25wt% ammonia water and 10mL of deionized water into 100mL of the mixed solution, and stirring at 50 ℃ for 5 to obtain modified SiO 2 Precursor sol;
(3) Adding 1mol of diethanolamine into 500mL of isopropanol, stirring and mixing uniformly, then adding 1mol of zinc acetate, and stirring and reacting at 60 ℃ for 3 hours until the solution is completely clarified to obtain ZnO precursor sol;
(4) Adding the ZnO precursor sol obtained in the step (3) into the modified SiO obtained in the step (2) 2 Stirring the precursor sol for 3 hours at normal temperature, adjusting the pH of the sol to 8, sealing and aging for 8 days at 30 ℃, and then heating and refluxing for 10 hours to obtain modified SiO 2 ZnO composite sol (modified SiO) 2 With ZnOThe molar ratio of (2) is 6: 1) The method comprises the steps of carrying out a first treatment on the surface of the
(5) Modified SiO at 25deg.C and humidity of 30% 2 The ZnO composite sol is used for preparing a double-sided modified coating on the photovoltaic glass by a dipping and pulling method, the pulling speed is 1000 mu m/s, and then annealing treatment is carried out at 400 ℃ for 1.5 hours, so that the antireflection film is obtained on the photovoltaic glass.
Comparative example 1
The preparation method of the antireflection film comprises the following steps:
(1) 1mol of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane and 1mol of hexamethyldisilazane are added to 500mL of methanol at 60℃N 2 Stirring and reacting for 24 hours in the atmosphere, and removing unreacted substances by rotary evaporation after the reaction is finished to obtain modified organic silicon;
(2) Uniformly mixing 10mol of tetramethoxysilane and 0.4mol of modified organic silicon to obtain a mixed solution, adding 1000mL of methanol, 50mL of 25wt% ammonia water and 10mL of deionized water into 100mL of the mixed solution, and stirring at 60 ℃ for 6h to obtain modified SiO 2 Precursor sol;
(3) The modified SiO obtained in the step (2) is treated 2 Stirring the precursor sol for 4 hours at normal temperature, adjusting the pH of the sol to 8, sealing and aging for 8 days at 35 ℃, and then heating and refluxing for 10 hours to obtain modified SiO 2 Sol;
(4) Modified SiO at 25deg.C and humidity of 30% 2 The sol is used for preparing a double-sided modified coating on the photovoltaic glass by a dipping and pulling method, the pulling speed is 1000 mu m/s, and then annealing treatment is carried out for 1.5 hours at 400 ℃, so that the antireflection film is obtained on the photovoltaic glass.
Comparative example 2
The preparation method of the antireflection film comprises the following steps:
(1) 1000mL of methanol, 50mL of 25wt% ammonia water, 10mL of deionized water were added to 100mL of tetramethoxysilane, and the mixture was stirred at 60℃for 6 hours to obtain SiO 2 Precursor sol;
(2) Adding 1mol of diethanolamine into 500mL of isopropanol, stirring and mixing uniformly, then adding 1mol of zinc acetate, and stirring and reacting for 4 hours at 70 ℃ until the solution is completely clarified to obtain ZnO precursor sol;
(3) The ZnO precursor sol obtained in the step (3) is preparedAdding the mixture into SiO obtained in the step (2) 2 Stirring the precursor sol for 4 hours at normal temperature, adjusting the pH of the sol to 8, sealing and aging for 8 days at 35 ℃, and then heating and refluxing for 10 hours to obtain SiO 2 ZnO composite Sol (SiO) 2 The molar ratio of ZnO to ZnO is 8: 1) The method comprises the steps of carrying out a first treatment on the surface of the
(4) SiO was prepared at 25℃and 30% humidity 2 The ZnO composite sol is used for preparing a double-sided modified coating on the photovoltaic glass by a dipping and pulling method, the pulling speed is 1000 mu m/s, and then annealing treatment is carried out at 400 ℃ for 1.5 hours, so that the antireflection film is obtained on the photovoltaic glass.
Comparative example 3
The preparation method of the antireflection film comprises the following steps:
(1) Adding 1mol of diethanolamine into 500mL of isopropanol, stirring and mixing uniformly, then adding 1mol of zinc acetate, and stirring and reacting for 4 hours at 70 ℃ until the solution is completely clarified to obtain ZnO precursor sol;
(2) Stirring the ZnO precursor sol obtained in the step (1) for 4 hours at normal temperature, adjusting the pH of the sol to 8, sealing and aging for 8 days at 35 ℃, and then heating and refluxing for 10 hours to obtain ZnO sol;
(3) Preparing a double-sided modified coating on the photovoltaic glass by a ZnO sol through a dipping and pulling method at 25 ℃ and humidity of 30%, wherein the pulling speed is 1000 mu m/s, and then annealing at 400 ℃ for 1.5 hours to obtain the antireflection film on the photovoltaic glass.
Performance tests are carried out on the antireflection films prepared in examples 1 to 4 and comparative examples 1 to 3, and the average light transmittance of the antireflection films in the visible light range is measured by using a UV757CRT ultraviolet-visible spectrophotometer; determining the hardness of the antireflection film by using a QHQ-A pencil hardness tester; measuring the water contact angle of the antireflection film by using a PT-705A water contact angle meter; after 200 times of friction by using an alcohol cotton ball loaded with a weight of 100g, respectively measuring the light transmittance and the water contact angle of the antireflection film; immersing the photovoltaic glass plated with the antireflection film in 80mL methyl orange solution with concentration of 5mg/L, pH of 3, adsorbing for 1 hr, and using 20W ultraviolet germicidal lamp (lambda) max =253.7 nm) at a distance of 10cm from the film, and the photocatalytic degradation rate of methyl orange was measured using a type 722 spectrophotometer (catalytic time 4 h); the specific data are shown in Table 1.
TABLE 1 anti-reflective film Performance test results
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The preparation method of the antireflection film is characterized by comprising the following steps:
(1) Adding 3- (2, 3-epoxypropoxy) propyl trimethoxy silane and hexamethyldisilazane into methanol, and continuously introducing N 2 Stirring for reaction to obtain modified organic silicon;
(2) Uniformly mixing tetramethoxysilane and modified organic silicon to obtain a mixed solution, then adding methanol, ammonia water and deionized water, and uniformly stirring to obtain modified SiO 2 Precursor sol;
(3) Adding diethanolamine into isopropanol, stirring and mixing uniformly, then adding zinc acetate, and stirring and reacting until the solution is completely clear to obtain ZnO precursor sol;
(4) Adding the ZnO precursor sol obtained in the step (3) into the modified SiO obtained in the step (2) 2 In the precursor sol, stirring uniformly, regulating the pH of the sol, sealing, aging, heating and refluxing to obtain modified SiO 2 -ZnO composite sol;
(5) Modified SiO 2 The ZnO composite sol is used for preparing a double-sided modified coating on a transparent substrate by a dip-and-pull method, and then annealing treatment is carried out, namely, an antireflection film is obtained on the transparent substrate.
2. The method according to claim 1, wherein in the step (1), the molar ratio of 3- (2, 3-glycidoxy) propyltrimethoxysilane to hexamethyldisilazane is 1:1.
3. the process according to claim 1, wherein in the step (1), the stirring reaction is carried out at 40 to 60℃for 18 to 24 hours.
4. The method according to claim 1, wherein in the step (2), the molar ratio of tetramethoxysilane to modified silicone is 10:0.1 to 0.4; the volume ratio of the mixed solution to the methanol to the ammonia water to the deionized water is 1: 5-10: 0.2 to 0.5:0.1; stirring for 4-6 h at 40-60 ℃.
5. The method according to claim 1, wherein in the step (3), the molar ratio of diethanolamine to zinc acetate is 1:1.
6. the process according to claim 1, wherein in the step (3), the stirring reaction is carried out at 50 to 70℃for 2 to 4 hours.
7. The method according to claim 1, wherein in the step (4), siO is modified 2 SiO in ZnO composite sol 2 The mol ratio of ZnO to ZnO is 4-8: 1.
8. the method according to claim 1, wherein in the step (4), the pH of the sol is adjusted to 7.5 to 9.5, the aging condition is aging at 25 to 35 ℃ for 5 to 10 days, and the heat reflux time is 8 to 12 hours.
9. The method according to claim 1, wherein in the step (5), the temperature at the time of the pulling impregnation is 15 to 35 ℃, the humidity is 20 to 40%, the pulling speed is 800 to 2000 μm/s, the annealing temperature is 200 to 500 ℃, and the annealing time is 1 to 2 hours.
10. An antireflection film produced by the production method according to any one of claims 1 to 9.
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