CN101012107A - Method of preparing high refractive index nanocrystalline TiO2 collosol-gel film - Google Patents
Method of preparing high refractive index nanocrystalline TiO2 collosol-gel film Download PDFInfo
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- CN101012107A CN101012107A CN 200710061505 CN200710061505A CN101012107A CN 101012107 A CN101012107 A CN 101012107A CN 200710061505 CN200710061505 CN 200710061505 CN 200710061505 A CN200710061505 A CN 200710061505A CN 101012107 A CN101012107 A CN 101012107A
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- colloidal sol
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- nanocrystalline
- tio
- refractive index
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- 238000000034 method Methods 0.000 title claims abstract description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title 2
- 239000010408 film Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 6
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 11
- 238000004528 spin coating Methods 0.000 claims description 10
- 206010013786 Dry skin Diseases 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000012530 fluid Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 abstract description 7
- -1 Titanium alkoxides Chemical class 0.000 abstract description 4
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- 239000010936 titanium Substances 0.000 abstract description 4
- 238000007747 plating Methods 0.000 abstract description 3
- 239000012788 optical film Substances 0.000 abstract 2
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Landscapes
- Surface Treatment Of Glass (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
一种高折射率纳米晶TiO2溶胶－凝胶薄膜制备的方法，钛醇盐先进行快速水解，然后用无机酸胶溶，在溶胶－凝胶过程中形成晶相TiO2纳米颗粒，从而显著提高目标光学薄膜的折射率。本发明具有操作简单、反应条件温和、大面积无规则镀制、设备成本低和光学薄膜折射率高的优点。A method for preparing high-refractive-index nanocrystalline TiO 2 sol-gel films. Titanium alkoxides are first hydrolyzed rapidly, and then peptized with inorganic acids to form crystalline TiO 2 nanoparticles during the sol-gel process, thereby significantly Increase the refractive index of the target optical film. The invention has the advantages of simple operation, mild reaction conditions, large-area random plating, low equipment cost and high refractive index of the optical film.
Description
Technical field
The invention belongs to TiO
2The preparation method of optical thin film specifically forms nanocrystalline TiO in sol-gel process
2, be coated with film then, thereby obviously improve the method for the specific refractory power of film.
Technical background
TiO
2Chemical stability and high refractive index with height, the while has high-clarity and low the absorption at visible and near infrared region, uses always and does the optical thin film material, is widely used in highly reflecting films, antireflective coating, optical fiber and waveguide material.The method that is used to prepare optical thin film at present is a lot, comprises electron beam evaporation plating, cathode vacuum spraying plating, chemical vapour deposition and sol-gel method deposition etc.Wherein sol-gel method has the following advantages: homogeneity is good, composition is controlled easily, low temperature prepares and equipment cost is low.Especially sol-gel process is implemented in easily that big area is coated with film in the substrate of irregularly shaped, differing materials.Yet traditional sol-gel process often adopts intercalating agent and the complexing of titanium alkoxide, hydrolysis, the polycondensation process of control titanium alkoxide, thus form the higher loose amorphous TiO of degree of crosslinking
2Colloidal sol, this TiO
2The film refractive index that colloidal sol is coated with is lower, has limited TiO greatly
2As the application of high-index material in optical device.
For same chemical constitution material, the crystalline specific refractory power generally will be higher than amorphous material far away, so if can form crystalline phase TiO in sol-gel process
2Will obviously improve the specific refractory power of film.
Summary of the invention
The object of the invention provides a kind of simple to operate, low temperature and the low high refractive index nanocrystalline TiO of equipment cost
2The method of colloidal sol-gel film preparation.
The object of the present invention is achieved like this: at first make titanium alkoxide complete hydrolysis with a large amount of water, add the mineral acid peptization then, form nanocrystalline colloidal sol through water-heat process, be coated with high refractive index TiO with spin-coating method again
2Optical thin film.
Preparation method of the present invention is as follows:
(1) nanocrystalline colloidal sol preparation:
Titanium isopropylate (TTIP) and ethanol 0.5～1: 1 reaction in molar ratio obtained transparent liquid in 2～10 minutes, this fluid drips is added in the deionized water, the mol ratio that makes titanium isopropylate and water is 1: 80～120, the while violent stirring, after forming white suspension liquid, with inorganic acid for adjusting pH value between 1～3, then through 10～30 minutes supersound process, 80～160 ℃ of reactions 5～20 hours, obtain nanocrystalline colloidal sol;
(2) optical thin film is coated with:
Nanocrystalline colloidal sol is concentrated into TiO under 50～80 ℃
2Mass concentration is 3～5%, adopts spin-coating method between rotating speed 2000～4000rpm, and the nanocrystalline colloidal sol after concentrating is coated with on the substrate, continues rotation 10～30 minutes, and the gained film was 110～120 ℃ of dryings 10～30 minutes.
Aforesaid mineral acid is HCl or HNO
3
The present invention compared with prior art has following advantage:
1. simple to operate, reaction conditions is gentle;
2. can on the irregular substrate of big area, be coated with film;
3. plated film required equipment cost is low;
4. the film refractive index that is coated with of nanocrystalline colloidal sol can reach more than 1.9.
Embodiment
Embodiment 1
The reaction in 0.5: 1 in molar ratio of titanium isopropylate (TTIP) and ethanol obtained transparent liquid in 2 minutes.Afterwards, this fluid drips is added in the deionized water, the mol ratio that makes TTIP and water is 1: 80, simultaneously violent stirring.After forming white suspension liquid, regulating the pH value with HCl is 1, then through 10 minutes supersound process, 160 ℃ of reactions 5 hours, obtains nanocrystalline colloidal sol.
Be concentrated into TiO with under 50 ℃ of the nanocrystalline colloidal sols
2Mass concentration is 3%.Adopt spin-coating method under rotating speed 2000rpm, the nanocrystalline colloidal sol after concentrating is coated with on the K9 glass substrate, continue rotation 10 minutes, the gained film was 110 ℃ of dryings 10 minutes.Film is measured through ellipsometer, and the specific refractory power at the 550nm place is 1.9126.
Embodiment 2
The reaction in 0.5: 1 in molar ratio of titanium isopropylate (TTIP) and ethanol obtained transparent liquid in 5 minutes.Afterwards, this fluid drips is added in the deionized water, the mol ratio that makes TTIP and water is 1: 100, simultaneously violent stirring.After forming white suspension liquid, regulating the pH value with HCl is 2, then through 15 minutes supersound process, 100 ℃ of reactions 10 hours, obtains nanocrystalline colloidal sol.
Be concentrated into TiO with under 50 ℃ of the nanocrystalline colloidal sols
2Mass concentration is 4%.Adopt spin-coating method under rotating speed 3000rpm, the nanocrystalline colloidal sol after concentrating is coated with on the K9 glass substrate, continue rotation 10 minutes, the gained film was 110 ℃ of dryings 15 minutes.Film is measured through ellipsometer, and the specific refractory power at the 550nm place is 1.9022.
Embodiment 3
The reaction in 1: 1 in molar ratio of titanium isopropylate (TTIP) and ethanol obtained transparent liquid in 3 minutes.Afterwards, this fluid drips is added in the deionized water, the mol ratio that makes TTIP and water is 1: 100, simultaneously violent stirring.After forming white suspension liquid, use HNO
3Regulating the pH value is 1.5, then through 15 minutes supersound process, 150 ℃ of reactions 5 hours, obtains nanocrystalline colloidal sol.
Be concentrated into TiO with under 80 ℃ of the nanocrystalline colloidal sols
2Mass concentration is 3%.Adopt spin-coating method under rotating speed 2000rpm, the nanocrystalline colloidal sol after concentrating is coated with on the quartz glass substrate, continue rotation 10 minutes, the gained film was 120 ℃ of dryings 10 minutes.Film is measured through ellipsometer, and the specific refractory power at the 550nm place is 1.9102.
Embodiment 4
The reaction in 0.8: 1 in molar ratio of titanium isopropylate (TTIP) and ethanol obtained transparent liquid in 5 minutes.Afterwards, this fluid drips is added in the deionized water, the mol ratio that makes TTIP and water is 1: 120, simultaneously violent stirring.After forming white suspension liquid, regulating the pH value with HCl is 2, then through 30 minutes supersound process, 150 ℃ of reactions 6 hours, obtains nanocrystalline colloidal sol.
Be concentrated into TiO with under 60 ℃ of the nanocrystalline colloidal sols
2Mass concentration is 5%.Adopt spin-coating method under rotating speed 4000rpm, the nanocrystalline colloidal sol after concentrating is coated with on the K9 glass substrate, continue rotation 15 minutes, the gained film was 110 ℃ of dryings 30 minutes.Film is measured through ellipsometer, and the specific refractory power at the 550nm place is 1.9081.
Embodiment 5
The reaction in 0.8: 1 in molar ratio of titanium isopropylate (TTIP) and ethanol obtained transparent liquid in 5 minutes.Afterwards, this fluid drips is added in the deionized water, the mol ratio that makes TTIP and water is 1: 100, simultaneously violent stirring.After forming white suspension liquid, use HNO
3Regulating the pH value is 2, then through 15 minutes supersound process, 80 ℃ of reactions 20 hours, obtains nanocrystalline colloidal sol.
Be concentrated into TiO with under 70 ℃ of the nanocrystalline colloidal sols
2Mass concentration is 4%.Adopt spin-coating method under rotating speed 3000rpm, the nanocrystalline colloidal sol after concentrating is coated with on the K9 glass substrate, continue rotation 30 minutes, the gained film was 115 ℃ of dryings 20 minutes.Film is measured through ellipsometer, and the specific refractory power at the 550nm place is 1.9065.
Embodiment 6
The reaction in 1: 1 in molar ratio of titanium isopropylate (TTIP) and ethanol obtained transparent liquid in 10 minutes.Afterwards, this fluid drips is added in the deionized water, the mol ratio that makes TTIP and water is 1: 110, simultaneously violent stirring.After forming white suspension liquid, regulating the pH value with HCl is 1.5, then through 15 minutes supersound process, 120 ℃ of reactions 8 hours, obtains nanocrystalline colloidal sol.
Be concentrated into TiO with under 60 ℃ of the nanocrystalline colloidal sols
2Mass concentration is 3%.Adopt spin-coating method under rotating speed 2000rpm, the nanocrystalline colloidal sol after concentrating is coated with on the quartz glass substrate, continue rotation 20 minutes, the gained film was 115 ℃ of dryings 20 minutes.Film is measured through ellipsometer, and the specific refractory power at the 550nm place is 1.9138.
Embodiment 7
The reaction in 0.5: 1 in molar ratio of titanium isopropylate (TTIP) and ethanol obtained transparent liquid in 5 minutes.Afterwards, this fluid drips is added in the deionized water, the mol ratio that makes TTIP and water is 1: 120, simultaneously violent stirring.After forming white suspension liquid, use HNO
3Regulating the pH value is 3, then through 10 minutes supersound process, 150 ℃ of reactions 5 hours, obtains nanocrystalline colloidal sol.
Be concentrated into TiO with under 50 ℃ of the nanocrystalline colloidal sols
2Mass concentration is 5%.Adopt spin-coating method under rotating speed 4000rpm, the nanocrystalline colloidal sol after concentrating is coated with on the quartz glass substrate, continue rotation 20 minutes, the gained film was 110 ℃ of dryings 20 minutes.Film is measured through ellipsometer, and the specific refractory power at the 550nm place is 1.9082.
Claims (2)
1, a kind of high refractive index nanocrystalline TiO
2The method of colloidal sol-gel film preparation is characterized in that comprising the steps:
(1) nanocrystalline colloidal sol preparation:
Titanium isopropylate and ethanol 0.5～1: 1 reaction in molar ratio obtained transparent liquid in 2～10 minutes, this fluid drips is added in the deionized water, the mol ratio that makes titanium isopropylate and water is 1: 80～120, the while violent stirring, after forming white suspension liquid, with inorganic acid for adjusting pH value between 1～3, then through 10～30 minutes supersound process, 80～160 ℃ of reactions 5～20 hours, obtain nanocrystalline colloidal sol;
(2) optical thin film is coated with:
Nanocrystalline colloidal sol is concentrated into TiO under 50～80 ℃
2Mass concentration is 3～5%, adopts spin-coating method between rotating speed 2000～4000rpm, and the nanocrystalline colloidal sol after concentrating is coated with on the substrate, continues rotation 10～30 minutes, and the gained film was 110～120 ℃ of dryings 10～30 minutes.
2, a kind of high refractive index nanocrystalline TiO as claimed in claim 1
2The method of colloidal sol-gel film preparation is characterized in that described mineral acid is HCl or HNO
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710061505A CN100593524C (en) | 2007-02-07 | 2007-02-07 | Preparation Method of High Refractive Index Nanocrystalline TiO2 Sol-Gel Thin Film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710061505A CN100593524C (en) | 2007-02-07 | 2007-02-07 | Preparation Method of High Refractive Index Nanocrystalline TiO2 Sol-Gel Thin Film |
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| Publication Number | Publication Date |
|---|---|
| CN101012107A true CN101012107A (en) | 2007-08-08 |
| CN100593524C CN100593524C (en) | 2010-03-10 |
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|---|---|---|---|
| CN200710061505A Expired - Fee Related CN100593524C (en) | 2007-02-07 | 2007-02-07 | Preparation Method of High Refractive Index Nanocrystalline TiO2 Sol-Gel Thin Film |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108117273A (en) * | 2017-12-26 | 2018-06-05 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of high reflectance glass microballoon and preparation method thereof |
| CN114561113A (en) * | 2022-03-08 | 2022-05-31 | 南京安淮创新药物研究院有限公司 | Preparation method of high-refractive-index titanium oxide transparent coating |
| CN117363063A (en) * | 2023-10-12 | 2024-01-09 | 夸泰克(广州)新材料有限责任公司 | Preparation method of nano titanium oxide spin-on material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6238738B1 (en) * | 1996-08-13 | 2001-05-29 | Libbey-Owens-Ford Co. | Method for depositing titanium oxide coatings on flat glass |
| CN1166451C (en) * | 2001-09-21 | 2004-09-15 | 清华大学 | Preparation method of nanocrystalline titanium dioxide photocatalyst supported on the surface of large particles |
| CN1390636A (en) * | 2002-07-25 | 2003-01-15 | 上海交通大学 | Photocatalyst of TiO film for purifying water and its preparing process |
| CN1304107C (en) * | 2004-10-22 | 2007-03-14 | 马贞亮 | Preparation process of photocatalyzing active nano TiO2 collosol |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108117273A (en) * | 2017-12-26 | 2018-06-05 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of high reflectance glass microballoon and preparation method thereof |
| CN108117273B (en) * | 2017-12-26 | 2019-10-29 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of high reflectance glass microballoon and preparation method thereof |
| CN114561113A (en) * | 2022-03-08 | 2022-05-31 | 南京安淮创新药物研究院有限公司 | Preparation method of high-refractive-index titanium oxide transparent coating |
| CN117363063A (en) * | 2023-10-12 | 2024-01-09 | 夸泰克(广州)新材料有限责任公司 | Preparation method of nano titanium oxide spin-on material |
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| CN100593524C (en) | 2010-03-10 |
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Granted publication date: 20100310 Termination date: 20130207 |