CN104445970A - Method for rapidly stripping fluoride film from surface of optical fused quartz base - Google Patents
Method for rapidly stripping fluoride film from surface of optical fused quartz base Download PDFInfo
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- CN104445970A CN104445970A CN201410621218.9A CN201410621218A CN104445970A CN 104445970 A CN104445970 A CN 104445970A CN 201410621218 A CN201410621218 A CN 201410621218A CN 104445970 A CN104445970 A CN 104445970A
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- fused quartz
- acid
- fluoride film
- demoulding
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Abstract
The invention discloses a method for rapidly stripping a fluoride film from the surface of an optical fused quartz base, and belongs to the technical field of preparation methods of optical elements. According to the method, a replacement reaction or a complex reaction is performed at room temperature or at a heating condition, so that fluoride on the surface of the optical fused quartz base can have a chemical reaction so as to be completely removed; the film can be removed within at least 20-30 minutes by reaction in a hot water bath, can be removed within 1.5-2.5 hours by reaction in a warm water bath and can be removed within 3-7 hours by reaction at room temperature. After the film is removed, the optical fused quartz base has no obvious changes in surface roughness and no detectable physical or chemical damages in comparison with an uncoated optical base.
Description
Technical field
The present invention relates to optical element preparation method technical field, be specifically related to the quick method for demoulding of a kind of fused quartz optical substrate surface fluoride film.
Background technology
In 193nm excimer lithography optical system, employ that substrate is fused quartz material, film is the optical element of fluoride materials in a large number.These optical elements due to different reason need the existing fluoride film in removing surface more again plated film time, realize film removing usually through optical polish method.Optical polish method not only time-consuming, cost is high, and can change optical element surface face type to a certain extent, the imaging characteristic affecting optical element even makes optical element lose recycle value completely.And if loseless method can be adopted to be removed fast by fused quartz optical substrate surface fluoride film, then the fused quartz optical substrate after can making demoulding utilizes again, effectively cost-saving, produces considerable economic benefit.A kind of beyond doubt economic, effective method for demoulding of chemistry striping.For the fluoride film of fused quartz optical substrate surface, the selection of chemical process must be determined according to concrete fluoride film material.For the optical element of 193nm excimer lithography optical system, its fluoride film major ingredient comprises magnesium fluoride, aluminum fluoride and lanthanum fluoride.Their character is as follows respectively: magnesium fluoride is a kind of colourless tetragonal crystal or powder, tasteless, is insoluble in water and alcohol, is slightly soluble in diluted acid, be dissolved in nitric acid.Aluminum fluoride: colourless or white crystals, water insoluble, be insoluble to bronsted lowry acids and bases bronsted lowry, character is very stable, heats altogether with liquefied ammonia or the vitriol oil, or all reactionless with potassium hydroxide congruent melting.Lanthanum fluoride: white powder, water insoluble, be insoluble in hydrochloric acid, nitric acid and sulfuric acid, but can perchloric acid be dissolved in.From the character of three kinds of fluorochemicals, adopt during chemical reaction demoulding and also have more limitation, such as aluminum fluoride, character is very stable, and strong acid, highly basic do not react, moreover alkali can etch quartz sheet.In addition, except hydrofluoric acid, hot phosphoric acid, silica glass has good acid resistance to general acid.
Summary of the invention
The object of the invention is to the method proposing the quick demoulding of a kind of fused quartz optical substrate surface fluoride film, the method uses conventional mineral acid and inorganic salt as reagent, greatly reduce cost, simplify laboratory operating procedures, shorten the reaction times, there is the features such as easy quick, safe and efficient, with low cost, environmental protection.
To achieve these goals, the quick method for demoulding of a kind of fused quartz optical substrate surface fluoride film of the present invention, step is as follows:
Pipette the mineral acid of certain volume, be poured in the deionized water of certain volume, make mineral acid ultimate density be 1.0-5.0mol/L.Inorganic acid solution is mixed with surfactant soln (0.0 – 20mmol/L) or metal salt solution (0.1-5.0mol/L), forms liquid parting.The optical element of fused quartz substrate fluoride film is inserted in liquid parting, under room temperature, warm water bath or hot water bath condition, reacts 10 – take out after 500 minutes and adopt washed with de-ionized water, obtain the fused quartz optical component of thorough demoulding.
Wherein said mineral acid is the vitriol oil or concentrated nitric acid or strong phosphoric acid or concentrated hydrochloric acid or boric acid;
The preparation method of surfactant soln is wherein: pipette or take a certain amount of tensio-active agent, is dissolved in the deionized water of certain volume, makes tensio-active agent ultimate density be 0.0 – 20mmol/L.
Described tensio-active agent is anionic surfactant sodium dodecylbenzene sulfonate or cats product cetyl trimethylammonium bromide or zwitterionics or non-ionic surfactant Tween 40;
The preparation method of metal salt solution is wherein: take a certain amount of trivalent metal salt hydrate, be dissolved in the deionized water of certain volume, makes inorganic salt ultimate density be 0.1-5.0mol/L.
Described inorganic salt are iron chloride hexahydrate or trichloride hydrate aluminium.
Further, the ratio of the amount of reactant species is mineral acid: tensio-active agent=1:0.0-0.05; Mineral acid: inorganic salt=1:0.1 – 1.0.
Further, bath temperature 40-100 DEG C.
Further, heating equipment used is thermostat water bath or hydrothermal reaction kettle.
Principle of the present invention is:
Industrial employing fluorite (Calcium Fluoride (Fluorspan) CaF
2) and the vitriol oil is heated to 700 DEG C time prepare hydrofluoric acid (Zhang Qinglian, " inorganic chemistry book series " the 6th volume: Science Press, 1995:30-31)
Chemical equation is as follows:
CaF
2+ H
2sO
4(heat is dense) → 2HF+CaSO
4(1)
This realizes based on replacement(metathesis)reaction, and heating is conducive to reaction and carries out; Equally, remove fluorochemical based on complex reaction and need heating equally.As H
3bO
3-HCl and Calcium Fluoride (Fluorspan) Hybrid Heating are dissolved, and Calcium Fluoride (Fluorspan) proceeds in solution, and now boron and fluorine are combined into complex ion.
2CaF
2+4HCl+H
3BO
3＝2CaCl
2+HBF
4+3H
2O (2)
When continuing evaporating solns, fluorine is with BF
3form is overflowed.
Visible, aforesaid method all be unable to do without heating, and heating is conducive to reaction and carries out, and fluorochemical can be made again to evaporate effusion, make reaction product solubleness increase simultaneously, be unlikely to be deposited in optical substrate.
Utilize F-in the solution with Al
3+, Fe
3+etc. forming AlF
6 3-, plating filmed metals fluorochemical is reacted and forms soluble fluoride, reaction equation is as follows:
MgF
2+3HCl+AlCl
3＝3MgCl
2+H
3AlF
6(3)
Research finds, this reaction has higher speed of reaction at ambient temperature, is suitable for room temperature membrane removal, suitably improves temperature of reaction, can fast reaction speed, prevents reaction product from depositing.
Compared with prior art, the advantage of the inventive method is:
Method for demoulding of the present invention is simple to operate, and raw material is cheaply easy to get, and adopts hot water bath method fast reaction speed, can within very short time demoulding, be suitable for the emergent membrane removal of compact optical element, namely remove i.e. use, the film that warm water bath and room temperature method are suitable for the fused quartz optical substrate surface of larger area is removed.
Accompanying drawing explanation
Fig. 1 is the ultraviolet-visible optical transmission spectra figure of quick membrane removal in hot water bath, and the transmitance wherein during compound film floride-free using fused quartz optical substrate surface is as 100% baseline.
Fig. 2 is the ultraviolet-visible optical transmission spectra figure of very fast membrane removal in warm water bath, and the transmitance wherein during compound film floride-free using fused quartz optical substrate surface is as 100% baseline.
Fig. 3 is the ultraviolet-visible optical transmission spectra figure removing plated film under room temperature condition, and the transmitance wherein during compound film floride-free using fused quartz optical substrate surface is as 100% baseline.
Embodiment
Below in conjunction with specific embodiment, the inventive method is described in further detail.Following examples are preferred implementations more of the present invention, and object is to set forth content of the present invention better, instead of produces any restriction to protection scope of the present invention.
Embodiment 1
The quick method for demoulding of a kind of fused quartz optical substrate surface fluoride film, its concrete steps are as follows:
Pipette the 11.1mL vitriol oil, slowly pour in the beaker be equipped with in appropriate amount of deionized water along walls of beaker, suitably transfer in 100mL volumetric flask after cooling, be settled to 100mL, strength of solution is 2M.Pipette this solution 12mL, pipette the tensio-active agent cetyl trimethylammonium bromide solution 8mL of 2mM in beaker, the fused quartz optical component being coated with fluoride film is put into beaker, this beaker is put into 95 DEG C of water-baths and heat different time, take out fused quartz optical component and clean, measuring the transmitance of fused quartz optical component.Find that reaction 20 minutes plated films are thoroughly removed, ultraviolet-visible optical transmission spectra curve is got back near baseline.
In embodiment 1, bath temperature is 95 DEG C, sulfuric acid concentration 1.2M and above time, 20-30 minute can thoroughly membrane removal (the results are shown in Figure 1).
Embodiment 2
The quick method for demoulding of a kind of fused quartz optical substrate surface fluoride film, its concrete steps are as follows:
Pipette 27mL concentrated hydrochloric acid in 100mL volumetric flask, be settled to 100mL, strength of solution is 3.24M.Taking 12.07 grams, trichloride hydrate aluminium is dissolved in this hydrochloric acid soln, and aluminum trichloride concentration is 1M.Pipette this mixed solution 10mL, be heated to 55 DEG C, the fused quartz optical component being coated with fluoride film is put into beaker and reacts different time, take out fused quartz optical component and clean, measure the transmitance of fused quartz optical component.Find reaction 2.0 hours, plated film is thoroughly removed, and ultraviolet-visible optical transmission spectra curve is got back near baseline.
In example 2, when the mol ratio of hydrochloric acid and aluminum chloride be 3:1 and above time, under room temperature condition 3-7 hour can thoroughly membrane removal (the results are shown in Figure 3).If want, shortened in the reaction times, suitably can improve temperature of reaction, in warm water bath, react membrane removal, when bath temperature is 55 DEG C, can thoroughly remove plated film (the results are shown in Figure 2) within 1.5-2.5 hour.
Embodiment 3
The quick method for demoulding of a kind of fused quartz optical substrate surface fluoride film, its concrete steps are as follows:
Pipette 27mL concentrated hydrochloric acid in 100mL volumetric flask, be settled to 100mL, strength of solution is 3.24M.Taking 12.07 grams, trichloride hydrate aluminium is dissolved in this hydrochloric acid soln, and aluminum trichloride concentration is 1M.Pipette this mixed solution 10mL, the fused quartz optical component being coated with fluoride film is put into beaker, under room temperature condition, react different time, take out fused quartz optical component and clean, measure the transmitance of fused quartz optical component.Find reaction 7.0 hours, plated film is thoroughly removed, and ultraviolet-visible optical transmission spectra curve is got back near baseline (the results are shown in Figure 3).
Claims (4)
1. the quick method for demoulding of fused quartz optical substrate surface fluoride film, is characterized in that step is as follows:
Pipette the mineral acid of certain volume, be poured in the deionized water of certain volume, mineral acid ultimate density is made to be 1.0-5.0mol/L, inorganic acid solution is mixed with 0.0 – 20mmol/L surfactant soln or 0.1-5.0mol/L metal salt solution, form liquid parting, the optical element of fused quartz substrate fluoride film is inserted in liquid parting, under room temperature, warm water bath or hot water bath condition, react 10 – take out after 500 minutes and adopt washed with de-ionized water, obtain the fused quartz optical component of thorough demoulding;
Wherein said mineral acid is the vitriol oil or concentrated nitric acid or strong phosphoric acid or concentrated hydrochloric acid or boric acid or fluoroboric acid;
The preparation method of surfactant soln is wherein: pipette or take a certain amount of tensio-active agent, is dissolved in the deionized water of certain volume, makes tensio-active agent ultimate density be 0.0 – 20mmol/L;
Described tensio-active agent is anionic surfactant sodium dodecylbenzene sulfonate or cats product cetyl trimethylammonium bromide or zwitterionics or non-ionic surfactant Tween 40;
The preparation method of metal salt solution is wherein: take a certain amount of trivalent metal salt hydrate, be dissolved in the deionized water of certain volume, makes inorganic salt ultimate density be 0.1-5.0mol/L;
Described inorganic salt are iron chloride hexahydrate or trichloride hydrate aluminium.
2. the quick method for demoulding of a kind of fused quartz optical substrate surface fluoride film according to claim 1, is characterized in that: the ratio of the amount of reactant species is mineral acid: tensio-active agent=1:0.0-0.05; Mineral acid: inorganic salt=1:0.1 – 1.0.
3. the quick method for demoulding of a kind of fused quartz optical substrate surface fluoride film according to claim 1, is characterized in that: bath temperature 40-100 DEG C.
4. the quick method for demoulding of a kind of fused quartz optical substrate surface fluoride film according to claim 1, is characterized in that: heating equipment used is thermostat water bath or hydrothermal reaction kettle.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107065175A (en) * | 2017-05-19 | 2017-08-18 | 中国工程物理研究院激光聚变研究中心 | The method for removing the anti-reflection chemical film of silica in fused quartz optical component |
| CN111233346A (en) * | 2018-11-28 | 2020-06-05 | 惠州比亚迪电子有限公司 | Deplating agent and preparation method, deplating method and application thereof |
-
2014
- 2014-11-06 CN CN201410621218.9A patent/CN104445970B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 徐珍: "方解石基羟基磷灰石的制备及其对水中氟化物的去除效能研究", 《环境污染与防治》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107065175A (en) * | 2017-05-19 | 2017-08-18 | 中国工程物理研究院激光聚变研究中心 | The method for removing the anti-reflection chemical film of silica in fused quartz optical component |
| CN111233346A (en) * | 2018-11-28 | 2020-06-05 | 惠州比亚迪电子有限公司 | Deplating agent and preparation method, deplating method and application thereof |
| CN111233346B (en) * | 2018-11-28 | 2022-12-02 | 惠州比亚迪电子有限公司 | Deplating agent and preparation method, deplating method and application thereof |
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