CN117331150A - Multilayer composite SiO 2 Preparation method of antireflection film - Google Patents
Multilayer composite SiO 2 Preparation method of antireflection film Download PDFInfo
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- 229910004298 SiO 2 Inorganic materials 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000013307 optical fiber Substances 0.000 claims abstract description 13
- 230000003287 optical effect Effects 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 230000000694 effects Effects 0.000 claims abstract description 4
- 230000003595 spectral effect Effects 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000007747 plating Methods 0.000 claims description 27
- 239000002585 base Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000002834 transmittance Methods 0.000 claims description 22
- 238000004140 cleaning Methods 0.000 claims description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 18
- 101100203596 Caenorhabditis elegans sol-1 gene Proteins 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- 210000002381 plasma Anatomy 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 74
- 238000004891 communication Methods 0.000 abstract description 9
- 238000001514 detection method Methods 0.000 abstract description 3
- 239000002356 single layer Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 230000003749 cleanliness Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
Classifications
-
- 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
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
-
- 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
-
- 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
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
Abstract
The invention discloses a multilayer composite SiO 2 The preparation method of the antireflection film comprises the following steps: A/A/B/B four-layer SiO is prepared by a sol-gel pulling coating method 2 Films wherein A is acid catalyzed SiO 2 Sol and base catalyzed SiO 2 Sol is prepared by mixing, and alkali-catalyzed SiO 2 Sol and acid catalyzed SiO 2 The volume ratio of the sol is 1:9, and B is prepared from the HSNs sol treated by HMDS, and the strong anti-reflection effect in a wide spectral range is realized through the sequential four-layer lifting superposition of A/A/B/B. The four-layer composite SiO prepared by the invention 2 The anti-reflection film has various performance indexes in the infrared wavelength range of 1300 nm-1600 nm superior to those of the traditional single-layer, double-layer or four-layer SiO 2 The antireflection film is suitable for optical communication components such as an optical fiber connector, a wavelength division multiplexer and the like in the field of optical fiber communication,and can be widely applied to the infrared optical fields such as military, atmospheric detection, aerospace and the like.
Description
Technical Field
The invention belongs to the technical field of optics, in particular to a multilayer composite SiO 2 A method for preparing antireflection film.
Background
The infrared technology is mainly used in the military field at first, and with the development of technology, the infrared technology also plays an important role in the civil fields of atmosphere detection, aerospace, aviation and the like gradually, and more optical devices are required to work in the infrared band. In an infrared optical system, the transmittance of infrared light energy determines the performance of the system; the reflection of the surface of the optical element is reduced, and the transmittance of the optical system in the working band is increased, so that the method has great significance for production practice. Light in the predominantly infrared region is used in fiber optic communications, typically in the wavelength range 800nm to 1600nm, with 1310nm and 1550nm being the most common wavelengths. However, because of the high optical fiber loss and reflection in the optical fiber communication system, the attenuation of the signal in the optical fiber transmission is caused, and the effective distance and volume of the data transmission are affected. Therefore, an antireflection film having a broad spectrum and a high transmittance in the infrared wavelength range needs to be plated on the surface of an optical fiber communication component such as an optical fiber connector or a wavelength division multiplexer; meanwhile, due to the variability of the application environment of optical fiber communication, the antireflection film is also required to have better environmental stability. Therefore, it is required to design an antireflection film having a high transmittance in the infrared wavelength range of 1310nm to 1550nm. SiO (SiO) 2 The antireflection film is widely applied to the development process of the antireflection film because of the advantages of simple preparation, high film forming efficiency, firm film layer, good antireflection effect and the like, but single SiO 2 The antireflection film material has limited parameter optimization space, is difficult to obtain higher transmittance, and has stronger hygroscopicity due to the surface belonging to an open pore structure, so that the environment stability is poor, optical components in the optical fiber communication system are damaged, and the service life of the optical components is shortened; double-layer SiO 2 Although the anti-reflection film can obtain higher transmittance, the transmittance spectrum is a lambda-shaped curve, and the effective anti-reflection wavelength range is narrower; for exampleThe Chinese patent application No. 202211335660.6 discloses a preparation method of a silicon dioxide antireflection film, and the application discloses a preparation scheme of 2-6 layers of silicon dioxide films, in the specific embodiment scheme, siO is catalyzed by using acid 2 Sol and base catalyzed SiO 2 The sol is mixed to be used as the raw material of the bottom layer film A, and acid catalyzes SiO 2 Sol and base catalyzed SiO 2 The volume ratio of the sol is 1:4, HMDS/TEOS sol is used as the raw material of the upper layer film B, and then the bottom layer film A and the upper layer film A are subjected to pulling plating to obtain the double-layer silicon dioxide antireflection film, and the high light transmittance wave bands of the double-layer silicon dioxide antireflection film are concentrated at the positions of 351nm, 527nm, 1053nm and 1064nm of the central wavelength, so that the double-layer silicon dioxide antireflection film does not have high transmittance for light in the infrared wavelength range. Therefore, in order to meet the requirement of high transmittance in the infrared wavelength range of 1310nm to 1550nm, it is necessary to prepare a multi-layer composite SiO with high transmittance, high surface quality and good environmental stability 2 An antireflection film.
Disclosure of Invention
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided a multi-layered composite SiO 2 The preparation method of the antireflection film comprises the following steps:
A/A/B/B four-layer SiO is prepared by a sol-gel pulling coating method 2 Films wherein A is acid catalyzed SiO 2 Sol and base catalyzed SiO 2 Sol is prepared by mixing, and alkali-catalyzed SiO 2 Sol and acid catalyzed SiO 2 The volume ratio of the sol is 1:9, and B is prepared from the HSNs sol treated by HMDS, and the strong anti-reflection effect in a wide spectral range is realized through the sequential four-layer lifting superposition of A/A/B/B.
Preferably, the method specifically comprises the following steps:
step one, preparing base catalyzed SiO 2 The sol comprises the following specific steps: mixing proper amount of ethyl orthosilicate, absolute ethyl alcohol, deionized water and ammonia water to obtain a solution, sealing the solution in a reactor, and under certain temperature conditionMagnetically stirring for a certain time, then placing at room temperature for aging for a certain time to obtain base-catalyzed SiO 2 Sol;
step two, preparing acid-catalyzed SiO 2 The sol comprises the following specific steps: mixing proper amount of ethyl orthosilicate, absolute ethyl alcohol and deionized water uniformly, wherein the deionized water contains a certain amount of concentrated hydrochloric acid to obtain a reaction liquid, sealing the reaction liquid in a reactor, stirring and reacting for a certain time under a certain temperature condition, and then standing and aging for a certain time under a room temperature condition to obtain acid-catalyzed SiO 2 Sol;
step three, base catalyzing SiO 2 Reflux condensing sol, reflux condensing for a certain time to remove ammonia gas, suction filtering with polytetrafluoroethylene filter paper, and catalyzing SiO with alkali 2 Sol and acid catalyzed SiO 2 Mixing the sol according to the volume ratio of 1:9 to obtain acid-base composite sol, and marking the acid-base composite sol as sol 1;
step four, treating the HSNs sol by using HMDS, wherein the specific method comprises the following steps: dissolving a proper amount of polyacrylic acid in ammonia water, then adding the ammonia water into absolute ethyl alcohol to obtain a reaction solution, dividing tetraethoxysilane into five parts, adding the five parts of tetraethoxysilane into the reaction solution, setting the adding time interval of each part of tetraethoxysilane, continuously stirring the mixture during the adding time interval, finally adding hexamethyldisilazane, and aging the mixture to obtain HMDS-treated HSNs sol which is marked as sol 2;
step five, placing the substrate into a PCE-6 type plasma cleaning machine to clean the substrate by plasma;
step six, placing the substrate cleaned by the plasmas into an ethanol solution for ultrasonic cleaning, and blowing, spraying and drying;
step seven, immersing the dried substrate in the sol 1, and then plating a first layer of film A on the surface of the substrate at a certain lifting speed; then plating a film A on the first film A at the same speed; immersing the substrate plated with the two films A in sol 2 for a certain time, and plating a third film B on the surface of the second film A at a certain lifting speed; immersing the substrate coated with the third layer of film B in sol 1 for a certain time, and coating a fourth layer of film B on the surface of the third layer of film B at a certain lifting speed to obtainFour layers of composite SiO are obtained 2 An antireflection film.
Preferably, in the first step, the volume ratio of the ethyl orthosilicate to the absolute ethyl alcohol to the deionized water to the ammonia water is 1:10:0.5:0.3, the stirring temperature is 50 ℃, the magnetic stirring time is 6 hours, and the aging time in the room temperature environment is 48 hours.
Preferably, in the second step, the volume ratio of the ethyl orthosilicate, the absolute ethyl alcohol, the deionized water and the concentrated hydrochloric acid is 1:10:0.4:0.02, the stirring temperature is 50 ℃, the stirring time is 6 hours, and the mixture is aged for 48 hours in a room temperature environment.
Preferably, in the third step, the SiO is base-catalyzed 2 The sol reflux condensation time is 6 hours, and the reflux condensation temperature is 90 ℃; the pore diameter of the polytetrafluoroethylene is 0.22 mu m, and the suction filtration pressure is 0.09MPa.
Preferably, in the fourth step, the mass-volume ratio of polyacrylic acid, ammonia water, tetraethoxysilane, absolute ethyl alcohol and hexamethyldisilazane is 0.06-0.08 g:6-8 mL:180mL:1mL:10mL, tetraethoxysilane is added in 5 times, each time is 1h apart, stirring is carried out for 6h at room temperature, and finally hexamethyldisilazane is added, and the aging time is 48h.
Preferably, in the fifth step, the cleaning power of the substrate placed in the PCE-6 type plasma cleaning machine is 10W.
Preferably, in the seventh step, the method specifically includes: immersing the dried substrate in the sol 1 for 1min, and then plating a first layer of film A on the surface of the substrate at a lifting speed of 100 mm/min; then plating a film A on the first film A at the same speed; immersing the substrate plated with the two films A in sol 2 for 30s, and plating a third film B on the surface of the second film A at a lifting speed of 80 mm/min; immersing the substrate plated with the third layer film B in the sol 1 for 30s, and plating a fourth layer film B on the surface of the third layer film B at the same lifting speed to obtain an A/A/B/B four-layer composite SiO 2 An antireflection film.
Multilayer composite SiO 2 Application of antireflection film, multi-layer composite SiO 2 The antireflection film is applied to an infrared optical system and comprises an optical fiber connector and a wavelength division multiplexer,and multilayer composite SiO 2 Transmittance of the antireflection film in the infrared wavelength range of 1300 nm-1600 nm>99%, reflectance of<0.5 percent, the water contact angle is more than or equal to 125 DEG
The invention at least comprises the following beneficial effects: the invention firstly adopts a sol-gel method to prepare acid catalytic SiO 2 Sol and base catalyzed SiO 2 The sol is used for cleaning a substrate by using a PEC-6 plasma cleaning machine, and the two sols are subjected to composite plating by a pulling method to prepare the A/A/B/B four-layer composite SiO with high transmittance, high surface quality and good environmental stability 2 An antireflection film having a light transmittance in an infrared wavelength range of 1300nm to 1600nm>99%, reflectance of<0.5%; the water contact angle is more than or equal to 125 degrees; the roughness is lower, and the surface evenness is high. Such a multilayer composite SiO 2 The anti-reflection film has various performance indexes in the infrared wavelength range of 1300 nm-1600 nm superior to that of the traditional single-layer or double-layer SiO 2 The antireflection film is also superior to the traditional four-layer antireflection film, is suitable for optical communication components such as an optical fiber connector, a wavelength division multiplexer and the like in the field of optical fiber communication, and can be widely applied to the fields of infrared optics such as military, atmospheric detection, aerospace and the like.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 shows a four-layer composite SiO of A/A/B/B prepared in example 1 of the present invention 2 Transmittance map of antireflection film;
FIG. 2 shows a four-layer composite SiO of A/A/B/B prepared in example 1 of the present invention 2 Reflectance map of the antireflection film;
FIG. 3 is a schematic diagram showing the A/A/B/B four-layer composite SiO prepared in comparative example 1 of the present invention 2 Transmittance map of antireflection film;
FIG. 4 shows a four-layer composite SiO of A/B/A/B prepared in comparative example 1 of the present invention 2 Reflectivity map of antireflection film
FIG. 5 is a schematic illustration of a/B/A/B four-layer composite SiO prepared in comparative example 2 of the present invention 2 Transmittance of antireflection filmA figure;
FIG. 6 is a schematic diagram of a/B/A/B four-layer composite SiO prepared in comparative example 2 of the present invention 2 Reflectance map of the antireflection film;
FIG. 7 shows a four-layer composite SiO of A/B/A/B prepared in example 1 of the present invention 2 AFM image of antireflection film;
FIG. 8 shows a four-layer composite SiO of A/B/A/B prepared in example 1 of the present invention 2 Contact angle diagram of antireflection film.
Detailed Description
The present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1
The embodiment provides an A/A/B/B four-layer composite SiO 2 The preparation method of the antireflection film comprises the following steps:
step one, preparing base catalyzed SiO 2 The sol comprises the following specific steps: mixing 5mL of tetraethoxysilane, 50mL of absolute ethyl alcohol and 2.5mL of deionized water with 1.5mL of ammonia water to obtain a solution, sealing the solution in a reactor, magnetically stirring for 6h at 50 ℃, then standing and aging for 48h at room temperature to obtain base-catalyzed SiO 2 Sol;
step two, preparing acid-catalyzed SiO 2 The sol comprises the following specific steps: uniformly mixing 5mL of tetraethoxysilane, 50mL of absolute ethyl alcohol and 2mL of deionized water, wherein the deionized water contains 0.1mL of concentrated hydrochloric acid to obtain a reaction liquid, sealing the reaction liquid in a reactor, stirring and reacting for 6h at 50 ℃, then standing and aging for 48h at room temperature to obtain acid-catalyzed SiO 2 Sol;
step three, base catalyzing SiO 2 Reflux condensing the sol at 90deg.C for 6h to remove ammonia gas, filtering with polytetrafluoroethylene filter paper with pore diameter of 0.22 μm under suction filtration pressure of 0.09Mpa, and collecting the filtered alkali-catalyzed SiO 2 Sol and acidCatalytic SiO 2 Mixing the sol according to the volume ratio of 1:9 to obtain acid-base composite sol, and marking the acid-base composite sol as sol 1;
step four, treating the HSNs sol by using HMDS, wherein the specific method comprises the following steps: first, 0.06g of polyacrylic acid was dissolved in 7mL of aqueous ammonia, then added to 180mL of absolute ethanol, and then 1.0mL of TEOS was added to the above reaction solution in five aliquots at a time interval of 1 hour. Continuously stirring for 6 hours, and finally adding 10mL of Hexamethyldisilazane (HMDS) into the sol, and aging for 48 hours to obtain an HMDS-treated HSNs sol which is marked as sol 2;
step five, placing the substrate into a PCE-6 type plasma cleaning machine to carry out plasma cleaning on the substrate, wherein the cleaning power is 10W, and the cleanliness of the substrate and the surface water-cleaning property of the film layer are improved;
step six, placing the substrate cleaned by the plasmas into an ethanol solution for ultrasonic cleaning, and blowing, spraying and drying;
step seven, firstly immersing the dried substrate in the sol 1 for 1min, and then plating a first layer of film A on the surface of the substrate at a lifting speed of 100 mm/min; then a film A was further coated at a speed of 80 mm/min. Immersing the substrate plated with the two films A in the sol 2 for 30s, and plating a third film B on the surface of the two films A at a lifting speed of 100 mm/min; finally, plating a fourth layer of film B at the speed of 80mm/min to finally prepare the A/A/B/B four-layer composite antireflection film.
Four layers of composite SiO prepared in example 1 2 The four-layer composite SiO is measured by an ultraviolet spectrophotometer, an atomic force microscope and a water contact measuring instrument on the antireflection film sample 2 The transmittance of the antireflection film sample is greater than 99% at the center wavelength of 1200 nm-1500 nm, as shown in figure 1; as shown in fig. 2, the minimum reflectance for light in the 900nm to 1800nm wavelength range may be less than 0.5%; as shown in fig. 7, the surface roughness RMS is equal to 1.53nm; as shown in FIG. 8, the water contact angle is equal to 125.99 DEG
Comparative example 1
The embodiment provides an A/A/B/B four-layer composite SiO 2 The preparation method of the antireflection film comprises the following steps:
step one, preparing base catalyzed SiO 2 Sol, particularly methodThe method comprises the following steps: mixing 5mL of tetraethoxysilane, 50mL of absolute ethyl alcohol, 2.5mL of deionized water and 1.5mL of ammonia water to obtain a solution, sealing the solution in a 250mL double-neck round-bottom flask, magnetically stirring for 6h at 50 ℃, then placing at room temperature for aging for 48h to obtain base-catalyzed SiO 2 Sol;
step two, preparing acid-catalyzed SiO 2 The sol comprises the following specific steps: uniformly mixing 5mL of tetraethoxysilane, 50mL of absolute ethyl alcohol and 2mL of deionized water, wherein the deionized water contains 0.1mL of concentrated hydrochloric acid to obtain a reaction liquid, sealing the reaction liquid in a reactor, stirring and reacting for 6h at 50 ℃, then standing and aging for 48h at room temperature to obtain acid-catalyzed SiO 2 Sol;
step three, base catalyzing SiO 2 Reflux condensing the sol at 90deg.C for 6h to remove ammonia gas, filtering with polytetrafluoroethylene filter paper with pore diameter of 0.22 μm under suction filtration pressure of 0.09Mpa, and collecting the filtered alkali-catalyzed SiO 2 Sol and acid catalyzed SiO 2 Mixing the sol according to the volume ratio of 1:9 to obtain acid-base composite sol, and marking the acid-base composite sol as sol 1;
step four, preparing HMDS/TEOS sol, and the specific method is as follows: mixing 50ml of absolute ethyl alcohol, 0.5ml of ammonia water, 1.5ml of deionized water, 0.5ml of hexamethyldisilazane and 5ml of ethyl orthosilicate, adding the reagents into a reactor, stirring for 6 hours at 50 ℃, standing and aging for 48 hours at room temperature, and adding absolute ethyl alcohol accounting for 50% of the total volume of the absolute ethyl alcohol, the ammonia water, the deionized water, the hexamethyldisilazane and the ethyl orthosilicate to obtain HMDS/TEOS sol which is recorded as sol 2;
step five, placing the substrate into a PCE-6 type plasma cleaning machine to carry out plasma cleaning on the substrate, wherein the cleaning power is 10W, and the cleanliness of the substrate and the surface water-cleaning property of the film layer are improved;
step six, placing the substrate cleaned by the plasmas into an ethanol solution for ultrasonic cleaning, and blowing, spraying and drying;
step seven, firstly immersing the dried substrate in the sol 1 for 1min, and then plating a first layer of film A on the surface of the substrate at a lifting speed of 100 mm/min; then at the same speed on the first filmA layer of film A is plated on the film A; immersing the substrate plated with the two films A in sol 2 for 30s, and plating a third film B on the surface of the second film A at a lifting speed of 80 mm/min; immersing the substrate plated with the third layer film B in the sol 1 for 30s, and plating a fourth layer film B on the surface of the third layer film B at the same lifting speed to obtain an A/A/B/B four-layer composite SiO 2 An antireflection film.
As shown in FIG. 3 and FIG. 4, the A/A/B/B four-layer composite SiO prepared in this example 2 The transmittance of the antireflection film is equal to 99.32% at the 130nm center wavelength, but the wavelength range with the transmittance more than 99% is obviously smaller than that of the A/A/B/B four-layer composite SiO of the embodiment 1 2 The range of the reflectance of the antireflection film, which is 0.48% at the minimum, is also significantly smaller than that of example 1.
Comparative example 2
The embodiment provides an A/B/A/B four-layer composite SiO 2 The preparation method of the antireflection film comprises the following steps:
step one, preparing base catalyzed SiO 2 The sol comprises the following specific steps: mixing 5ml of ethyl orthosilicate and 50ml of absolute ethyl alcohol with 1.5ml of ammonia water to obtain a solution, sealing the solution in a reactor, magnetically stirring for 6 hours at 50 ℃, then standing and aging for 48 hours at room temperature to obtain the base-catalyzed SiO 2 Sol;
step two, preparing acid-catalyzed SiO 2 The sol comprises the following specific steps: mixing 5ml of ethyl orthosilicate, 50ml of absolute ethyl alcohol and 2ml of deionized water uniformly, wherein the deionized water contains 0.1ml of concentrated hydrochloric acid to obtain a reaction liquid, sealing the reaction liquid in a reactor, stirring and reacting for 6 hours at 50 ℃, then standing and aging for 48 hours at room temperature to obtain acid-catalyzed SiO 2 Sol;
step three, base catalyzing SiO 2 Reflux condensing the sol, reflux condensing at 90 deg.c for 6 hr to eliminate ammonia and then base catalyzing SiO 2 Sol and acid catalyzed SiO 2 Mixing the sol according to the volume ratio of 1:9 to obtain acid-base composite sol, and marking the acid-base composite sol as sol 1;
step four, preparing HMDS/TEOS sol, and the specific method is as follows: mixing 50ml of absolute ethyl alcohol, 0.5ml of ammonia water, 1.5ml of deionized water, 0.5ml of hexamethyldisilazane and 5ml of ethyl orthosilicate, adding the reagents into a reactor, stirring for 6 hours at 50 ℃, standing and aging for 48 hours at room temperature, and adding absolute ethyl alcohol accounting for 50% of the total volume of the absolute ethyl alcohol, the ammonia water, the deionized water, the hexamethyldisilazane and the ethyl orthosilicate to obtain HMDS/TEOS sol which is recorded as sol 2;
step five, placing the substrate into a PCE-6 type plasma cleaning machine to carry out plasma cleaning on the substrate, wherein the cleaning power is 10W, and the cleanliness of the substrate and the surface water-cleaning property of the film layer are improved;
step six, placing the substrate cleaned by the plasmas into an ethanol solution for ultrasonic cleaning, and blowing, spraying and drying;
step seven, firstly immersing the dried substrate in the sol 1 for 1min, and then plating a first layer of film A on the surface of the substrate at a lifting speed of 100 mm/min; immersing the substrate plated with the first layer film A in sol 2 for 1min, and plating a second layer film B on the surface of the first layer film A at a lifting speed of 80 mm/min; immersing the substrate plated with the second layer film B in the sol 1 for 30s, and plating a third layer film A on the surface of the second layer film B at a lifting speed of 100 mm/min; finally immersing the substrate plated with the third layer film A in sol 2 for 30s, and then plating a fourth layer film B on the surface of the third layer film A at a lifting speed of 80mm/min to prepare the A/B/A/B four-layer composite SiO 2 An antireflection film.
Four-layer composite SiO of A/B/A/B is prepared in comparative example 2 2 The four-layer composite SiO is measured by an ultraviolet spectrophotometer, an atomic force microscope and a water contact measuring instrument on the antireflection film sample 2 The transmittance of the sample of the antireflection film at the center wavelength of 1500nm is equal to 99.21%, but the wavelength range with the transmittance of more than 99% is also lower than that of the A/A/B/B four-layer antireflection film prepared in example 1, as shown in FIG. 5; as shown in FIG. 6, the minimum reflectance is only 0.68%, which is significantly smaller than the A/A/B/B four-layer antireflection film prepared in example 1.
The number of equipment and the scale of processing described herein are intended to simplify the description of the present invention. Applications, modifications and variations of the present invention will be readily apparent to those skilled in the art.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (9)
1. Multilayer composite SiO 2 The preparation method of the antireflection film is characterized by comprising the following steps: A/A/B/B four-layer SiO is prepared by a sol-gel pulling coating method 2 Films wherein A is acid catalyzed SiO 2 Sol and base catalyzed SiO 2 Sol is prepared by mixing, and alkali-catalyzed SiO 2 Sol and acid catalyzed SiO 2 The volume ratio of the sol is 1:9, and B is prepared from the HSNs sol treated by HMDS, and the strong anti-reflection effect in a wide spectral range is realized through the sequential four-layer lifting superposition of A/A/B/B.
2. The multilayer composite SiO of claim 1 2 The preparation method of the antireflection film is characterized by comprising the following steps of:
step one, preparing base catalyzed SiO 2 The sol comprises the following specific steps: mixing proper amount of ethyl orthosilicate, absolute ethyl alcohol, deionized water and ammonia water to obtain a solution, sealing the solution in a reactor, magnetically stirring for a certain time at a certain temperature, standing and aging for a certain time at room temperature to obtain base-catalyzed SiO 2 Sol;
step two, preparing acid-catalyzed SiO 2 The sol comprises the following specific steps: mixing proper amount of ethyl orthosilicate, absolute ethyl alcohol and deionized water uniformly, wherein the deionized water contains a certain amount of concentrated hydrochloric acid to obtain a reaction liquid, sealing the reaction liquid in a reactor, stirring and reacting for a certain time under a certain temperature condition, and then standing and aging for a certain time under a room temperature condition to obtain acid-catalyzed SiO 2 Sol;
step three, alkali is catalyzedChemical SiO 2 Reflux condensing sol, reflux condensing for a certain time to remove ammonia gas, suction filtering with polytetrafluoroethylene filter paper, and catalyzing SiO with alkali 2 Sol and acid catalyzed SiO 2 Mixing the sol according to the volume ratio of 1:9 to obtain acid-base composite sol, and marking the acid-base composite sol as sol 1;
step four, treating the HSNs sol by using HMDS, wherein the specific method comprises the following steps: dissolving a proper amount of polyacrylic acid in ammonia water, then adding the ammonia water into absolute ethyl alcohol to obtain a reaction solution, dividing tetraethoxysilane into five parts, adding the five parts of tetraethoxysilane into the reaction solution, setting the adding time interval of each part of tetraethoxysilane, continuously stirring the mixture during the adding time interval, finally adding hexamethyldisilazane, and aging the mixture to obtain HMDS-treated HSNs sol which is marked as sol 2;
step five, placing the substrate into a PCE-6 type plasma cleaning machine to clean the substrate by plasma;
step six, placing the substrate cleaned by the plasmas into an ethanol solution for ultrasonic cleaning, and blowing, spraying and drying;
step seven, immersing the dried substrate in the sol 1, and then plating a first layer of film A on the surface of the substrate at a certain lifting speed; then plating a film A on the first film A at the same speed; immersing the substrate plated with the two films A in sol 2 for a certain time, and plating a third film B on the surface of the second film A at a certain lifting speed; immersing the substrate plated with the third layer film B in the sol 1 for a certain time, and plating a fourth layer film B on the surface of the third layer film B at a certain lifting speed to obtain four layers of composite SiO 2 An antireflection film.
3. The multilayer composite SiO of claim 2 2 The preparation method of the antireflection film is characterized in that in the first step, the volume ratio of the tetraethoxysilane to the absolute ethyl alcohol to the deionized water to the ammonia water is 1:10:0.5:0.3, the stirring temperature is 50 ℃, the magnetic stirring time is 6 hours, and the aging time in a room temperature environment is 48 hours.
4. The multilayer composite SiO of claim 2 2 The preparation method of the antireflection film is characterized in that the second stepIn the method, the volume ratio of the tetraethoxysilane to the absolute ethyl alcohol to the deionized water to the concentrated hydrochloric acid is 1:10:0.4:0.02, the stirring temperature is 50 ℃, the stirring time is 6 hours, and the mixture is aged for 48 hours in a room temperature environment.
5. The multilayer composite SiO of claim 2 2 The preparation method of the antireflection film is characterized in that in the third step, the SiO is catalyzed by alkali 2 The sol reflux condensation time is 6 hours, and the reflux condensation temperature is 90 ℃; the pore diameter of the polytetrafluoroethylene is 0.22 mu m, and the suction filtration pressure is 0.09MPa.
6. The multilayer composite SiO of claim 2 2 The preparation method of the antireflection film is characterized in that in the fourth step, the mass volume ratio of polyacrylic acid, ammonia water, tetraethoxysilane, absolute ethyl alcohol and hexamethyldisilazane is 0.06-0.08 g:6-8 mL:180mL:1mL:10mL, the tetraethoxysilane is added for 5 times, each time is 1h, stirring is carried out for 6h at room temperature, and finally the hexamethyldisilazane is added, and the aging time is 48h.
7. The multilayer composite SiO of claim 2 2 The preparation method of the antireflection film is characterized in that in the fifth step, the cleaning power of the substrate placed in a PCE-6 plasma cleaning machine is 10W.
8. The multilayer composite SiO of claim 2 2 The preparation method of the antireflection film is characterized by comprising the following steps: immersing the dried substrate in the sol 1 for 1min, and then plating a first layer of film A on the surface of the substrate at a lifting speed of 100 mm/min; then plating a film A on the first film A at the same speed; immersing the substrate plated with the two films A in sol 2 for 30s, and plating a third film B on the surface of the second film A at a lifting speed of 80 mm/min; immersing the substrate plated with the third layer film B in the sol 1 for 30s, and plating a fourth layer film B on the surface of the third layer film B at the same lifting speed to obtain an A/A/B/B four-layer composite SiO 2 An antireflection film.
9. A multilayer composite SiO according to any one of claims 1 to 8 2 Multilayer composite SiO prepared by preparation method of antireflection film 2 The application of the antireflection film is characterized in that the multilayer composite SiO 2 The antireflection film is applied to an infrared optical system and comprises an optical fiber connector and a wavelength division multiplexer, and is a multilayer composite SiO 2 Transmittance of the antireflection film in the infrared wavelength range of 1300 nm-1600 nm>99%, reflectance of<The contact angle of water is more than or equal to 125 degrees and is 0.5 percent.
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