CN104609738A - Method used for increasing silicon dioxide antireflection film hole stability - Google Patents
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Abstract
The invention relates to a method used for increasing silicon dioxide antireflection film hole stability, and belongs to the technical field of optical thin film preparation. Sol-gel method is adopted for preparing a silicon dioxide antireflection film, and comprises following steps: a sol is prepared firstly; high borosilicate glass is subjected to cleaning and surface treatment; film preparation is carried out through pulling; and thin film heat treatment and thin film surface hydrophobic treatment are carried out; wherein 1) organic siloxane R'xSi(OR)4-x is added into the sol so as to modify the sol; and 2) in thin film heat treatment processes, a gel thin film is subjected to step thermal insulation heat processing at 90 to 350 DEG C. The method is capable of increasing film forming rate of porous silicon dioxide thin films, and ensuring transmittance of workpieces provided with antireflection films.
Description
Technical field
The present invention relates to a kind of method improving antireflecting silicon dioxide film hole stability, belong to Deposition Techniques for Optical Thin Films field.
Background technology
Anti-reflection film is also known as antireflective coating, namely on optical element surface, plating optical thin film, for reducing the reflection of optical element surface, increasing the transmitance of light, thus improve the performance of optical element in operation wavelength or wave band, on optical element, therefore add plating anti-reflection film is very necessary.
At present, titanium dioxide, silicon nitride, magnesium fluoride, silicon-dioxide, tantalum pentoxide, zinc sulphide, zirconium dioxide, cerium oxide etc. are mainly contained for anti-reflection Coating Materials, for silicon-dioxide, because it is with low cost, specific refractory power is moderate, surface strength advantages of higher, become the preferred material preparing anti-reflection film at glass surface, as patent CN102674704A, CN102838287A, CN101423934A, CN102603205A all prepare antireflecting silicon dioxide film at glass surface.
The preparation method of antireflecting silicon dioxide film is varied, common are vacuum-evaporation, magnetron sputtering, chemical vapour deposition, ion beam assisted depositing and sol-gel etc.Compared with other film coating method, sol-gel method has the equipment not needing complex and expensive, technique is simple, with low cost, structure-controllable, applicable large-area coating film, and can from features such as molecular level design and cuttings, become and be coated with the most frequently used method of antireflecting silicon dioxide film, as patent CN1197928A, CN1843999A, CN102491648A etc. all adopt sol-gel method to prepare anti-reflection film.
Prepare in the process of antireflecting silicon dioxide film in sol-gel method, gel-film is deposited on substrate surface through the gelation process of colloidal sol, a certain amount of liquid composition of gel-film internal residual, therefore needs to heat-treat gel-film.In heat treatment process, except liquid in gel evaporation and decompose except, also has the polyreaction between micelle, namely shrink or acetal reaction, the water that condensation is got off or alcohol also evaporate in the lump, when be evaporated to produce meniscus in gel inside aperture time, the surface tension of liquid in gel hole on phase change interface can make the nano aperture in gel-film produce strong kapillary contraction, namely capillarity or capillary force is produced, powerful capillary force can cause the void collapse of the nanometer scale of gelinite, hole is disappeared so that density of film increase, What is more can cause film peeling, thus make anti-reflection film produce a desired effect.
Summary of the invention
The object of the invention is to propose a kind of method improving antireflecting silicon dioxide film hole stability.
Adopt sol-gel method to prepare antireflecting silicon dioxide film, generally comprise following steps: first prepare colloidal sol, then carry out high-boron-silicon glass cleaning and surface treatment, then lift masking, finally carry out film thermal process and film surface hydrophobic treatment.
The present invention improves the method for antireflecting silicon dioxide film hole stability, realizes by taking at following 2:
1) in colloidal sol, organo-siloxane R ' is added
xsi (OR)
4-x, modification is carried out to colloidal sol;
2) in film thermal treating processes, in 90 DEG C ~ 350 DEG C, the process of ladder heat preservation hot is carried out to gel film.
Wherein, organo-siloxane R '
xsi (OR)
4-xin, x=1,2 or 3, Si-OR be facile hydrolysis base, R is H, alkyl, acyl group etc., and as methyl, ethyl, propyl group, formyl radical, ethanoyl, propionyl etc., R '-Si is hydrophobic group, and R ' is alkyl and aryl radical etc., as methyl, ethyl, propyl group, phenyl etc.Organo-siloxane R ' is added in colloidal sol
xsi (OR)
4-x, carry out organically-modified to colloidal sol, organo-siloxane R '
xsi (OR)
4-xthe surface of the silica network that can have been formed in colloidal sol is hydrolyzed and copolycondensation, hydrophobic grouping R ' is made organically to be combined with silica matrices, organic group is made to be dispersed in the surface of silica matrices under mild conditions, in heat treatment process, the existence of hydrophobic grouping R ', can reduce film capillary pressure, reduces the internal stress of gel network, thus avoid subsiding of silicon oxide hole, improve hole stability.
Wherein, organo-siloxane R '
xsi (OR)
4-xbe selected from Union carbide A-162, trimethylethoxysilane, trimethylmethoxysilane, trimethylacetoxysilane, dimethyldiacetoxy silane, methyl triacetoxysilane, trimethylammonium propionyloxy silane, phenyl triethoxysilane, diphenyl diethoxy silane, phenyl triacetoxysilane, phenylbenzene diacetoxy silane, trimethyl silanol, triethyl silanol, triphenyl silanol, one or more in tert-butyl dimethyl-silicon alkanol and diphenyl silanodiol.
Wherein, in colloidal sol, organo-siloxane R '
xsi (OR)
4-xvolumetric molar concentration be 0.03mol/L ~ 0.2mol/L, be preferably 0.03mol/L ~ 0.1mol/L.Along with the increase of hydrophobic grouping R ' concentration in colloidal sol; the hydrophobicity of silica dioxide granule strengthens; intermiscibility between silica dioxide granule and dispersion medium is deteriorated; this species diversity develops into and to a certain degree namely causes the silica dioxide granule with non-polar group to assemble mutually, grow up; then be precipitated out from dispersion medium; thus make sol system demonstrate certain unstable, therefore, by organo-siloxane R '
xsi (OR)
4-xconcentration control in suitable scope, to improve collosol stability.
Wherein, when carrying out the process of ladder heat preservation hot to gel-film, in 90 DEG C ~ 350 DEG C intervals, get 3 ~ 6 temperature spots, carry out the isothermal heat preservation hot process of certain hour at each temperature spot, as the temperature head between each temperature spot (containing 40 DEG C) more than 40 DEG C, it can be equal-difference arrangement.In silica dioxide gel film, remain a certain amount of liquid composition, the evaporation of liquid composition and decomposition temperature many places are in 90 DEG C ~ 350 DEG C intervals, and, different liquid phase can be evaporated at different temperature and decompose, therefore, in this temperature range, multiple holding temperature is set, liquid composition is allowed to evaporate at a slow speed at lower and rational temperature and to decompose, liquid composition effectively can be avoided to evaporate and decompose the gel-film internal stress inequality caused, and then prevent subsiding of silicon oxide hole, improve hole stability.
Wherein, the process of ladder heat preservation hot is 10 ~ 90min in the soaking time of each temperature spot.
Wherein, in ladder heat preservation hot process temperature-rise period, namely previous insulation point terminates in follow-up next one insulation point temperature-rise period, and temperature rise rate is 0.5 DEG C/min ~ 1.5 DEG C/min.Lower temperature rise rate can slow down remaining organic volatilization and decomposition rate in gel-film equally, prevents subsiding of silicon oxide hole, improves hole stability.
The present invention improves the method for antireflecting silicon dioxide film hole stability, comprises following concrete steps:
(1) colloidal sol is prepared: by tetraethoxy, deionized water, organo-siloxane R '
xsi (OR)
4-x, triton x-100 joins in dehydrated alcohol, using hydrochloric acid as catalyzer, configuration colloidal sol, carries out heating in water bath process to described colloidal sol, then by described colloidal sol at room temperature sealing and standing;
(2) high-boron-silicon glass cleaning and surface treatment: respectively ultrasonic cleaning is carried out to high borosilicate sheet with deionized water, acetone and dehydrated alcohol, with the hydrofluoric acid aqueous solution of volume fraction 5%, surface treatment is carried out to high borosilicate sheet again, deionized water ultrasonic cleaning is used after process, then, high borosilicate sheet is placed in drying in oven;
(3) lift masking: in glove box, the high borosilicate sheet that the colloidal sol obtained by step (1) and step (2) process carries out lift masking, and high borosilicate sheet floods in colloidal sol, then lifts, and is left standstill by the film lifted in glove box;
(4) film thermal process: the high borosilicate sheet with gel film that step (3) is obtained puts into retort furnace, carries out the process of ladder heat preservation hot, be then warmed up to 500 DEG C of thermal treatments in 90 DEG C ~ 350 DEG C;
(5) film surface hydrophobic treatment: the high-boron-silicon glass with anti-reflection film that step (4) is obtained takes out in retort furnace, in glove box, adopts Best-Effort request machine, carries out surface hydrophobicity process with hexamethyldisilazane to film.
Prepare antireflecting silicon dioxide film void collapse problem for sol-gel method, the present invention prevents subsiding of anti-reflection film hole by following two kinds of approach, improves hole stability:
The first, in colloidal sol preparation process, in colloidal sol, add a certain amount of organo-siloxane R '
xsi (OR)
4-x, the Si-OR in organo-siloxane is facile hydrolysis base, and R is H, alkyl, acyl group etc.; as methyl, ethyl, propyl group, formyl radical, ethanoyl, propionyl etc.; R '-Si is hydrophobic group, and R ' is alkyl and aryl radical etc., as methyl, ethyl, propyl group, phenyl etc.Organo-siloxane R '
xsi (OR)
4-xthe surface of the silica network that can have been formed in colloidal sol is hydrolyzed and copolycondensation, hydrophobic grouping R ' is made organically to be combined with silica matrices, organic group is made to be dispersed in the surface of silica matrices under mild conditions, in heat treatment process, the existence of hydrophobic grouping R ', can reduce film capillary pressure, reduces the internal stress of gel network, thus avoid subsiding of silicon oxide hole, improve hole stability;
Second, at gel-film heat treatment stages, in gel-film, residual liquid phase composition usually evaporates and decomposes between 90 DEG C ~ 350 DEG C, therefore, 3 ~ 6 stopping temperatures are selected between 90 DEG C ~ 350 DEG C, in each temperature, the process of isothermal heat preservation hot is carried out to film, the low temperature rise rate of 0.5 DEG C/min ~ 1.5 DEG C/min is selected in the temperature rise period, the heterogeneity of remaining liquid phase in gel-film is made to evaporate at a slow speed respectively at lower and rational temperature and decompose, reduce gel-film drying rate with this and reduce surface tension, prevent the void collapse of film in heat treatment process and cracking further, improve hole stability.
By introducing organo-siloxane R ' in colloidal sol
xsi (OR)
4-xhydrophobic grouping R ' is made organically to be combined with silica matrices, organic group is made to be dispersed in the surface of silica matrices under mild conditions, the existence of hydrophobic grouping R ', capillary pressure in film thermal treating processes can be reduced, reduce the internal stress of gel network, prevent subsiding of silicon oxide hole, improve hole stability.In addition, by controlling gel-film heat treatment process, multiple holding temperature is set in lower temperature range, and reduce temperature rise rate in heat treatment process, strict control organism evaporation and decomposition rate, make organism in gel-film evaporate at a slow speed and decompose, and effectively avoids organism to evaporate and decompose the gel-film internal stress inequality caused, prevent subsiding of silicon oxide hole further, and improve hole stability.Method described in the present invention effectively can maintain SiO
2the integrity of anti-reflection film hole, and and then ensure with the transmitance of anti-reflection film workpiece.
By anti-reflection film prepared by the inventive method, film hole is evenly distributed, and the peak transmittance with the high-boron-silicon glass of antireflective coating is greater than 97%, and visible light wave range average transmittances is greater than 96%, effective raising microporous silica film yield polymer films, and ensure the transmitance with anti-reflection film workpiece.
Accompanying drawing explanation
Fig. 1-a, Fig. 1-b are anti-reflection film surface topography map, Fig. 1-a: magnification 100k, Fig. 1-b: magnification 200k.
Fig. 2 is antireflective effect comparison diagram.
Embodiment
Following examples further illustrate content of the present invention, but should not be construed as limitation of the present invention.
If do not specialize, the conventional means that technique means used in embodiment and equipment are well known to the skilled person and equipment.
In embodiment, pulling machine used is that Qingdao Zhongrui Intelligent Instrument Co., Ltd. produces ZR-4200 type Best-Effort request coating equipment; Tetraethoxy, triton x-100, Union carbide A-162, trimethylethoxysilane, methyl triacetoxysilane, trimethyl silanol, phenyl triethoxysilane and diphenyl silanodiol are Sigma-Aldrich reagent; Dehydrated alcohol and hydrochloric acid are that Beijing Chemical Plant produces reagent.
Embodiment one
Present embodiments provide a kind of method improving antireflecting silicon dioxide film hole stability, comprise the following steps:
Step 1: prepare stand-by colloidal sol, the organo-siloxane added in colloidal sol is Union carbide A-162;
By tetraethoxy, deionized water, Union carbide A-162, triton x-100 in molar ratio 1:4.53:0.25:0.2 join in dehydrated alcohol, using hydrochloric acid as catalyzer, configuration 100mL colloidal sol, wherein, the volumetric molar concentration of Union carbide A-162 is 0.075mol/L, water bath processing is carried out to described colloidal sol, bath temperature is 55 DEG C, and the time is 2 hours, then, by described colloidal sol at room temperature sealing and standing 2 days, complete the preparation of stand-by colloidal sol.
Step 2: high-boron-silicon glass cleaning and surface treatment;
Successively respectively ultrasonic cleaning is carried out to high borosilicate sheet with deionized water, acetone and dehydrated alcohol, often walking scavenging period is 15 minutes, then, with the hydrofluoric acid aqueous solution of volume fraction 5%, surface treatment is carried out to high borosilicate sheet, time is 1 minute, and use deionized water ultrasonic cleaning after process, the time is 15 minutes, high borosilicate sheet is placed in drying in oven, stand-by.
Step 3: lift masking;
In glove box, the colloidal sol obtained by step 1 carries out lift masking to the high borosilicate sheet that step 2 processes, and the dipping time of high borosilicate sheet in colloidal sol is 1 minute, then lifts, and pull rate is 10cm/min, and the film lifted is left standstill 3 minutes in glove box.
Step 4: film thermal process;
The high borosilicate sheet with gel-film that step 3 is obtained puts into retort furnace, from room temperature, with the temperature rise rate of 1 DEG C/min, film is heat-treated, 30 minutes are respectively stopped 200 DEG C, 250 DEG C, 300 DEG C three temperature, then be warmed up to 500 DEG C of thermal treatments 15 minutes, close retort furnace, make film cool to room temperature with the furnace.
Step 5: film surface hydrophobic treatment;
The high-boron-silicon glass with anti-reflection film that step 4 is obtained takes out in retort furnace, in glove box, adopt Best-Effort request machine, carry out surface hydrophobicity process with hexamethyldisilazane to film, the high-boron-silicon glass with anti-reflection film floods 15 minutes in hexamethyldisilazane, allows hexamethyldisilazane and microporous silica film fully react, then lift, pull rate is 19cm/min, and film preparation is complete, waits until structural characterization and performance test.
The hydrophobic grouping methyl in Union carbide A-162 is utilized organically to be combined with silica matrices in embodiment, methyl is made to be dispersed in the surface of silica matrices under mild conditions, the existence of methyl, film capillary pressure can be reduced, reduce the internal stress of gel network, thus avoid subsiding of silicon oxide hole, improve hole stability.In film thermal treating processes, the temperature rise rate at a slow speed of 1 DEG C/min and 200 DEG C, 250 DEG C, 300 DEG C three the ladder holding temperature points according to the setting of TG-DT A spectrum curve, the at a slow speed volatilization of organism in heat treatment process and decomposition in effective guarantee gel-film, prevent subsiding of silicon oxide hole further, improve hole stability.
Fig. 1-a, Fig. 1-b are the surface topography photos of the porous silica anti-reflection film that embodiment one obtains, Fig. 1-a: magnification 100k, Fig. 1-b: magnification 200k.As seen from the figure, film surface hole distribution is even, and does not completely have crackle; Fig. 2 is the transmittance curve with porous silica anti-reflection film high-boron-silicon glass that embodiment one obtains, and as can be seen from curve, high-boron-silicon glass vertex transmitance is greater than 97%, and visible light wave range average transmittances is greater than 96.5%.Said structure and performance characterization illustrate that the present embodiment method effectively can improve the stability of silicon oxide anti-reflection film hole, and and then ensure that the high-boron-silicon glass with anti-reflection film has excellent translucidus energy.
Embodiment two
Present embodiments provide a kind of method improving antireflecting silicon dioxide film hole stability, comprise the following steps:
Step 1 ': substantially identical with embodiment one step 1, difference is, the organo-siloxane added in colloidal sol is trimethylethoxysilane, and trimethylethoxysilane concentration is 0.03mol/L.
Step 2 ' with step 3 ' is identical with step 3 with embodiment one step 2.
Step 4 ': film thermal process;
By step 3 ' the obtained high borosilicate sheet with gel-film puts into retort furnace, from room temperature, with the temperature rise rate of 0.5 DEG C/min, film is heat-treated, 10 minutes are respectively stopped 130 DEG C, 200 DEG C, 250 DEG C, 300 DEG C four temperature, then be warmed up to 500 DEG C of thermal treatments 15 minutes, close retort furnace, make film cool to room temperature with the furnace.
Step 5 ' identical with embodiment one step 5.
The coated glass surface topography that the present embodiment obtains and optical property reach the effect identical with embodiment one.
Embodiment three
Present embodiments provide a kind of method improving antireflecting silicon dioxide film hole stability, comprise the following steps:
Step 1 ' ': substantially identical with embodiment one step 1, difference is, the organo-siloxane added in colloidal sol is methyl triacetoxysilane, and methyl triacetoxysilane concentration is 0.2mol/L.
Step 2 ' ' with step 3 ' ' is identical with step 3 with embodiment one step 2.
Step 4 ' ': film thermal process;
By step 3 ' ' the obtained high borosilicate sheet with gel-film puts into retort furnace, from room temperature, with the temperature rise rate of 1 DEG C/min, film is heat-treated, 40 minutes are respectively stopped 145 DEG C, 200 DEG C, 250 DEG C, 300 DEG C four temperature, then be warmed up to 500 DEG C of thermal treatments 15 minutes, close retort furnace, make film cool to room temperature with the furnace.
Step 5 ' ' identical with embodiment one step 5.
The coated glass surface topography that the present embodiment obtains and optical property reach the effect identical with embodiment one.
Embodiment four
Present embodiments provide a kind of method improving antireflecting silicon dioxide film hole stability, comprise the following steps:
Step 1 ' ' ': substantially identical with embodiment one step 1, difference is, the organo-siloxane added in colloidal sol is trimethyl silanol, and trimethyl silicane determining alcohol is 0.04mol/L.
Step 2 ' ' ' and step 3 ' ' ' identical with step 3 with embodiment one step 2.
Step 4 ' ' ': film thermal process;
The high borosilicate sheet with gel-film that ' ' ' is obtained by step 3 puts into retort furnace, from room temperature, with the temperature rise rate of 1.5 DEG C/min, film is heat-treated, 20 minutes are respectively stopped 150 DEG C, 200 DEG C, 250 DEG C, 300 DEG C four temperature, then be warmed up to 500 DEG C of thermal treatments 15 minutes, close retort furnace, make film cool to room temperature with the furnace.
Step 5 ' ' ' identical with embodiment one step 5.
The coated glass surface topography that the present embodiment obtains and optical property reach the effect identical with embodiment one.
Embodiment five
Present embodiments provide a kind of method improving antireflecting silicon dioxide film hole stability, comprise the following steps:
Step 1 ' ' ' ': substantially identical with embodiment one step 1, difference is, the organo-siloxane added in colloidal sol is phenyl triethoxysilane, and phenyl triethoxysilane concentration is 0.1mol/L.
Step 2 " ' ' with step 3 " ' ' identical with step 3 with embodiment one step 2.
Step 4 " ' ': film thermal process;
By step 3 " ' ' the obtained high borosilicate sheet with gel-film puts into retort furnace; from room temperature; with the temperature rise rate of 0.5 DEG C/min, film is heat-treated; respectively stop 90 minutes 160 DEG C, 200 DEG C, 250 DEG C, 300 DEG C four temperature; be then warmed up to 500 DEG C of thermal treatments 15 minutes; close retort furnace, make film cool to room temperature with the furnace.
Step 5 " ' ' identical with embodiment one step 5.
The present embodiment utilizes the hydrophobic grouping phenyl in phenyl triethoxysilane to be organically combined with silica matrices, avoids silicon oxide void collapse, improves hole stability.In film thermal treating processes, 160 DEG C, 200 DEG C, 250 DEG C that arrange according to TG-DT A spectrum curve, 300 DEG C four step temperature points can improve the stability of silicon oxide hole further.The coated glass surface topography that the present embodiment obtains and optical property reach the effect identical with embodiment one.
Embodiment six
Present embodiments provide a kind of method improving antireflecting silicon dioxide film hole stability, comprise the following steps:
Step 1 ' ' ' ' ': substantially identical with embodiment one step 1, difference is, the organo-siloxane added in colloidal sol is diphenyl silanodiol, and diphenyl silanodiol concentration is 0.06mol/L.
Step 2 " ' ' ' and step 3 " ' ' ' identical with step 3 with embodiment one step 2.
Step 4 " ' ' ': film thermal process;
By step 3 " ' ' ' obtained high borosilicate sheet with gel-film puts into retort furnace; from room temperature; with the temperature rise rate of 0.5 DEG C/min, film is heat-treated; respectively stop 75 minutes 90 DEG C, 140 DEG C, 200 DEG C, 250 DEG C, 300 DEG C, 350 DEG C six temperature; be then warmed up to 500 DEG C of thermal treatments 15 minutes; close retort furnace, make film cool to room temperature with the furnace.
Step 5 " ' ' ' identical with embodiment one step 5.
The coated glass surface topography that the present embodiment obtains and optical property reach the effect identical with embodiment one.
The present invention passes through to SiO
2organo-siloxane R ' is added in colloidal sol
xsi (OR)
4-x, hydrophobic grouping R ' can reduce gel-film capillary force, reduces gel network internal stress, avoids gel-film heat treatment process Hole to subside, and improves hole stability; The process of ladder heat preservation hot is carried out to gel-film simultaneously, multistage insulation is carried out between 90 DEG C ~ 350 DEG C, make remaining liquid phase slow evaporation and decomposition at a lower temperature in gel-film, prevent void collapse further, improve hole stability, thus effectively improve microporous silica film yield polymer films, and ensure the transmitance with anti-reflection film workpiece.
Although above with a general description of the specific embodiments to invention has been detailed description, on basis of the present invention, can make some amendments to it or improve, this will be apparent to those skilled in the art.Therefore, some done without departing from theon the basis of the spirit of the present invention amendments or improvement, all belong to the scope of protection of present invention.
Claims (10)
1. one kind is improved the method for antireflecting silicon dioxide film hole stability, sol-gel method is adopted to prepare antireflecting silicon dioxide film, comprise and first prepare colloidal sol, then high-boron-silicon glass cleaning and surface treatment is carried out, lift masking again, finally carry out film thermal process and film surface hydrophobic treatment, it is characterized in that:
1) in colloidal sol, organo-siloxane R ' is added
xsi (OR)
4-x, modification is carried out to colloidal sol;
2) in film thermal process, in 90 DEG C ~ 350 DEG C, the process of ladder heat preservation hot is carried out to gel film.
2. the method for raising antireflecting silicon dioxide film hole stability according to claim 1, is characterized in that: organo-siloxane R '
xsi (OR)
4-xin, x=1,2 or 3, Si-OR be facile hydrolysis base, R '-Si is hydrophobic group.
3. the method for raising antireflecting silicon dioxide film hole stability according to claim 2, is characterized in that: organo-siloxane R '
xsi (OR)
4-xin, R is H, alkyl or acyl group, and R ' is alkyl or aryl radical.
4. the method for raising antireflecting silicon dioxide film hole stability according to claim 3, is characterized in that: organo-siloxane R '
xsi (OR)
4-xin, R is methyl, ethyl, propyl group, formyl radical, ethanoyl or propionyl, and R ' is methyl, ethyl, propyl group or phenyl.
5. the method for raising antireflecting silicon dioxide film hole stability according to claim 4, is characterized in that: organo-siloxane R '
xsi (OR)
4-xbe selected from Union carbide A-162, trimethylethoxysilane, trimethylmethoxysilane, trimethylacetoxysilane, dimethyldiacetoxy silane, methyl triacetoxysilane, trimethylammonium propionyloxy silane, phenyl triethoxysilane, diphenyl diethoxy silane, phenyl triacetoxysilane, phenylbenzene diacetoxy silane, trimethyl silanol, triethyl silanol, triphenyl silanol, one or more in tert-butyl dimethyl-silicon alkanol and diphenyl silanodiol.
6. the method for raising antireflecting silicon dioxide film hole stability according to claim 1, is characterized in that: organo-siloxane R '
xsi (OR)
4-xvolumetric molar concentration be 0.03mol/L ~ 0.2mol/L.
7. the method for raising antireflecting silicon dioxide film hole stability according to claim 1, is characterized in that: when carrying out the process of ladder heat preservation hot, gets 3 ~ 6 temperature spots, carry out heat preservation hot process at each temperature spot to film in 90 DEG C ~ 350 DEG C intervals.
8. the method for raising antireflecting silicon dioxide film hole stability according to claim 6, is characterized in that: be 10 ~ 90min in the soaking time of each temperature spot.
9. the method for raising antireflecting silicon dioxide film hole stability according to claim 7, is characterized in that: in the process of ladder heat preservation hot, temperature rise rate is 0.5 DEG C/and min ~ 1.5 DEG C/min.
10. the method for the raising antireflecting silicon dioxide film hole stability according to any one of claim 1-9, is characterized in that comprising following concrete steps:
(1) colloidal sol is prepared: by tetraethoxy, deionized water, organo-siloxane R '
xsi (OR)
4-x, triton x-100 joins in dehydrated alcohol, using hydrochloric acid as catalyzer, configuration colloidal sol, carries out heating in water bath process to described colloidal sol, then by described colloidal sol at room temperature sealing and standing;
(2) high-boron-silicon glass cleaning and surface treatment: respectively ultrasonic cleaning is carried out to high borosilicate sheet with deionized water, acetone and dehydrated alcohol, with the hydrofluoric acid aqueous solution of volume fraction 5%, surface treatment is carried out to high borosilicate sheet again, deionized water ultrasonic cleaning is used after process, then, high borosilicate sheet is placed in drying in oven;
(3) lift masking: in glove box, carry out lift masking with the high borosilicate sheet of obtained colloidal sol and process, high borosilicate sheet floods in colloidal sol, then lifts, and is left standstill by the film lifted in glove box;
(4) film thermal process: the obtained high borosilicate sheet with gel film is put into retort furnace, carries out the process of ladder heat preservation hot in 90 DEG C ~ 350 DEG C, be then warmed up to 500 DEG C of thermal treatments;
(5) film surface hydrophobic treatment: taken out in retort furnace by the obtained high-boron-silicon glass with anti-reflection film, in glove box, adopts Best-Effort request machine, carries out surface hydrophobicity process with hexamethyldisilazane to film.
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| CN107540241A (en) * | 2017-08-24 | 2018-01-05 | 福建农林大学 | A kind of method that the controllable hydrophobic silica anti-reflection film of refractive index is prepared with phenyl triethoxysilane |
| CN108663729A (en) * | 2018-05-22 | 2018-10-16 | 中国工程物理研究院激光聚变研究中心 | A kind of preservation method of chemical films optical element |
| CN110176503A (en) * | 2019-06-05 | 2019-08-27 | 浙江力晟玻璃科技有限公司 | A kind of cadmium telluride power generating glass |
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| CN106810082A (en) * | 2016-11-28 | 2017-06-09 | 佛山市尚好门窗有限责任公司 | A kind of preparation method of solar energy film anti-reflection film |
| CN107540241A (en) * | 2017-08-24 | 2018-01-05 | 福建农林大学 | A kind of method that the controllable hydrophobic silica anti-reflection film of refractive index is prepared with phenyl triethoxysilane |
| CN108663729A (en) * | 2018-05-22 | 2018-10-16 | 中国工程物理研究院激光聚变研究中心 | A kind of preservation method of chemical films optical element |
| CN108663729B (en) * | 2018-05-22 | 2019-12-13 | 中国工程物理研究院激光聚变研究中心 | Fresh-keeping method for chemical film optical element |
| WO2020124714A1 (en) * | 2018-12-21 | 2020-06-25 | 深圳市华星光电技术有限公司 | Color filter substrate, liquid crystal display panel and liquid crystal display device |
| CN110183114A (en) * | 2019-04-30 | 2019-08-30 | 太仓耀华玻璃有限公司 | A kind of anti-reflection coated glass and preparation method thereof |
| CN110176503A (en) * | 2019-06-05 | 2019-08-27 | 浙江力晟玻璃科技有限公司 | A kind of cadmium telluride power generating glass |
| CN111362587A (en) * | 2020-04-28 | 2020-07-03 | 东莞南玻太阳能玻璃有限公司 | High-hardness moisture-proof anti-reflection solar glass and preparation method thereof |
| CN111362587B (en) * | 2020-04-28 | 2022-05-24 | 东莞南玻太阳能玻璃有限公司 | High-hardness moisture-proof anti-reflection solar glass and preparation method thereof |
| CN114345662A (en) * | 2021-12-16 | 2022-04-15 | 中建材蚌埠玻璃工业设计研究院有限公司 | Antireflection film, preparation method thereof and antireflection film preparation device |
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