CN107942414A - A kind of bottom is the double-deck wideband anti-reflection film of organic inorganic hybridization film - Google Patents
A kind of bottom is the double-deck wideband anti-reflection film of organic inorganic hybridization film Download PDFInfo
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- CN107942414A CN107942414A CN201711442668.1A CN201711442668A CN107942414A CN 107942414 A CN107942414 A CN 107942414A CN 201711442668 A CN201711442668 A CN 201711442668A CN 107942414 A CN107942414 A CN 107942414A
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- 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
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
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Abstract
The present invention provides the double-deck wideband anti-reflection film that a kind of bottom is organic inorganic hybridization film, the bottom of double-deck wideband anti-reflection film and top layer are organic inorganic hybridization film, bottom is phenyl triethoxysilane/ethyl orthosilicate hybrid film, and top layer is vinyltriethoxysilane/ethyl orthosilicate hybrid film.Its preparation method is：Glass substrate is immersed in phenyl triethoxysilane/ethyl orthosilicate hybrid collosol, with certain pull rate plated film, bottom is plated in glass substrate surface；The glass substrate for being coated with bottom is immersed in vinyltriethoxysilane/ethyl orthosilicate hybrid collosol, with certain pull rate plated film, is made and is coated with bottom and the double layer antireflection coating on top layer, and it is heat-treated.The bilayer wideband anti-reflection film has good wideband antireflective effect and good optical stability.
Description
Technical field
The invention belongs to use optics field of film preparation, a kind of bottom is particularly related to as the double of organic-inorganic hybrid film
Slice width frequency anti-reflection film.
Background technology
Anti-reflection film is widely used in such as optics of high energy laser system, flat-panel screens and camera optical system member
Part surface.With the expansion of application range, it can realize that anti-reflection wideband anti-reflection film is widely studied in wider wave-length coverage.
Silica wideband anti-reflection film made from sol-gel process is that currently the only one kind is applied to high energy laser system
Wideband anti-reflection film.Common sol-gel silica anti-reflection film is mostly inorganic thin film, its polarity is strong, in the mistake used
Easily only attached polar contaminants, its optical stability are poor from environment in journey.Can be to colloidal sol-solidifying by hybrid inorganic-organic
Substantial amounts of organic group is introduced in glue method antireflecting silicon dioxide film, is conducive to suppression anti-reflection film and polarity pollution is adsorbed from environment
Thing.At present, the sol-gel silica wideband anti-reflection film applied to high energy laser system is double-decker, its top layer is
Hybrid inorganic-organic silica membrane, can relatively efficiently ensure the optical stability of anti-reflection film；But closed due to lacking
Suitable film material, its bottom are purely inorganic silica membrane, its optical stability needs to be further improved.
For it is mentioned above the problem of, it is main at present in terms of the optical stability of double-deck wideband anti-reflection film is further improved
It is to carry out ammonia treatment to bottom to want method, occurs to take off by the hydroxyl of adjacent silicon dioxide particle in bottom film by the catalysis of ammonia
Water reacts, to reduce the quantity of the hydroxyl of bottom film.But ammonia treatment process takes and complexity, is unfavorable for industrial applications.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to a kind of bottom is provided as organic-inorganic hybrid film
Double-deck wideband anti-reflection film.The present invention use have high index of refraction phenyl triethoxysilane/ethyl orthosilicate hybrid film for
Bottom, double-deck wideband is prepared by top layer of the vinyltriethoxysilane with low-refraction/ethyl orthosilicate hybrid film
Anti-reflection film.The bottom of double layer antireflection coating and top layer are organic-inorganic hybrid film, have more preferably optical stability.
In order to achieve the above object, the present invention adopts the following technical scheme that：
A kind of bottom is the double-deck wideband anti-reflection film of organic-inorganic hybrid film, and bottom and top layer are that hybrid inorganic-organic is thin
Film, bottom are phenyl triethoxysilane/ethyl orthosilicate hybrid film, and top layer is vinyltriethoxysilane/positive silicic acid
Ethyl ester hybrid film.
A kind of bottom is the preparation method of the double-deck wideband anti-reflection film of organic-inorganic hybrid film, is concretely comprised the following steps：
（1）The preparation of colloidal sol：
（a）The preparation of phenyl triethoxysilane/ethyl orthosilicate hybrid collosol：By phenyl triethoxysilane, positive silicic acid second
Ester, absolute ethyl alcohol, ammonium hydroxide, water 1-10 in mass ratio:5-20:50-300:0.5-2:0-5 is sequentially added into reaction vessel, close
0.5-5 h are reacted in stirring at 20-60 DEG C under conditions of closing, then in ageing 3-20 days under room temperature.
（b）The preparation of vinyltriethoxysilane/ethyl orthosilicate hybrid collosol：By vinyltriethoxysilane,
Ethyl orthosilicate, absolute ethyl alcohol, ammonium hydroxide, water 1-10 in mass ratio:5-20:50-300:0.5-2:0-5, which is sequentially added to reaction, to be held
In device, reaction 0.5-5 h are stirred at 20-60 DEG C under conditions of closed, then in ageing 3-20 days under room temperature.
（2）The preparation of double-deck wideband anti-reflection film
Glass substrate is immersed in phenyl triethoxysilane/ethyl orthosilicate hybrid collosol, with certain pull rate plated film,
Bottom is plated in glass substrate surface；The glass substrate for being coated with bottom is immersed into vinyltriethoxysilane/ethyl orthosilicate
In hybrid collosol, with certain pull rate plated film, it is made and is coated with bottom and the double layer antireflection coating on top layer, and hot place is carried out to it
Reason.
The pull rate is 50-400 mm/min, and heat treatment temperature is 60-150 DEG C, heat treatment time 1-24
h。
Compared with prior art, its distinguishing feature of the invention is：
The present invention use have high index of refraction phenyl triethoxysilane/ethyl orthosilicate hybrid film for bottom, with
The vinyltriethoxysilane of low-refraction/ethyl orthosilicate hybrid film prepares double-deck wideband anti-reflection film for top layer.It is double-deck
The bottom of anti-reflection film and top layer are organic-inorganic hybrid film, have more preferably optical stability.
Brief description of the drawings
Fig. 1 is the transmittance curve of each embodiment bilayer wideband anti-reflection film.
Embodiment
The present invention is further described with reference to embodiment.It is necessarily pointed out that the present embodiment is served only for
The present invention is further described, it is impossible to be interpreted as limiting the scope of the invention, the person skilled in the art in the field
Content it can make some nonessential modifications and adaptations according to the present invention.
Comparative example 1
By ethyl orthosilicate, absolute ethyl alcohol, water and ammonium hydroxide in mass ratio 15：150：4：1 sequentially adds into reaction vessel, closed
Under conditions of at 30 DEG C stirring reaction 2 h, then under room temperature be aged 7 days.It is molten that base catalysis inorganic silicon dioxide is made
Glue.
By ethyl orthosilicate, absolute ethyl alcohol and concentrated hydrochloric acid in mass ratio 5：100：0.1 sequentially adds into reaction vessel, close
2 h are reacted in stirring at 30 DEG C under conditions of closing, then in ageing 7 days under room temperature.Acid catalysis inorganic silicon dioxide is made
Colloidal sol.
Glass substrate is immersed in acid catalysis inorganic silicon dioxide colloidal sol, with the pull rate plated film of 250 mm/min,
Glass substrate surface plates bottom；The glass substrate for being coated with bottom is immersed in base catalysis inorganic silicon dioxide colloidal sol, with 150
The pull rate plated film of mm/min, obtained bottom and top layer are the double layer antireflection coating of inorganic thin film, and hot at a temperature of 120 DEG C
Handle 3 h.
Comparative example 2
By ethyl orthosilicate, absolute ethyl alcohol and concentrated hydrochloric acid in mass ratio 5：100：0.1 sequentially adds into reaction vessel, closed
Under the conditions of at 30 DEG C stirring reaction 2 h, then under room temperature be aged 7 days.It is molten that acid catalysis inorganic silicon dioxide is made
Glue.
By methyltriethoxysilane, ethyl orthosilicate, absolute ethyl alcohol, ammonium hydroxide, water in mass ratio 1:10:150:1:2 according to
Secondary addition stirs 2 h of reaction, then in ageing 7 days under room temperature under conditions of closed into reaction vessel at 30 DEG C.
Methyltriethoxysilane/ethyl orthosilicate hybrid collosol is made.
Glass substrate is immersed in acid catalysis inorganic silicon dioxide colloidal sol, with the pull rate plated film of 250 mm/min,
Glass substrate surface plates bottom；By be coated with bottom glass substrate immerse methyltriethoxysilane/ethyl orthosilicate it is organic-
In inorganic hybridization colloidal sol, with the pull rate plated film of 90 mm/min, obtained bottom is inorganic thin film and top layer is organic and inorganic
The double layer antireflection coating of hybrid film, and 3 h are heat-treated at a temperature of 120 DEG C.
Embodiment 1
By phenyl triethoxysilane, ethyl orthosilicate, absolute ethyl alcohol, ammonium hydroxide, water in mass ratio 3:10:100:0.5:1 successively
Add into reaction vessel, 2 h of reaction are stirred at 30 DEG C under conditions of closed, then in ageing 8 days under room temperature.System
Obtain phenyl triethoxysilane/ethyl orthosilicate hybrid collosol.
By vinyltriethoxysilane, ethyl orthosilicate, absolute ethyl alcohol, ammonium hydroxide, water in mass ratio 5:10:150:1:2
Sequentially add into reaction vessel, it is closed under conditions of at 35 DEG C 3 h of stirring reaction, then in being aged 5 under room temperature
My god.Vinyltriethoxysilane/ethyl orthosilicate hybrid collosol is made.
Glass substrate is immersed in phenyl triethoxysilane/ethyl orthosilicate hybrid collosol, with the lifting of 80 mm/min
Speed plated film, bottom is plated in glass substrate surface；The glass substrate for being coated with bottom is immersed into vinyltriethoxysilane/just
In silester hybrid collosol, with the pull rate plated film of 150 mm/min, it is made and is coated with bottom and the double layer antireflection coating on top layer,
And 2 h are heat-treated at a temperature of 100 DEG C.
Embodiment 2
By phenyl triethoxysilane, ethyl orthosilicate, absolute ethyl alcohol, ammonium hydroxide, water in mass ratio 6:10:150:0.8:2 successively
Add into reaction vessel, 4 h of reaction are stirred at 40 DEG C under conditions of closed, then in ageing 5 days under room temperature.System
Obtain phenyl triethoxysilane/ethyl orthosilicate hybrid collosol.
By vinyltriethoxysilane, ethyl orthosilicate, absolute ethyl alcohol, ammonium hydroxide, water in mass ratio 7:10:200:2:3
Sequentially add into reaction vessel, it is closed under conditions of at 45 DEG C 4 h of stirring reaction, then in being aged 9 under room temperature
My god.Vinyltriethoxysilane/ethyl orthosilicate hybrid collosol is made.
Glass substrate is immersed in phenyl triethoxysilane/ethyl orthosilicate hybrid collosol, with carrying for 150 mm/min
Pulling rate degree plated film, bottom is plated in glass substrate surface；By be coated with bottom glass substrate immerse vinyltriethoxysilane/
In ethyl orthosilicate hybrid collosol, with the pull rate plated film of 250 mm/min, it is made and is coated with bottom and the double-layer anti-reflection on top layer
Film, and 10 h are heat-treated at a temperature of 120 DEG C.
Embodiment 3
By phenyl triethoxysilane, ethyl orthosilicate, absolute ethyl alcohol, ammonium hydroxide, water in mass ratio 9:10:200:1:4 add successively
Enter into reaction vessel, 5 h of reaction are stirred at 50 DEG C under conditions of closed, then in ageing 5 days under room temperature.It is made
Phenyl triethoxysilane/ethyl orthosilicate hybrid collosol.
By vinyltriethoxysilane, ethyl orthosilicate, absolute ethyl alcohol, ammonium hydroxide, water in mass ratio 8:10:300:2:4
Sequentially add into reaction vessel, it is closed under conditions of at 45 DEG C 5 h of stirring reaction, then in being aged 12 under room temperature
My god.Vinyltriethoxysilane/ethyl orthosilicate hybrid collosol is made.
Glass substrate is immersed in phenyl triethoxysilane/ethyl orthosilicate hybrid collosol, with carrying for 200 mm/min
Pulling rate degree plated film, bottom is plated in glass substrate surface；By be coated with bottom glass substrate immerse vinyltriethoxysilane/
In ethyl orthosilicate hybrid collosol, with the pull rate plated film of 3000 mm/min, it is made and is coated with bottom and the layer on top layer is anti-reflection
Film, and 20 h are heat-treated at a temperature of 150 DEG C.
Fig. 1 shows embodiment 1（a）, embodiment 2（b）With embodiment 3（c）Obtained hybrid inorganic-organic double layer antireflection coating
With good wideband effect, and the wideband effect of embodiment 3 is more excellent.As it can be seen that when phenyl triethoxysilane and positive silicic acid second
When ester and vinyltriethoxysilane and the quality of ethyl orthosilicate are than higher, the wideband effect of obtained wideband anti-reflection film
It is more excellent.
Wideband anti-reflection film made from 1 comparative example of table and each embodiment in wet environment use 1 month after in 400-1100
The drop-out value of nm wave-length coverage mean transmissivities
Table 1 shows, when the bottom of double layer antireflection coating and top layer are inorganic silicon dioxide film, its optical stability is poor,
After being used one month in wet environment, its mean transmissivity declines 3.8%.When the bottom of double layer antireflection coating is inorganic thin film and table
When layer is organic-inorganic hybrid film, its optical stability increases compared with comparative example 1, but one is used in wet environment
After month, its mean transmissivity still declines 1.23%.Embodiment 1, embodiment 2 and hybrid inorganic-organic made from embodiment 3 are double-deck
Wideband anti-reflection film mean transmissivity declines 0.50%, 0.36% and 0.21% respectively, illustrates that hybrid inorganic-organic bilayer wideband is anti-reflection
Film has more preferably optical stability.Meanwhile embodiment 3 is because introducing more organic groups, therefore there is optimal optics
Stability.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, should all belong to the covering scope of the present invention.
Claims (8)
1. a kind of bottom is the double-deck wideband anti-reflection film of organic-inorganic hybrid film, it is characterised in that：Double-deck wideband anti-reflection film
Bottom and top layer are organic-inorganic hybrid film, and bottom is phenyl triethoxysilane/ethyl orthosilicate hybrid film.
2. bottom according to claim 1 is the double-deck wideband anti-reflection film of organic-inorganic hybrid film, it is characterised in that：
Top layer is vinyltriethoxysilane/ethyl orthosilicate hybrid film.
A kind of 3. side for preparing the double-deck wideband anti-reflection film that bottom as claimed in claim 1 or 2 is organic-inorganic hybrid film
Method, it is characterised in that：Glass substrate is immersed in phenyl triethoxysilane/ethyl orthosilicate hybrid collosol, is carried with certain
Pulling rate degree plated film, bottom is plated in glass substrate surface；By be coated with bottom glass substrate immerse vinyltriethoxysilane/
In ethyl orthosilicate hybrid collosol, with certain pull rate plated film, it is made and is coated with bottom and the double layer antireflection coating on top layer, and it is right
It is heat-treated.
4. the method according to claim 3 for preparing the double-deck wideband anti-reflection film that bottom is organic-inorganic hybrid film, its
It is characterized in that：The preparation method of the phenyl triethoxysilane/ethyl orthosilicate hybrid collosol is：By phenyl triethoxy
Silane, ethyl orthosilicate, absolute ethyl alcohol, ammonium hydroxide, water 1-10 in mass ratio:5-20:50-300:0.5-2:0-5 sequentially add to
In reaction vessel, it is closed under conditions of at 20-60 DEG C stirring reaction 0.5-5 h, then in being aged 3-20 under room temperature
My god, colloidal sol is made.
5. the method for the double-deck wideband anti-reflection film that bottom is organic-inorganic hybrid film of preparing described in claim 3, its feature
It is：The preparation method of the vinyltriethoxysilane/ethyl orthosilicate hybrid collosol is：By vinyl triethoxyl
Silane, ethyl orthosilicate, absolute ethyl alcohol, ammonium hydroxide, water 1-10 in mass ratio:5-20:50-300:0.5-2:0-5 sequentially add to
In reaction vessel, it is closed under conditions of at 20-60 DEG C stirring reaction 0.5-5 h, then in being aged 3-20 under room temperature
My god, colloidal sol is made.
6. the method for the double-deck wideband anti-reflection film that bottom is organic-inorganic hybrid film of preparing described in claim 3, its feature
It is：The pull rate is 50-400 mm/min.
7. the method for the double-deck wideband anti-reflection film that bottom is organic-inorganic hybrid film of preparing described in claim 3, its feature
It is：Its temperature of the heat treatment is 60-150 DEG C.
8. the method for the double-deck wideband anti-reflection film that bottom is organic-inorganic hybrid film of preparing described in claim 3, its feature
It is：Its time of the heat treatment is 1-24 h.
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| CN201711442668.1A CN107942414B (en) | 2017-12-27 | 2017-12-27 | A kind of bottom is the double-deck wideband anti-reflection film of organic-inorganic hybrid film |
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| CN201711442668.1A CN107942414B (en) | 2017-12-27 | 2017-12-27 | A kind of bottom is the double-deck wideband anti-reflection film of organic-inorganic hybrid film |
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| US6521677B2 (en) * | 1998-11-06 | 2003-02-18 | Dsm N.V. | Radiation-curable metal particles and curable resin compositions comprising these particles |
| CN104755570A (en) * | 2012-10-30 | 2015-07-01 | 乐金华奥斯有限公司 | Anti-reflective coating composition including siloxane compound, and anti-reflective film adjusting surface energy by using same |
| CN106630668A (en) * | 2016-10-12 | 2017-05-10 | 福建农林大学 | Method for preparing SiO2 antireflection film with controllable refractive index by using propyltriethoxysilane |
-
2017
- 2017-12-27 CN CN201711442668.1A patent/CN107942414B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6521677B2 (en) * | 1998-11-06 | 2003-02-18 | Dsm N.V. | Radiation-curable metal particles and curable resin compositions comprising these particles |
| CN104755570A (en) * | 2012-10-30 | 2015-07-01 | 乐金华奥斯有限公司 | Anti-reflective coating composition including siloxane compound, and anti-reflective film adjusting surface energy by using same |
| CN106630668A (en) * | 2016-10-12 | 2017-05-10 | 福建农林大学 | Method for preparing SiO2 antireflection film with controllable refractive index by using propyltriethoxysilane |
Non-Patent Citations (1)
| Title |
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| 李 坚，刘佳一，张阳德: "一种新型纳米增透防雾膜对光学镜片的表面改性", 《中国组织工程研究与临床康复》 * |
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