CN1084481C - Process for preparing zirconium oxide-silicon oxide film with high resistance to laser damage and high reflectivity - Google Patents
Process for preparing zirconium oxide-silicon oxide film with high resistance to laser damage and high reflectivity Download PDFInfo
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- CN1084481C CN1084481C CN98124659A CN98124659A CN1084481C CN 1084481 C CN1084481 C CN 1084481C CN 98124659 A CN98124659 A CN 98124659A CN 98124659 A CN98124659 A CN 98124659A CN 1084481 C CN1084481 C CN 1084481C
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- zirconia
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- reflecting film
- laser damage
- zirconium oxide
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Abstract
The present invention relates to a method for preparing a zirconium oxide/silicon oxide film with high resistance to laser damage and high reflectivity. A plurality of zirconium oxide (ZrO2) and silicon oxide (SiO2) films are alternatively prepared on a glass substrate by a chemical film plating method. A preparation method of zirconium oxide (ZrO2) sol film plating liquid comprises: tetrapropyl zirconate Zr(O-nC3H7)4 is used as a precursor; under the condition of alkaline or neutral catalysis, a certain amount of diglycol (DEG) is added, and after uniform stirring, water and absolute alcohol are added according to a certain proportion; after added solutions are mixed, an obtained solution is sufficiently stirred, and then, and the solution is loaded in a closed container for ageing under proper temperature. The present invention has the advantages of simple and convenient preparing process, needed film layers for achieving the purpose of high reflectivity are reduced and a damage threshold value of laser proofing of the films is 5 to 25 J/cm<2>(1064 nm, 3 ns).
Description
The invention belongs to a kind of preparation method of high-reflecting film, relate in particular to the preparation method that a kind of zirconia/monox is high resisting laser damage high-reflecting film.
Make high-reflecting film and adopt physical vaccum deposite and colloidal sol-gel plated film usually.
Physical vaccum deposite is with inorganic material high temperature evaporation in vacuum chamber, to glass substrate, form coating in the effect of electric field deposit then, because of its equipment complexity, involve great expense, institute's coatings is even inadequately, the micromechanism of wayward rete, and the not high shortcoming that is difficult to overcome of threshold for resisting laser damage, practical application is restricted.
The sol-gel processing plated film is with the colloid for preparing in advance, by rotation, lift or process such as meniscus plated film obtains rete.Researchist (international optical engineering proceedings Vol.2114,232; Vol.2253,764) select for use several different materials as high-index material, monox has prepared high-reflecting film as low-index material with sol-gel processing.Wherein thoria-monox can both meet the demands aspect optical property and the damage threshold two, but dangerous; Titanium dioxide-monox system provides the good optical performance, but does not have high damage threshold; Aluminium oxide-monox system can satisfy the requirement of damage threshold, but the refractive index of aluminium oxide has only 1.44, compares not very too greatly with monox refractive index 1.22, and reaching preferably, optical property then needs to plate a lot of tunics.The focus of research just progressively turns to zirconia/monox system at present, and wherein zirconia sol adopts inorganic synthetic method more, and (its threshold for resisting laser damage is 8J/cm for international optical engineering proceedings Vol.2253,764 reports according to document
2(1064nm, 3ns), but preparation process is very loaded down with trivial details, influence factor is many, wayward.Though adopt organic oxidation zirconium colloidal sol to prepare high-reflecting film a small amount of report is arranged, do not have the application of resisting laser damage aspect.
Goal of the invention of the present invention provides that a kind of to have preparation process zirconia/monox simple, control easily be the preparation method of high resisting laser damage high-reflecting film.
The object of the present invention is achieved like this: this rete is by alternately the several layers of zirconia and the membranous layer of silicon oxide of preparation are formed with electroless plating on the substrate of glass.The used zirconia sol coating liquid of this method is characterised in that the hydrolysis with diglycol control zirconium-n-propylate, directly a step is synthesized colloidal sol in organic solvent, adding a certain amount of polyvinylpyrrolidone in addition in system fills the zirconia duct, the index of refraction of rete is increased, reflecting effect strengthens, rete reaches the high anti-required number of plies to be reduced to some extent, and, the anti-laser damage threshold of rete is improved greatly.
Preparation method of the present invention is as follows:
1. the preparation of zirconia sol coating liquid: with the zirconium-n-propylate is presoma, under alkalescence or neutral catalytic condition, add stabilizing agent, polymeric additive, after stirring, add entry and absolute ethyl alcohol, mix the back and fully stir, under 0-60 ℃, carried out in the closed container of packing into then ageing 15-100 days;
The material molar ratio of zirconia sol is:
Zirconium-n-propylate: absolute ethyl alcohol: water: diglycol: polyvinylpyrrolidone: ammoniacal liquor=1: 86-172: 1-2.78: 0.53-2.97: 2.0 * 10
-5-2.0 * 10
-3: 0-0.15;
Described stabilizing agent is a diglycol, and described polymeric additive is a polyvinylpyrrolidone.
2. the method for preparing the silica sol coating liquid is: with methyl silicate or ethyl orthosilicate is presoma, under alkalescence or acidic catalyst condition, add entry and absolute ethyl alcohol by a certain percentage, fully stir mixed back, pack into then and under proper temperature, carry out ageing in the closed container, the preparation method sees Chinese invention patent particularly, application number 98106504.X;
3. the preparation of high-reflecting film: on substrate of glass, adopt rotary process or czochralski method and meniscus method alternately to prepare zirconia and membranous layer of silicon oxide;
The present invention compared with prior art has following advantage:
1. because with the hydrolysis of diglycol control zirconium-n-propylate, thus directly in organic solvent synthetic colloidal sol preparation process of a step simple and convenient.
2. owing to add polyvinylpyrrolidone, the zirconia duct is filled, the index of refraction of rete is increased, reflecting effect strengthens, rete reaches the high anti-required number of plies to be reduced to some extent, but also the anti-laser damage threshold of rete is improved greatly, threshold for resisting laser damage is: 5～25J/cm
2(1064nm, 3ns).
3. raw material is easy to get, and cost is low.
Embodiments of the invention are as follows:
Embodiment 1
With 0.01mol zirconium-n-propylate, 0.0053mol diglycol, 2.77 * 10
-7After polyvinylpyrrolidone (mean molecular weight 360000) and 0.86mol ethanol mix and stirs 10 minutes, add 0.0083mol water, 1.38 * 10 again
-3Ammoniacal liquor also continues to stir 1 hour, changes over to then in the teflon closed container, and ageing at room temperature alternately was coated with high-reflecting film with silica sol after 20 days.At 1064nm place reflectivity 〉=98%, threshold for resisting laser damage is higher than 15J/cm
2(1064nm, 3ns).
Embodiment 2
After 0.01mol zirconium-n-propylate, 0.0106mol diglycol and the mixing of 1.20mol ethanol and stirring 10 minutes, add 0.0166mol water, 1.38 * 10 again
-3Ammoniacal liquor also continues to stir 1 hour, changes over to then in the teflon closed container, and ageing at room temperature added 5.54 * 10 after 12 days
-7Polyvinylpyrrolidone (mean molecular weight 360000) is treated to dissolve fully and is fully shaken up the back and alternately is coated with high-reflecting film with silica sol.At 1064nm place reflectivity 〉=98%, threshold for resisting laser damage is higher than 15J/cm
2(1064nm, 3ns).
Embodiment 3
With 0.01mol zirconium-n-propylate, 0.0297mol diglycol, 1.00 * 10
-6After polyvinylpyrrolidone (mean molecular weight 200000) and 1.72mol ethanol mix and stir 10 minutes, add 0.0278mol water again and continue and stirred 1 hour, change over to then in the teflon closed container, ageing at room temperature alternately was coated with high-reflecting film with silica sol after 80 days.At 1064nm place reflectivity 〉=98%, threshold for resisting laser damage is higher than 15J/cm
2(1064nm, 3ns).
Embodiment 4
With 0.01mol zirconium-n-propylate, 0.0297mol diglycol, 2.00 * 10
-5After polyvinylpyrrolidone (mean molecular weight 30000) and 0.86mol ethanol mix and stir 10 minutes, add 0.0194mol water again and continue and stirred 1 hour, change over to then in the teflon closed container, ageing at room temperature alternately was coated with high-reflecting film with silica sol after 60 days.At 1064nm place reflectivity 〉=98%, threshold for resisting laser damage is higher than 15J/cm
2(1064nm, 3ns).
Claims (2)
1. preparation method that zirconia/monox is high resisting laser damage high-reflecting film alternately is plated in zirconia and silica sol coating liquid with electroless plating and forms high-reflecting film on the substrate of glass, and concrete steps are as follows:
(1) preparation of zirconia sol coating liquid: with the zirconium-n-propylate is presoma, under alkalescence or neutral catalytic condition, add stabilizing agent, polymeric additive, after stirring, add entry and absolute ethyl alcohol, mix the back and fully stir, under 0-60 ℃ of temperature, carried out ageing 15-100 days in the closed container of packing into then;
(2) method for preparing the silica sol coating liquid is: with methyl silicate or ethyl orthosilicate is presoma, under alkalescence or acidic catalyst condition, add entry and absolute ethyl alcohol, fully stir mixed back, carries out ageing in the closed container of packing into then under proper temperature;
(3) preparation of high-reflecting film: on substrate of glass, adopt rotary process or czochralski method and meniscus method alternately to prepare several layers of zirconia and membranous layer of silicon oxide;
It is characterized in that A: material molar ratio is in the described zirconia sol coating liquid:
Zirconium-n-propylate: absolute ethyl alcohol: water: diglycol: polyvinylpyrrolidone: ammoniacal liquor=1: 86-172: 1-2.78: 0.53-2.97: 2.0 * 10
-5-2.0 * 10
-3: 0-0.15;
B: described stabilizing agent is a diglycol, and polymeric additive is a polyvinylpyrrolidone.
2. a kind of zirconia/monox according to claim 1 is the preparation method of high resisting laser damage high-reflecting film, it is characterized in that described polyvinylpyrrolidone is that molecular weight is 3～360,000 superpolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98124659A CN1084481C (en) | 1998-11-04 | 1998-11-04 | Process for preparing zirconium oxide-silicon oxide film with high resistance to laser damage and high reflectivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98124659A CN1084481C (en) | 1998-11-04 | 1998-11-04 | Process for preparing zirconium oxide-silicon oxide film with high resistance to laser damage and high reflectivity |
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| CN1253297A CN1253297A (en) | 2000-05-17 |
| CN1084481C true CN1084481C (en) | 2002-05-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98124659A Expired - Fee Related CN1084481C (en) | 1998-11-04 | 1998-11-04 | Process for preparing zirconium oxide-silicon oxide film with high resistance to laser damage and high reflectivity |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100576070C (en) * | 2005-10-21 | 2009-12-30 | 同济大学 | A kind of method of photosensitive gel film that prepare to realize that raster graphic shifts |
| CN100434937C (en) * | 2006-12-18 | 2008-11-19 | 中国科学技术大学 | High-temperature-resistant optical film doped with stabilized zirconia and method for preparing same |
| CN101840015B (en) * | 2010-04-30 | 2011-09-07 | 重庆天缔光电有限公司 | Phase compensation film |
| CN108227047B (en) * | 2018-01-24 | 2019-08-13 | 四川大学 | A kind of optical element slowed down or eliminate the damage of laser induced optical element rear surface |
| CN109851231A (en) * | 2019-01-24 | 2019-06-07 | 福建工程学院 | A kind of antireflective, resisting laser damage glass and preparation method thereof |
| CN113671609B (en) * | 2021-07-27 | 2023-08-04 | 上海灵曼信息科技有限公司 | High-laser-damage-threshold film and preparation method thereof |
| CN114477192B (en) * | 2021-12-17 | 2023-03-03 | 山东科缘新材料科技有限公司 | Silicon-zirconium composite sol, and preparation method and application thereof |
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Granted publication date: 20020508 Termination date: 20121104 |