CN1359032A - Photoinduction SiO2 gel preparation and microfine pattern making method thereof - Google Patents
Photoinduction SiO2 gel preparation and microfine pattern making method thereof Download PDFInfo
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- CN1359032A CN1359032A CN 01145262 CN01145262A CN1359032A CN 1359032 A CN1359032 A CN 1359032A CN 01145262 CN01145262 CN 01145262 CN 01145262 A CN01145262 A CN 01145262A CN 1359032 A CN1359032 A CN 1359032A
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Abstract
The present invention discloses a method for preparing light-sensitive SiO2 gel film and method for producing its microfine graph. In said ivnention, sol-gel method is adopted to prepare film, and added with chemical dressing agent to make it and Si form photosensitive chelate, when this film is irradiated by UV ray, the photosensitive chelated can be decomposed so as to make the dissolution property of said film produce change in the organic solvent, and can conveniently obtain the microfine graph of SiO2 film. It can be used for preparing refractive index modified derivative element, for example for preparing reflective index modified grating.
Description
One, technical field
The present invention relates to SiO
2A kind of photonasty colloidal sol of film fine-pattern technology, gel film and preparation method thereof, further relate to a kind of making that can be applicable to optical diffraction components and parts in the optical communication field such as grating, optical splitter, or be applied to making of the groove class substrate in microelectronics and the optoelectronic areas etc.
Two, background technology
Along with the development rapidly of optical communication cause, the beam splitting that is used for light is closed integrated optical elements such as bundle, wavelength-division multiplex and have higher requirement, and SiO
2Film becomes one of most important optical thin film in the integrated optics owing to have good light transmittance and low optical loss performance.But in concrete integrated optical circuit, usually need SiO
2Film is made slab waveguide or specific film pattern.In addition, the minute graphic representation of film also is one of gordian technique in microelectronics and the optoelectronic areas.
Existing SiO
2The film fine-pattern technology is to adopt traditional photoetching technique
[1,2,3], or ion etching technology
[4]Photoetching process prepares Micropicture will be by the system film, resist coating, and exposure is developed, and the HF acid corrosion removes operations such as glue.Operation is various, and in addition complex technical process, owing to also need to use Korrosionsmedium, causes environmental pollution on the one hand, also can corrode substrate on the other hand, is difficult to obtain high-quality Micropicture.Ion etching technology device therefor costliness, the etching inefficiency because the bombardment of ion beam easily causes pattern edge to subside, is difficult to obtain the regular figure in edge
[4]
Prepare SiO in conjunction with the sol-gel masking technique
2The research of film fine-pattern also has report, mainly contains mold pressing and casting.Die pressing at first adds organism and prepares soft gel in colloidal sol, suppress Micropicture with mould again, removes organism through bakingout process at last.The required Micropicture mould of this method prepares just very difficult, and organic content is too high, is easy to cause the film cracking in the heat treatment process
[5]And casting can not prepare film on specific substrate
[6], almost do not have practical value for the preparation Micropicture.
In recent years also useful Ultra-Violet Laser or energetic particle beam are induced the chemcor glass film
[7]Or chemcor glass
[8]Form the method for fine waveguide and prepare SiO with the group of molecules packing technique
2The method of film fine-pattern
[9]These method and technology difficulty are big, and very big difficulty is arranged in actual applications.
Three, summary of the invention
SiO
2The film fine-pattern technology has crucial application at optical communication, microelectronics, optoelectronic areas, and prepares SiO at present
2All there is defective in various degree in the technology of film fine-pattern, has a lot of scientists still to be devoted to the research of this respect at present.Thereby, develop and a kind ofly need not photoresist, need not the burn into of Korrosionsmedium and can prepare SiO simply, efficiently
2Film and high-quality minute graphic representation technology have important practical value.
The present invention has taken all factors into consideration SiO
2The making of film and microfabrication process.Adopt sol-gel process to prepare the SiO of photoinduction in conjunction with the method for chemical modification
2Gel film, and adopt method such as ultraviolet lighting can at a low price and obtain SiO in high quality
2Film and Micropicture thereof.
Can also utilize the photonasty colloidal sol of this invention, prepare photonasty SiO
2Gel film, ultraviolet light is by mask irradiation photonasty SiO
2Gel film imposes suitable thermal treatment again, can form different refractive index zones in film, utilizes this principle can prepare refractive index modified tone shape grating.
The technical solution adopted in the present invention is: the method that sol-gel combines with chemical modification prepares photoinduction colloidal sol, utilizes this gel to prepare photoinduction SiO on various substrates such as silicon plate or quartz base plate
2Gel film, further by illumination, organicly dissolve and wash away, Micropicture that process such as thermal treatment obtains film.Or by illumination and thermal treatment acquisition refractive index modified tone type Micropicture.
Detailed process is carried out by the following method:
(1) photonasty SiO
2The colloidal sol preparation
At first adopt chemical modification method to prepare photonasty colloidal sol, the component and the proportioning of its colloidal sol are as follows:
TEOS∶H
2O∶HCl∶EeOH∶Ph＝1∶(2-4)∶(0.05-0.2)∶(10-40)∶(0.5-2)
TEOS------ethyl orthosilicate (Si (OC
2H
5)
4) generation SiO
2Base stock
EeOH------ethanol (C
2H
5OH) solvent
Ph--------phenanthroline (C
12H
8N
2) form the chemical modifier of photonasty chelate
H
2O-------water and TEOS add the base stock of water reaction
The catalyst of HCl-------hydrochloric acid accelerated reaction
Behind the chemical reagent mixing stirring 4h with above component, just can obtain the photonasty SiO of homogeneous transparent
2Colloidal sol;
(2) SiO
2Film preparation and Micropicture preparation
Use the colloidal sol of (1) preparation, can on various glass or silicon substrate, make SiO with czochralski method
2Gel film, Zhi Bei film has stronger absorption peak near 274nm in this way, and during with corresponding UV-irradiation, absorption peak weakens and fades away, with this film of ultraviolet pre-irradiation solubilized in organic solvent such as ethanol, can not dissolve after the irradiation, according to this phenomenon, ultraviolet light shines this photonasty gel film by mask, then it being soaked the back in organic solvent takes out a moment, local dissolved by illumination not, and the place of illumination remains, and obtains SiO
2The Micropicture of gel film;
(3) further carry out 500 ℃-600 ℃ thermal treatment 20min, make in the film residual organic volatilization remove the back and just can obtain SiO
2The Micropicture of film; (4) refractive index modified tone type Micropicture preparation
(4) use the colloidal sol of (1) to prepare film, illumination is decomposed with the chelate in the rear film, makes the variation of residual organic matter in the heat treatment process be different from the film of not illumination.When ultraviolet light by mask or laser interferance method irradiate, impose 200-450 ℃ thermal treatment again, will be in film and cause the light area with not according to the difference of areas diffract rate; Utilize this phenomenon can prepare refractive index modified tone type grating or refractive index modified tone type Micropicture.
Prepare SiO with the present invention
2Micropicture need not valuable equipment, need not Korrosionsmedium, having reduced process procedure, is that the preparation technology of Micropicture greatly simplifies, and can prepare high-quality Micropicture simultaneously, can be applied to groove class substrate, diffraction components and parts such as groove class grating, optical splitter etc.
Prepare refractive index modified tone type Micropicture with the present invention, technology is simple, and is with low cost, can be applicable to the preparation of diffraction class components and parts such as refractive index modified tone type grating.
Four, description of drawings
Fig. 1 is SiO
2The ultraviolet spectrum of gel film and with ultraviolet ray according to the time variation diagram;
Fig. 2 utilizes photonasty SiO
2Film preparation SiO
2The synoptic diagram of film fine-pattern process;
Fig. 3 be the ultraviolet radiation zone territory of film and not the refractive index of irradiation area with the variation diagram of heat treatment temperature;
Fig. 4 is the SiO for preparing on silicon substrate with the present invention
2The light micrograph of Micropicture;
Fig. 5 is the SiO for preparing on silicon substrate with the present invention
2The light micrograph of minute groove;
Fig. 6 is the SiO for preparing on silicon substrate with the present invention
2The light micrograph of waveguide optical grating;
Fig. 7 is the light micrograph of the refractive index modified tone type Micropicture for preparing on silicon substrate of the principle according to Fig. 3.
Five, embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.The inventor has provided following examples, but the invention is not restricted to these embodiment.
Embodiment 1: referring to Fig. 1～3, and photoinduction SiO of the present invention
2Gel film preparation and minute pattern production method thereof are carried out: (1) photonasty SiO by the following method
2The colloidal sol preparation
At first adopt chemical modification method to prepare photonasty colloidal sol, the component and the proportioning of its colloidal sol are as follows:
TEOS∶H
2O∶HCl∶EeOH∶Ph＝1∶4∶0.05∶20∶0.5
TEOS:---ethyl orthosilicate (Si (OC
2H
5)
4) generation SiO
2Base stock
EeOH:----ethanol (C
2H
5OH) solvent
Ph:---phenanthroline (C
12H
8N
2) form the chemical modifier of photonasty chelate
H
2O---water and TEOS add the base stock of water reaction
The catalyst of HCl---hydrochloric acid accelerated reaction.
Behind the chemical reagent mixing stirring 4h with above component, just can obtain the colloidal sol of homogeneous transparent.(2) SiO
2Film preparation and Micropicture preparation
Use the colloidal sol of (1) preparation, can on various glass or silicon substrate, make film with czochralski method, Zhi Bei film has stronger absorption peak as shown in Figure 1 near 274nm in this way, during with corresponding UV-irradiation, absorption peak weakens and fades away, with this film of ultraviolet pre-irradiation solubilized in organic solvent such as ethanol, can not dissolve after the irradiation, according to this phenomenon, ultraviolet light shines this photonasty gel film by mask, then it is soaked in organic solvent moments later and to take out, not local dissolved by illumination, and the place of illumination remains, and obtains SiO
2The Micropicture of gel film.Further carry out 500-600 ℃ thermal treatment, make the organism volatilization remove the back and just can obtain SiO
2The Micropicture of film, whole film fine-pattern preparation process as shown in Figure 2.
The absorption peak of 274nm and phenanthroline (C among Fig. 1
12H
8N
2) β ' absorption peak (264nm) compare, red shift 10nm, phenanthroline (C is described
12H
8N
2) chelatropic reaction has taken place with Si, along with the irradiation of ultraviolet light, the absorption peak at 274nm place descends until disappearance, illustrates that containing Si photonasty chelate decomposes, and film has shown tangible sensitometric characteristic.
Fig. 2 utilizes photonasty SiO
2Film preparation SiO
2The synoptic diagram of Micropicture.
Ultraviolet light for the thick film of 0.6 μ m, is used 200W/cm by mask irradiation photonasty gel film
2The about 30min of spherical high-pressure mercury lamp irradiation (Fig. 2 a), take out after will putting into absolute ethyl alcohol immersion 30sec through the film that Fig. 2 a shone, dry up raffinate, just can obtain SiO
2The Micropicture of gel film (Fig. 2 b), further at 600 ℃ of following thermal treatment 20min, residual organic disappears in the film, just can obtain SiO
2The Micropicture of film (Fig. 2 c).(3) refractive index modified tone type Micropicture preparation
Use the colloidal sol of (1) preparation, can on various glass or silicon substrate, make SiO with czochralski method
2Film, chelate decomposes after illumination, residual organic is changed is different from the part of not illumination, thus cause illumination with not according to the difference of area light refractive index.As shown in Figure 3.As shown in Figure 3, between 200 ℃-450 ℃, heat-treat, the light area with significant difference is not arranged according to the refractive index in zone, one of utilize phenomenon can prepare refractive index modified tone type grating.Ultraviolet light shines this photonasty gel film by mask, then with it 450 ℃ of thermal treatments, will in film, cause the higher and lower zone of refractive index, Fig. 7 is the light micrograph of the refractive index modified tone type Micropicture for preparing on silicon substrate, light rectangle striped among the figure is that (refractive index: 1.531) higher part, dark part are the refractive index (refractive indexes: 1.355) lower part without illumination through the refractive index of illumination.This refractive index modified tone type Micropicture and employed mask graph are in full accord.Present embodiment can be applied to the preparation of diffraction class components and parts such as refractive index modified tone class grating.
Embodiment 2: present embodiment is with 1 different are photonasty SiO
2The component of its colloidal sol and proportioning changed to some extent when colloidal sol prepared, that is:
TEOS∶H
2O∶HCl∶EeOH∶Ph＝1∶3∶0.1∶30∶1
TEOS:---ethyl orthosilicate (Si (OC
2H
5)
4) generate the base stock of SiO2
EeOH:----ethanol (C
2H
5OH) solvent
Ph:---phenanthroline (C
12H
8N
2) form the chemical modifier of photonasty chelate
H
2O---water and TEOS add the base stock of water reaction
The catalyst of HCl---hydrochloric acid accelerated reaction.
Other can reach the purpose of embodiment 1 equally all with embodiment 1.
Embodiment 3: present embodiment is with 1 different are photonasty SiO
2The component of its colloidal sol and proportioning changed to some extent when colloidal sol prepared, that is:
TEOS∶H
2O∶HCl∶EeOH∶Ph＝1∶2∶0.2∶40∶2
TEOS:---ethyl orthosilicate (Si (OC
2H
5)
4) generate the base stock of SiO2
EeOH:----ethanol (C
2H
5OH) solvent
Ph:---phenanthroline (C
12H
8N
2) form the chemical modifier of photonasty chelate
H
2O---water and TEOS add the water reaction and generate raw material
The catalyst of HCl---hydrochloric acid accelerated reaction.
Other can reach the purpose of embodiment 1 equally all with embodiment 1.
Certainly, can also adjust the component and the proportioning of its colloidal sol, as TEOS: H
2O: HCl: EeOH: Ph=1: 2.5: 0.15: 25: 1.5 or TEOS: H
2O: HCl: EeOH: Ph=1: 3.5: 0.2: 40: 1 ..., in the described scope of technical scheme, can reach the purpose of embodiment 1.
Fig. 4 is the SiO for preparing on silicon substrate with the present invention
2The light micrograph of Micropicture, the dark rectangle striped among the figure is SiO
2Film, light-colored part are silicon substrates, and be very regular with the Micropicture of the present invention's preparation as can be seen by photo.The about 3 μ m of the thinnest width of fringe.
Fig. 5 is the SiO for preparing on silicon substrate with the present invention
2The light micrograph of minute groove, the dark rectangle striped among the figure is SiO
2Film, light-colored part are silicon substrates.This technology can application and the making of groove class substrate such as hard disk substrate, plasma TV substrate.
Fig. 6 is the SiO for preparing on silicon substrate with the present invention
2The light micrograph of waveguide optical grating, the dark rectangle striped among the figure is SiO
2Film, light-colored part are silicon substrates.
Fig. 7 is the light micrograph of the refractive index modified tone type Micropicture for preparing on silicon substrate of the principle according to Fig. 3, light rectangle striped among the figure is that (refractive index: 1.531) higher part, dark part are the refractive index (refractive indexes: 1.355) lower part without illumination through the refractive index of illumination.Sample is through 450 ℃ of thermal treatments.
List of references of the present invention
1. Ma Ruzhang, Jiang Minhua, ancestral ruler of great talent and bold vision Xu compiles, and functional material is learned outline, P265-268, metallurgical worker
The industry publishing house, in September, 1999 first published.
2.Ian?M.Barton，Jerald?A.Britten?et?al.，Fabrication?of?large-aperture
lightweight?diffractive?lenses?for?use?in?space，Applied?Optics，Vol?40，No.4，
447-451(2001).
3.Shigehisa?Ohki，Masatoshi?Oda?and?Toshitaka?Shibata，A?new?ultrafine
groove?fabrication?method?utilizing?electron?cyclotron?resonance?plasma
deposition?and?ion?etching，J.Vac.Sci.Technol.B6(2)，533-536(1988).
4. horse is few outstanding, civilian rainwater, and Fu Shaojun, Zhao Wei, Fan Junqing loses the glass optical waveguide grating deeply
Research, hi-tech communication, 31-34, September nineteen ninety-five.
5.Nobrou?TOHGE，Atsunori?Matsuda?and?Tustomu?MINAMI?et?al.，Fine-
patteming?on?glass?substrates?by?the?sol-gel?method，J.Non-Cryst.Solids，
100，501-505(1988).
6. Shen is the people, Chen Linsen, and the application of sol-gel technique in optics is made, optical technology,
No6，61-65.51，(1998).
7.J.Nishii?and?H.yamanaka?et.al，Preparation?of?Bragg?gratings?in?sputter-
deposited?GeO
2-SiO
2?glasses?by?excimer-laser?irradiation，Optics?Letters，
Vol.21，No.17，1360-1362(1996).
8.Keiji?Tsunetomo?and?Tadashi?Koyama，Direct?formation?of?a?surface-relief
grating?on?glass?by?ultraviolet-visible?laser?irradiation，Optics?Letters，Vol.
22，No.6，411-413(1997).9.Ilhan?A.Aksay，et.Al.Biomimetic?pathways?for?assembling?inorganic?thin films?and?oriented?mesoscopic?silicate?patterns?through?guided?growth， United?States?Patent，Patent?No.：US6,228,248?B1?May?8，2001.
Claims (1)
1. photoinduction SiO
2Gel film preparation and minute pattern production method thereof, carry out by the following method:
(1) photonasty SiO
2The colloidal sol preparation
At first adopt chemical modification method to prepare photonasty colloidal sol, the component and the proportioning of its colloidal sol are as follows:
TEOS∶H
2O∶HCl∶EeOH∶Ph＝1∶(2-4)∶(0.05-0.2)∶(10-40)∶(0.5-2)
TEOS:------ethyl orthosilicate (Si (OC
2H
5)
4) generate the base stock of SiO2
EeOH:------ethanol (C
2H
5OH) solvent
Ph:------phenanthroline (C
12H
8N
2) form the chemical modifier of photonasty chelate
H
2O------water and TEOS add the base stock of water reaction
The catalyst of HCl------hydrochloric acid accelerated reaction
Behind the chemical reagent mixing stirring 4h with above component, just can obtain the photonasty SiO of homogeneous transparent
2Colloidal sol;
(2) SiO
2Film preparation and Micropicture preparation
Use the colloidal sol of (1) preparation, can on various glass or silicon substrate, make SiO with czochralski method
2Film, Zhi Bei film has stronger absorption peak near 274nm in this way, during with corresponding UV-irradiation, absorption peak weakens and fades away, with this film of ultraviolet pre-irradiation solubilized in organic solvent such as ethanol, can not dissolve after the irradiation, this utilize mask irradiation after, in organic solvent, soak the back and take out, not local dissolved by illumination, and the place of illumination remains, and obtains SiO
2The Micropicture of gel film;
(3) further carry out 500 ℃-600 ℃ thermal treatment 20min, make in the film residual organic volatilization remove the back and just can obtain SiO
2The Micropicture of film;
(4) use the colloidal sol of (1) to prepare film, illumination is decomposed with the chelate in the rear film, makes the variation of residual organic matter in the heat treatment process be different from the film of not illumination.When ultraviolet light by mask or laser interferance method irradiate, impose 200-450 ℃ thermal treatment again, will be in film and cause the light area with not according to the difference of areas diffract rate; Utilize this phenomenon can prepare refractive index modified tone type grating or refractive index modified tone type Micropicture.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011452625A CN1175318C (en) | 2001-12-28 | 2001-12-28 | Photoinduction SiO2 gel preparation and microfine pattern making method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011452625A CN1175318C (en) | 2001-12-28 | 2001-12-28 | Photoinduction SiO2 gel preparation and microfine pattern making method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1359032A true CN1359032A (en) | 2002-07-17 |
| CN1175318C CN1175318C (en) | 2004-11-10 |
Family
ID=4678102
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299326C (en) * | 2004-07-30 | 2007-02-07 | 西安理工大学 | Tin-doped indium oxide film and making process of fine pattern |
| 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 |
| CN101174088B (en) * | 2007-10-19 | 2010-08-18 | 西安理工大学 | Polymethyl methacrylate-TiO2 hybrid material preparation and minute pattern production |
| CN106219483A (en) * | 2016-08-09 | 2016-12-14 | 福建师范大学 | A kind of preparation method of microelectrode array |
| WO2018103270A1 (en) * | 2016-12-07 | 2018-06-14 | 英诺激光科技股份有限公司 | Method for repairing laser cutting damage on glass surface |
| CN111333023A (en) * | 2020-03-02 | 2020-06-26 | 北京大学 | Preparation method and application of solvent-induced photoresponse polymer surface micro-nano structure |
-
2001
- 2001-12-28 CN CNB011452625A patent/CN1175318C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299326C (en) * | 2004-07-30 | 2007-02-07 | 西安理工大学 | Tin-doped indium oxide film and making process of fine pattern |
| 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 |
| CN101174088B (en) * | 2007-10-19 | 2010-08-18 | 西安理工大学 | Polymethyl methacrylate-TiO2 hybrid material preparation and minute pattern production |
| CN106219483A (en) * | 2016-08-09 | 2016-12-14 | 福建师范大学 | A kind of preparation method of microelectrode array |
| WO2018103270A1 (en) * | 2016-12-07 | 2018-06-14 | 英诺激光科技股份有限公司 | Method for repairing laser cutting damage on glass surface |
| CN111333023A (en) * | 2020-03-02 | 2020-06-26 | 北京大学 | Preparation method and application of solvent-induced photoresponse polymer surface micro-nano structure |
| CN111333023B (en) * | 2020-03-02 | 2023-09-26 | 北京大学 | Preparation method and application of solvent-induced photoresponsive polymer surface micro-nano structure |
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| Publication number | Publication date |
|---|---|
| CN1175318C (en) | 2004-11-10 |
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