CN101587297A - Preparation for titanium dioxide based organic-inorganic composite film and method for preparing micro-optic device by adopting film - Google Patents
Preparation for titanium dioxide based organic-inorganic composite film and method for preparing micro-optic device by adopting film Download PDFInfo
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Abstract
The invention discloses preparation for a titanium dioxide based organic-inorganic composite film and a method for preparing a micro-optic device by adopting the film. By combining the improved sol-gel technology and the low temperature organic-inorganic composite technology, an organic light-sensitive functional group is introduced to realize an organic-inorganic composite photoelectron material integrating light-sensitive property and light waveguide property. Based on the ultraviolet light-sensitive property of the composite material, the mask technology, hot melting reflow technology and stamping technology are combined to manufacture a ridge type light waveguide device and a micro-lens array with low cost. Particularly, the film is a single-layer optical quality waveguide film with the thickness of a few microns, adjustable refractive index and ultraviolet light-sensitive property at low temperature, so the film is quite favorable for integration and low-cost manufacture of photoelectron devices.
Description
Technical field
The present invention relates to a kind of preparation and application thereof, be specifically related to a kind of preparation of titania-based organic, inorganic composite film and adopt the method for this film preparation micro-optic device with low temperature organic and inorganic complex light electronics material of UV photosensitive characteristic.
Background technology
Increase, particularly optical communication system and rapid development of network technique and needs along with the growing of photonics and integrated optics and research interest have increased the demand to micro-optical device greatly.Micro optical element is the important optical element in the optoelectronic device, plays irreplaceable effect in application such as imaging, collimation, coupling and chromatic aberation correction, wavefront shape control.The micro optical element manufacturing technology is comparatively ripe at present, yet owing to use apparatus expensive, complex technical process because of price factor, causes the application of micro optical element, and especially the application aspect the product for civilian use is very limited.Become the manufacturing center in the world along with China, the processing of micro-optic and micro element and production will be shifted to China, the batch making technical need of cheap micro-optic device will be urgent day by day, impel and encourage people to carry out the research and development of photon and optical waveguide material and micro element.
In recent years based on the organic modified silicate based composites in the application aspect the integrated optoelectronics, caused that in the world scientists pays close attention to greatly.Organic modified silicate has good light transmittance, is by at SiO
2Introduce organic molecule in the structural network etc. inorganic material, the novel optical material of a kind of superior performance of acquisition is so demonstrate potential optoelectronics application prospect based on the sol-gel integrated optics of organic modified silicate.Compare with the unorganic glass host material, composite organic-inorganic material not only can improve physics, chemistry and the mechanical property of material along with the adding of organic group, but also can improve the structure of inorganic matrix, make that isomerization has bigger space to the organic photosensitive molecular radical.For example contain polymerisable unsaturated hydrocarbon or the epoxy material of comprising and the composite organic-inorganic material of organic group such as substitute by extensive studies and exploitation, because this class compound substance can write technology, laser holography or electron beam lithography etc. in conjunction with mask technique, laser according to the light sensitive characteristic of its ultraviolet light, directly carry out develop then and fall the making that is not realized fiber waveguide device and micro-optic device by illumination (not polymerization) zone.In addition, we utilize the PDMS elastomeric stamp can directly prepare the micro-optical device of all kinds of other shapes in conjunction with the ultraviolet light polymerization stamping technique on this class photochromics.This shows,, can save etching process necessary in the inorganic material, thereby can reduce the element manufacturing cost greatly and carry out simple and batch making based on the optical device manufacturing process of such photosensitive compound substance.So in conjunction with improved sol-gel technique and low temperature organic and inorganic complex technique realize its have good light guide properties and UV photosensitive characteristic the quick material of titania base organic-inorganic complex light and the research made of micro-optic device for the development of photonics and integrated optics with significant.
Summary of the invention
The object of the present invention is to provide a kind of preparation of the titania-based organic, inorganic composite film of low temperature with good light guide properties and UV photosensitive characteristic and based on the method for this film preparation micro-optic device.
The preparation method of the titania-based organic, inorganic composite film of low temperature of the present invention is as follows:
1) at first, 1 mole of butyl titanate and 3～5 moles of diacetone mixing and stirring are got solution A;
2) secondly, 1 mole of 3-(trimethoxy silane base) propyl methyl acid esters, 2～4 moles of isopropyl alcohols and 2～4 moles of deionized waters are mixed, add 0.01 mole of standard salt acid solution then, get solution B behind the hydrolysis-condensation that stirs as catalyzer;
3) then, 1 mole of methyl triethoxysilane, 3～5 moles of ethanol and 3～5 moles of deionized waters are mixed, add 0.01 mole standard hydrochloric acid then as catalyzer and constantly stir behind the hydrolysis-condensation as solution C;
4) be 1 by methyl triethoxysilane mol ratio in (trimethoxy silane base) propyl methyl acid esters of 3-in butyl titanate, the solution B in the solution A and the solution C: 2-3: 2-1 stirs solution A, solution B and solution C mixed room temperature down, gets the low temperature organic-inorganic composite ground mass mother liquor of siliceous titanium;
5) two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide light triggers of getting organic-inorganic composite ground mass mother liquor weight 3.0-4.0% join in the composite interstitial substance mother liquor, and stir under darkroom and room temperature and obtain suspension;
6) utilize spin coating technology under the situation that rotating speed changes for per minute 2500-4500 suspension to be deposited on silicon chip or the glass substrate, the film sample that deposition is good is placed on 70-85 ℃ and handles the titania-based organic, inorganic composite film that obtained having high optical quality and UV photosensitive characteristic in 3-5 minute down.
Adopt this laminated film to prepare the method for micro-optic device: utilize litho machine to pass through the ridge optical waveguide mask titania-based organic, inorganic composite film is adopted contact exposure 8-25 minute, development 12-60 obtains the ridge optical waveguide device second in absolute ethyl alcohol or acetone then.
Adopt this laminated film to prepare the method for micro-optic device:
1) utilize Taiwan forever light EPG533 type positive photoresist evenly be spin-coated on photoresist on the silicon chip with the rotating speed that per minute 1000-3000 changes, to deposit good photoresist film then handled 1-5 minute on 80-100 ℃ stove or hot plate, utilize litho machine to pass through the cylindrical-array mask at last this photoresist film is adopted contact exposure 50-80 second, development 25-120 obtains array of cylinders second in developer for positive photoresist;
2) the gained array of cylinders is refluxed in 150-180 ℃ obtain the microlens array mother matrix then;
3) PDMS prepolymer and hardening agent are mixed by 10: 1 weight ratio stir evenly, and put it in the vacuum drying chamber and remove fully, then, be cast in it on microlens array mother matrix and place room temperature to solidify and solidified 1 hour in 24 hours or 90 ℃ until bubble;
4) after the PDMS after will solidifying is cooled to room temperature, it is peeled off from the microlens array mother matrix, it is complementary fully to obtain microstructure and microlens array master pattern, the PDMS elastomeric stamp that size is equal to;
5) at first, 1 mole of butyl titanate and 3～5 moles of diacetone mixing and stirring are got solution A;
6) secondly, 1 mole of 3-(trimethoxy silane base) propyl methyl acid esters, 2～4 moles of isopropyl alcohols and 2～4 moles of deionized waters are mixed, add 0.01 mole of standard salt acid solution then, get solution B behind the hydrolysis-condensation that stirs as catalyzer;
7) then, 1 mole of methyl triethoxysilane, 3～5 moles of ethanol and 3～5 moles of deionized waters are mixed, add 0.01 mole standard hydrochloric acid then as catalyzer and constantly stir behind the hydrolysis-condensation as solution C;
8) be 1 by methyl triethoxysilane mol ratio in (trimethoxy silane base) propyl methyl acid esters of 3-in butyl titanate, the solution B in the solution A and the solution C: 2-3: 2-1 stirs solution A, solution B and solution C mixed room temperature down, gets the low temperature organic-inorganic composite ground mass mother liquor of siliceous titanium;
9) two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide light triggers of getting organic-inorganic composite ground mass mother liquor weight 3.0-4.0% join in the composite interstitial substance mother liquor, and stir under darkroom and room temperature and obtain suspension;
10) suspension is spun to 800-2000rpm rotation 120-60s forms laminated film on the silicon substrate, then the PDMS elastomeric stamp is impressed into above the laminated film, after ultraviolet lighting solidifies, the PDMS elastomeric stamp is obtained microlens array from the laminated film removal of solidifying, said ultraviolet lighting solid adopts the xenon short-act lamp emission, its electric current is 15mA, irradiation 10-15min.
Litho machine of the present invention adopts JKG-2A type litho machine; Ridge optical waveguide or cylindrical-array mask adopt the binary mask chromium plate.
The present invention adopts the improvement sol-gel technique to prepare the compound photosensitive performance film with good optical characteristic at low temperatures in conjunction with organic-inorganic compounding technology, and utilizes mask technique to prepare fiber waveguide device, and its preparation technology is simple, and good reproducibility.Adopt titania (to contain unsaturated carbon-carbon double bond as inorganic matrix and organic modified silicate methyl triethoxysilane and 3-(trimethoxy silane base) propyl methyl acid esters, the polymerization again of can rupturing of its carbon-carbon double bond under the irradiation of ultraviolet light generates stable polymer) be the compound photochromics of low temperature organic and inorganic of organic substrate, by based on its organic photosensitive functional group to realize having light sensitive characteristic while light harvesting guide properties organic and inorganic complex light electronics material.UV photosensitive characteristic by such low-temperature composite material is carried out the making of fiber waveguide device cheaply or other micro-optic device in conjunction with mask technique, stamping technique or other laser technology simultaneously.So the present invention is of great importance for the integrated and batch making of realizing the micro-nano optoelectronic device.
Description of drawings
The FFIR curve map of the titania-based organic, inorganic composite film that obtains under Fig. 1 different heat treatment temperature, wherein horizontal ordinate is wave number (cm
-1), ordinate is an absorptivity;
The ridge optical waveguide array based on this composite film material UV photosensitive characteristic making of Fig. 2 Philips-FEI Quanta200 scanning electron microscopy measurement;
The microlens array mother matrix based on the photoresist making of Fig. 3 Olympus BX51 optical microscope measuring;
Fig. 4 Olympus BX51 optical microscope measuring be the microstructure graph that mother matrix is transferred to gained on this photo-conductive film with Fig. 3.
Embodiment
Below in conjunction with accompanying drawing the present invention is described in further detail.
Embodiment 1:1) at first, 1 mole of butyl titanate and 3 moles of diacetone mixing and stirring are got solution A;
2) secondly, 1 mole of 3-(trimethoxy silane base) propyl methyl acid esters, 4 moles of isopropyl alcohols and 2 moles of deionized waters are mixed, add 0.01 mole of standard salt acid solution then, get solution B behind the hydrolysis-condensation that stirs as catalyzer;
3) then, 1 mole of methyl triethoxysilane, 5 moles of ethanol and 3 moles of deionized waters are mixed, add 0.01 mole standard hydrochloric acid then as catalyzer and constantly stir behind the hydrolysis-condensation as solution C;
4) be will solution A, solution B and solution C mixed room temperature down to stir at 1: 3: 1 by methyl triethoxysilane mol ratio in (trimethoxy silane base) propyl methyl acid esters of 3-in butyl titanate, the solution B in the solution A and the solution C, the low temperature organic-inorganic composite ground mass mother liquor of siliceous titanium;
5) two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide light triggers of getting organic-inorganic composite ground mass mother liquor weight 3% join in the composite interstitial substance mother liquor, and stir under darkroom and room temperature and obtain suspension;
6) utilize spin coating technology under the situation that rotating speed changes for per minute 2500, suspension to be deposited on silicon chip or the glass substrate, the film sample that deposition is good is placed on 85 ℃ and handles down and to obtain individual layer in 3 minutes and have about 1.65 micron thickness, and smooth surface is smooth and have an organic and inorganic complex light electronics membraneous material of UV photosensitive characteristic and waveguide properties.
Ridge optical waveguide preparation of devices: utilize the UV photosensitive characteristic of this composite film material itself can realize the ridge optical waveguide preparation of devices in conjunction with mask technique.Detailed process: at first, utilize optical lithography processes, wherein litho machine is that JKG-2A type, mask plate are traditional binary mask chromium plates, and i.e. exposure place of the UV photosensitive characteristic polymerization of bond material forms stable superpolymer.The rear film that will expose then is placed on development 12-60 second in the absolute ethyl alcohol, can obtain the ridge optical waveguide device.
The preparation of microlens array:
1) to prepare array of cylinders device process in conjunction with mask technique identical with above-mentioned photochromics, utilize Taiwan forever light EPG533 type positive photoresist evenly be spin-coated on photoresist on the silicon chip with the rotating speed that per minute 1000 changes, to deposit good photoresist film then handled 1 minute on 100 ℃ stove or hot plate, utilize litho machine to pass through cylindrical-array mask mask at last this photoresist film is adopted contact exposure 80 seconds, developing in developer for positive photoresist obtained array of cylinders in 25 seconds;
2) the gained array of cylinders is refluxed in 180 ℃ obtain the microlens array mother matrix then;
3) PDMS prepolymer and hardening agent are mixed by 10: 1 weight ratio stir evenly, and put it in the vacuum drying chamber (BIF-30 type) and remove fully until bubble, then, it is cast on the microlens array mother matrix and places room temperature to solidify and solidified 1 hour in 24 hours or 90 ℃;
4) after the PDMS after will solidifying is cooled to room temperature, it is peeled off from the microlens array mother matrix, it is complementary fully to obtain microstructure and microlens array master pattern, the PDMS elastomeric stamp that size is equal to;
5) 1 mole of butyl titanate and 3 moles of diacetone mixing and stirring are got solution A;
6) 1 mole of 3-(trimethoxy silane base) propyl methyl acid esters, 4 moles of isopropyl alcohols and 2 moles of deionized waters are mixed, add 0.01 mole of standard salt acid solution then, get solution B behind the hydrolysis-condensation that stirs as catalyzer;
7) 1 mole of methyl triethoxysilane, 5 moles of ethanol and 3 moles of deionized waters are mixed, add 0.01 mole standard hydrochloric acid then as catalyzer and constantly stir behind the hydrolysis-condensation as solution C;
8) be will solution A, solution B and solution C mixed room temperature down to stir at 1: 3: 1 by methyl triethoxysilane mol ratio in (trimethoxy silane base) propyl methyl acid esters of 3-in butyl titanate, the solution B in the solution A and the solution C, the low temperature organic-inorganic composite ground mass mother liquor of siliceous titanium;
9) two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide light triggers of getting organic-inorganic composite ground mass mother liquor weight 3% join in the composite interstitial substance mother liquor, and stir under darkroom and room temperature and obtain suspension;
10 are spun to suspension and form laminated film on the silicon substrate with 1000rpm rotation 60s, then the PDMS elastomeric stamp is impressed into above the laminated film, after ultraviolet lighting solidifies, the PDMS elastomeric stamp is obtained microlens array from the laminated film removal of solidifying, said ultraviolet lighting solid adopts the xenon short-act lamp emission, its electric current is 15mA, irradiation 10min.
Embodiment 2:1) at first, 1 mole of butyl titanate and 5 moles of diacetone mixing and stirring are got solution A;
2) secondly, 1 mole of 3-(trimethoxy silane base) propyl methyl acid esters, 2 moles of isopropyl alcohols and 3 moles of deionized waters are mixed, add 0.01 mole of standard salt acid solution then, get solution B behind the hydrolysis-condensation that stirs as catalyzer;
3) then, 1 mole of methyl triethoxysilane, 3 moles of ethanol and 5 moles of deionized waters are mixed, add 0.01 mole standard hydrochloric acid then as catalyzer and constantly stir behind the hydrolysis-condensation as solution C;
4) be will solution A, solution B and solution C mixed room temperature down to stir at 1: 2.5: 1.5 by methyl triethoxysilane mol ratio in (trimethoxy silane base) propyl methyl acid esters of 3-in butyl titanate, the solution B in the solution A and the solution C, the low temperature organic-inorganic composite ground mass mother liquor of siliceous titanium;
5) two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide light triggers of getting organic-inorganic composite ground mass mother liquor weight 3.5% join in the composite interstitial substance mother liquor, and stir under darkroom and room temperature and obtain suspension;
6) utilize spin coating technology under the situation that rotating speed changes for per minute 3500, suspension to be deposited on silicon chip or the glass substrate, the film sample that deposition is good is placed on 80 ℃ and handles down and to obtain individual layer in 4 minutes and have about 1.65 micron thickness, and smooth surface is smooth and have an organic and inorganic complex light electronics membraneous material of UV photosensitive characteristic and waveguide properties.
The preparation of microlens array:
1) utilize Taiwan forever light EPG533 type positive photoresist evenly be spin-coated on photoresist on the silicon chip with the rotating speed that per minute 3000 changes, to deposit good photoresist film then handled 3 minutes on 90 ℃ stove or hot plate, utilize litho machine to pass through cylindrical-array mask mask at last this photoresist film is adopted contact exposure 50 seconds, developing in developer for positive photoresist obtained array of cylinders in 120 seconds;
2) the gained array of cylinders is refluxed in 160 ℃ obtain the microlens array mother matrix then;
3) PDMS prepolymer and hardening agent are mixed by 10: 1 weight ratio stir evenly, and put it in the vacuum drying chamber (BIF-30 type) and remove fully until bubble, then, it is cast on the microlens array mother matrix and places room temperature to solidify and solidified 1 hour in 24 hours or 90 ℃;
4) after the PDMS after will solidifying is cooled to room temperature, it is peeled off from the microlens array mother matrix, it is complementary fully to obtain microstructure and microlens array master pattern, the PDMS elastomeric stamp that size is equal to;
5) 1 mole of butyl titanate and 5 moles of diacetone mixing and stirring are got solution A;
6) 1 mole of 3-(trimethoxy silane base) propyl methyl acid esters, 2 moles of isopropyl alcohols and 3 moles of deionized waters are mixed, add 0.01 mole of standard salt acid solution then, get solution B behind the hydrolysis-condensation that stirs as catalyzer;
7) 1 mole of methyl triethoxysilane, 3 moles of ethanol and 5 moles of deionized waters are mixed, add 0.01 mole standard hydrochloric acid then as catalyzer and constantly stir behind the hydrolysis-condensation as solution C;
8) be will solution A, solution B and solution C mixed room temperature down to stir at 1: 2.5: 1.5 by methyl triethoxysilane mol ratio in (trimethoxy silane base) propyl methyl acid esters of 3-in butyl titanate, the solution B in the solution A and the solution C, the low temperature organic-inorganic composite ground mass mother liquor of siliceous titanium;
9) two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide light triggers of getting organic-inorganic composite ground mass mother liquor weight 3.5% join in the composite interstitial substance mother liquor, and stir under darkroom and room temperature and obtain suspension;
10) suspension is spun to 800rpm rotation 90s forms laminated film on the silicon substrate, then the PDMS elastomeric stamp is impressed into above the laminated film, after ultraviolet lighting solidifies, the PDMS elastomeric stamp is obtained microlens array from the laminated film removal of solidifying, said ultraviolet lighting solid adopts the xenon short-act lamp emission, its electric current is 15mA, irradiation 12min.
Embodiment 3:1) at first, 1 mole of butyl titanate and 4 moles of diacetone mixing and stirring are got solution A;
2) secondly, 1 mole of 3-(trimethoxy silane base) propyl methyl acid esters, 3 moles of isopropyl alcohols and 4 moles of deionized waters are mixed, add 0.01 mole of standard salt acid solution then, get solution B behind the hydrolysis-condensation that stirs as catalyzer;
3) then, 1 mole of methyl triethoxysilane, 4 moles of ethanol and 4 moles of deionized waters are mixed, add 0.01 mole standard hydrochloric acid then as catalyzer and constantly stir behind the hydrolysis-condensation as solution C;
4) be will solution A, solution B and solution C mixed room temperature down to stir at 1: 2: 2 by methyl triethoxysilane mol ratio in (trimethoxy silane base) propyl methyl acid esters of 3-in butyl titanate, the solution B in the solution A and the solution C, the low temperature organic-inorganic composite ground mass mother liquor of siliceous titanium;
5) two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide light triggers of getting organic-inorganic composite ground mass mother liquor weight 4% join in the composite interstitial substance mother liquor, and stir under darkroom and room temperature and obtain suspension;
6) utilize spin coating technology under the situation that rotating speed changes for per minute 4500, suspension to be deposited on silicon chip or the glass substrate, the film sample that deposition is good is placed on 70 ℃ and handles down and to obtain individual layer in 5 minutes and have about 1.65 micron thickness, and smooth surface is smooth and have an organic and inorganic complex light electronics membraneous material of UV photosensitive characteristic and waveguide properties.
The preparation of microlens array:
1) utilize Taiwan forever light EPG533 type positive photoresist evenly be spin-coated on photoresist on the silicon chip with the rotating speed that per minute 2000 changes, to deposit good photoresist film then handled 5 minutes on 80 ℃ stove or hot plate, utilize litho machine to pass through cylindrical-array mask mask at last this photoresist film is adopted contact exposure 65 seconds, developing in developer for positive photoresist obtained array of cylinders in 70 seconds;
2) the gained array of cylinders is refluxed in 150 ℃ obtain the microlens array mother matrix then;
3) PDMS prepolymer and hardening agent are mixed by 10: 1 weight ratio stir evenly, and put it in the vacuum drying chamber (BIF-30 type) and remove fully until bubble, then, it is cast on the microlens array mother matrix and places room temperature to solidify and solidified 1 hour in 24 hours or 90 ℃;
4) after the PDMS after will solidifying is cooled to room temperature, it is peeled off from the microlens array mother matrix, it is complementary fully to obtain microstructure and microlens array master pattern, the PDMS elastomeric stamp that size is equal to;
5) 1 mole of butyl titanate and 4 moles of diacetone mixing and stirring are got solution A;
6) 1 mole of 3-(trimethoxy silane base) propyl methyl acid esters, 3 moles of isopropyl alcohols and 4 moles of deionized waters are mixed, add 0.01 mole of standard salt acid solution then, get solution B behind the hydrolysis-condensation that stirs as catalyzer;
7) 1 mole of methyl triethoxysilane, 4 moles of ethanol and 4 moles of deionized waters are mixed, add 0.01 mole standard hydrochloric acid then as catalyzer and constantly stir behind the hydrolysis-condensation as solution C;
8) be will solution A, solution B and solution C mixed room temperature down to stir at 1: 2: 2 by methyl triethoxysilane mol ratio in (trimethoxy silane base) propyl methyl acid esters of 3-in butyl titanate, the solution B in the solution A and the solution C, the low temperature organic-inorganic composite ground mass mother liquor of siliceous titanium;
9) two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide light triggers of getting organic-inorganic composite ground mass mother liquor weight 4% join in the composite interstitial substance mother liquor, and stir under darkroom and room temperature and obtain suspension;
10) suspension is spun to 2000rpm rotation 120s forms laminated film on the silicon substrate, then the PDMS elastomeric stamp is impressed into above the laminated film, after ultraviolet lighting solidifies, the PDMS elastomeric stamp is obtained microlens array from the laminated film removal of solidifying, said ultraviolet lighting solid adopts the xenon short-act lamp emission, its electric current is 15mA, irradiation 15min.
Fig. 1 is the FFIR curve map of the quick material of titania base organic-inorganic complex light that obtains under the different heat treatment temperature in the above-mentioned example, and wherein horizontal ordinate is wave number (cm
-1), ordinate is an absorptivity.As seen from the figure, handle the membraneous material that obtains down at 100 ℃, 200 ℃ and be about 1720cm in wave number
-1And 1630cm
-1The carbonic acyl radical ester group peak that the place is corresponding and the carbon-carbon bond of vinyl groups can be known and be observed, and the intensity at these peaks reduces along with the rising of temperature; Handle the membraneous material that obtains down at 300 ℃, 400 ℃, 500 ℃ and be about 1720cm in wave number
-1And 1630cm
-1The carbonic acyl radical ester group peak that the place is corresponding and the carbon-carbon bond of vinyl groups disappear substantially.These results show that the compound substance that obtains just may have the UV photosensitive characteristic under the thermal treatment temperature below 300 ℃.
Fig. 2 is the ridge optical waveguide array based on this laminated film host material UV photosensitive characteristic making that utilizes Philips-FEI Quanta 200 scanning electron microscopy measurements in the above-mentioned example 1.Ridge waveguide is to utilize JKG-2A type litho machine in conjunction with mask (reticle pattern is that diameter is 20 microns, is spaced apart 20 slab waveguide array) exposure 23 minutes, the strip optical waveguide array that development 16s obtains among Fig. 2.As can be seen from Fig. 2, the width of ridge optical waveguide is about 12 microns, is about 20 microns at interval.
The microlens array mother matrix based on the photoresist making of Fig. 3 Olympus BX51 optical microscope measuring.The preparation process and the parameter of photoresist microlens array mother matrix among Fig. 3: the rotating speed spin coating 60s with 1000rpm, prepare photoresist film on silicon substrate; With 100 ℃ of bakings before the photoresist film, 2 minutes; Utilize JKG-2A type litho machine in conjunction with mask (reticle pattern is that diameter is 20 microns, is spaced apart 8 microns circular array) exposure 60 seconds then, developed 25 seconds, thereby obtain array of cylinders.The photoresist microlens array mother matrix shown in Figure 3 that this array of cylinders is refluxed in 160 ℃ of environment and obtained in 30 minutes.
Fig. 4 Olympus BX51 optical microscope measuring be that mother matrix is transferred to gained microstructure graph on this photo-conductive film with Fig. 3.Comparison diagram 3 and Fig. 4 as can be seen can be with complete the transferring on the photo-conductive film of photoresist lenticule mother matrix array through the PDMS elastomeric stamp, and respond well.
In sum, low temperature organic-inorganic composite of the present invention is except having good waveguide properties, also tool The light-sensitive characteristic of ultraviolet light is arranged, and can be used as waveguide or other micro-optic device Material Used, and its device system Work has simple and characteristics cheaply.
Claims (5)
1, the preparation method of titania-based organic, inorganic composite film is characterized in that:
1) at first, 1 mole of butyl titanate and 3～5 moles of diacetone mixing and stirring are got solution A;
2) secondly, 1 mole of 3-(trimethoxy silane base) propyl methyl acid esters, 2～4 moles of isopropyl alcohols and 2～4 moles of deionized waters are mixed, add 0.01 mole of standard salt acid solution then, get solution B behind the hydrolysis-condensation that stirs as catalyzer;
3) then, 1 mole of methyl triethoxysilane, 3～5 moles of ethanol and 3～5 moles of deionized waters are mixed, add 0.01 mole standard hydrochloric acid then as catalyzer and constantly stir behind the hydrolysis-condensation as solution C;
4) be 1 by methyl triethoxysilane mol ratio in (trimethoxy silane base) propyl methyl acid esters of 3-in butyl titanate, the solution B in the solution A and the solution C: 2-3: 2-1 stirs solution A, solution B and solution C mixed room temperature down, gets the low temperature organic-inorganic composite ground mass mother liquor of siliceous titanium;
5) two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide light triggers of getting organic-inorganic composite ground mass mother liquor weight 3.0-4.0% join in the composite interstitial substance mother liquor, and stir under darkroom and room temperature and obtain suspension;
6) utilize spin coating technology under the situation that rotating speed changes for per minute 2500-4500 suspension to be deposited on silicon chip or the glass substrate, the film sample that deposition is good is placed on 70-85 ℃ and handles the titania-based organic, inorganic composite film that obtained having high optical quality and UV photosensitive characteristic in 3-5 minute down.
2, a kind of laminated film that makes based on the preparation method of claim 1 prepares the method for micro-optic device, it is characterized in that: utilize litho machine to pass through the ridge optical waveguide mask titania-based organic, inorganic composite film is adopted contact exposure 8-25 minute, development 12-60 obtains the ridge optical waveguide device second in absolute ethyl alcohol or acetone then.
3, a kind of preparation method of micro-optic device is characterized in that:
1) utilize Taiwan forever light EPG533 type positive photoresist evenly be spin-coated on photoresist on the silicon chip with the rotating speed that per minute 1000-3000 changes, to deposit good photoresist film then handled 1-5 minute on 80-100 ℃ stove or hot plate, utilize litho machine to pass through the cylindrical-array mask at last this photoresist film is adopted contact exposure 50-80 second, development 25-120 obtains array of cylinders second in developer for positive photoresist;
2) the gained array of cylinders is refluxed in 150-180 ℃ obtain the microlens array mother matrix;
3) PDMS prepolymer and hardening agent are mixed by 10: 1 weight ratio stir evenly, and put it in the vacuum drying chamber and remove fully, then, be cast in it on microlens array mother matrix and place room temperature to solidify and solidified 1 hour in 24 hours or 90 ℃ until bubble;
4) after the PDMS after will solidifying is cooled to room temperature, it is peeled off from the microlens array mother matrix, it is complementary fully to obtain microstructure and microlens array master pattern, the PDMS elastomeric stamp that size is equal to;
5) 1 mole of butyl titanate and 3～5 moles of diacetone mixing and stirring are got solution A;
6) 1 mole of 3-(trimethoxy silane base) propyl methyl acid esters, 2～4 moles of isopropyl alcohols and 2～4 moles of deionized waters are mixed, add 0.01 mole of standard salt acid solution then, get solution B behind the hydrolysis-condensation that stirs as catalyzer;
7) then, 1 mole of methyl triethoxysilane, 3～5 moles of ethanol and 3～5 moles of deionized waters are mixed, add 0.01 mole standard hydrochloric acid then as catalyzer and constantly stir behind the hydrolysis-condensation as solution C;
8) be 1 by methyl triethoxysilane mol ratio in (trimethoxy silane base) propyl methyl acid esters of 3-in butyl titanate, the solution B in the solution A and the solution C: 2-3: 2-1 stirs solution A, solution B and solution C mixed room temperature down, gets the low temperature organic-inorganic composite ground mass mother liquor of siliceous titanium;
9) two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide light triggers of getting organic-inorganic composite ground mass mother liquor weight 3.0-4.0% join in the composite interstitial substance mother liquor, and stir under darkroom and room temperature and obtain suspension;
10) suspension is spun to 800-2000rpm rotation 120-60s forms laminated film on the silicon substrate, then the PDMS elastomeric stamp is impressed into above the laminated film, after ultraviolet lighting solidifies, the PDMS elastomeric stamp is obtained microlens array from the laminated film removal of solidifying, said ultraviolet lighting solid adopts the xenon short-act lamp emission, its electric current is 15mA, irradiation 10-15min.
4, according to claim 2 or the 3 described methods that prepare micro-optic device, it is characterized in that: said litho machine adopts JKG-2A type litho machine.
5, according to claim 2 or the 3 described methods that prepare micro-optic device, it is characterized in that: said ridge optical waveguide or cylindrical-array mask adopt the binary mask chromium plate.
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| CN104407497A (en) * | 2014-12-19 | 2015-03-11 | 上海天马有机发光显示技术有限公司 | Mask plate as well as preparation method and cleaning method thereof |
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