KR101457185B1 - Inserting method of polymer precusor into nano scale holes using vacuum effect and the precise replication method of nano pattern using thereof - Google Patents
Inserting method of polymer precusor into nano scale holes using vacuum effect and the precise replication method of nano pattern using thereof Download PDFInfo
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- KR101457185B1 KR101457185B1 KR1020080098942A KR20080098942A KR101457185B1 KR 101457185 B1 KR101457185 B1 KR 101457185B1 KR 1020080098942 A KR1020080098942 A KR 1020080098942A KR 20080098942 A KR20080098942 A KR 20080098942A KR 101457185 B1 KR101457185 B1 KR 101457185B1
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Abstract
The present invention relates to a method of inserting a polymer precursor into a nanopore by using a vacuum effect and a method of precisely replicating a nano pattern using the same, and more particularly, to a method of precisely replicating a viscous fluid such as a polymer precursor in a fine hole having a size of several to several tens of nanometers The present invention relates to a technique for transferring a fine pattern into a precisely controlled form on a large-sized polymer substrate which is freely inserted and spans from several tens to several hundreds of centimeters. To this end, the present invention provides a method of inserting a viscous fluid into a mold having nano-scale fine holes, comprising the steps of exposing a specific gas to the fine holes and filling the same with a specific solvent, The solvent is filled in the micropores by the negative pressure effect (or vacuum effect) momentarily generated in the micropores, and the other solvents which are well mixed with the solvent are sequentially exposed to be finally exchanged with the viscous fluid Method.
Nanopattern, vacuum, aluminum anodization
Description
The present invention relates to a method of inserting a polymer precursor into a nanopore by using a vacuum effect and a method of precisely replicating a nano pattern using the same, and more particularly, to a method of precisely replicating a viscous fluid such as a polymer precursor in a fine hole having a size of several to several tens of nanometers The present invention relates to a technique for transferring a fine pattern into a precisely controlled form on a large-sized polymer substrate which is freely inserted and spans from several tens to several hundreds of centimeters.
Due to the enormous economic ripple effect of photolithography used in the fabrication of electronic devices, the technology of manufacturing fine patterns is not only the development of next generation lithography (NGL) It has been competitive all over the world for many years. As a result, it is possible to use electron beam lithography, scanning probe microscope (SPM), micro contact printing, nanoimprinting lithography (NIL), etc. Has been developed and based on the technique of manufacturing such fine patterns, recently various application studies using these have been carried out.
Such a change in the technical environment can be explained by how easily, in a large area, and in a large amount, a pattern of an appropriate resolution can be produced rather than increasing the resolution of the fine pattern competitively, To move the axis of development. In this sense, NIL technology, which can easily replicate patterns by using a template pattern once it is secured, can be applied to various applications such as patterns formed on a polymer substrate due to its advantages such as not requiring complicated and expensive equipment And is being actively used in the field of research.
Conventional optical technology for applying a photosensitive polymer and selectively exposing to a light source such as ultraviolet rays using a photomask prepared in advance and then forming a pattern on silicon through steps such as developing and etching Alternatively, NIL can be used to selectively etch resistivity, or a well-controlled nanometer-level hole pattern previously fabricated using anodization techniques such as polystyrene (PS) or polymethylmethacrylate -acrylate, and PMMA) to form a well-controlled pattern in the form of an engraved original. In particular, since PS has been used as a substrate for cell culture for a long time and various experimental results have been accumulated, the PS substrate transferred with nanopattern can be used for immobilization of biomaterial such as protein or DNA, It can be a key contributor to the development of research.
However, in the case of the conventional nanoimprint technique, there are some technical limitations. For example, when a hard polymer substrate is heated to a temperature higher than the Tg point and pressed at a high pressure, a pattern is produced. If the area of the transferred pattern is widened, The bubble is trapped and the shape of the pattern is distorted, and the transfer of the pattern is uneven depending on the degree of uniformity of the polymer substrate and the mold pattern itself. The problems associated with the non-uniformity of the transferred pattern usually occur because both sides of the mold pattern and the polymer substrate are both rigid when they are first contacted. In the case of liquid polymeric precursors, most of them can be solved, but in the case of liquid polymers, It is difficult to set the conditions of temperature and pressure. If the ultraviolet curing is attempted by simply pouring the solution into a pattern under normal temperature and pressure conditions, the problem of trapping bubbles can not be amplified.
Particularly, in order to realize the replication of such a pattern on a large area, there remains a very complicated technical problem such as the smoothness of the template and the substrate to be transferred, the problem of contact between them, and measures for preventing breakage.
On the other hand, in order to separate the polymer from the mold composed mostly of metal oxides and to complete separation of the polymer having completed the curing reaction, the metal surface is coated with a hydrophobic substance. Typical examples are a hydroxyl group and a covalent bond the silane (silane) surface groups corresponding to the end part from compounds which are capable of CF 3 - (CF 2) Let it immobilizing a molecule made up of the n- type a self-assembly film form easily separated from the surface are changed into hydrophobic . These properties, however, are interleaved with the previously introduced organic precursor, the polymer precursor, and the harmonization of the affinity between the surface, so that the polymer precursor can be strongly forced into the micropores regardless of affinity, Technology is required.
We try to solve the above technical difficulties such as bubble trap problem, nonuniformity problem, and pattern precision for the replication process of large area pattern.
In the case of replicating a pattern using a polymer precursor, it is important to ensure that the affinity between the polymer precursor and the surface of the fine pattern coincide with each other in securing the precision of the pattern. That is, when the polymer precursor has a polarity, the pattern surface must be kept hydrophilic. On the other hand, in the case of a non-polar material, the surface of the hydrophobic pattern provides a more favorable environment for inducing precursors to be precisely inserted into the microstructure of the pattern. However, even in this case, it is difficult to completely remove the bubbles generated by the pressure of the gas existing in the microstructure of the pattern due to the macroscopic pouring of the liquid polymer, which is the fluid, in the process, , That is, in the case of a pattern having a large aspect ratio, a technical assurance that the polymer precursor can be reliably filled up to the inside of the hole is required. If the surface of the fine pattern used as a master easily changes to a nonpolar surface, it becomes more difficult to fill the polar polymer precursor to the inside of the hole. In the present invention, a vacuum effect by ammonia or the like is used as a chemical approach for effective filling even when the affinities of the surface of the polymer precursor in vitro master pattern do not coincide with each other and do not coincide with each other.
To this end, the present invention provides a method of inserting a viscous fluid into a mold having nano-scale fine holes, comprising the steps of exposing a specific gas to the fine holes and filling the same with a specific solvent, The solvent is filled in the micropores by the negative pressure effect (or vacuum effect) momentarily generated in the micropores, and the other solvents which are well mixed with the solvent are sequentially exposed to be finally exchanged with the viscous fluid Method.
The solvent may be water, and another primary solvent capable of solvent exchange by diffusion with the water may be selected from the group consisting of alcohols, ketones and ethers. The alcohols may be selected from the group consisting of methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol and tertiary alcohol, and the ketones may be acetone, methyl ethyl ketone, diethyl ketone and methyl butyl ketone , The ethers may be selected from the group consisting of methyl ether, methyl ethyl ether, ethyl ether, propyl ether and butyl ether.
Further, another secondary solvent which can be exchanged with another primary solvent by diffusion may be selected from the group consisting of alcohols, ketones, ethers and polar aromatic solvents, and the aromatic solvent is selected from the group consisting of toluene and Xylene. ≪ / RTI >
On the other hand, the specific gas is preferably ammonia. Preferably, the viscous fluid is a photo-curable polymer precursor or a thermosetting polymer precursor, and the template is a template having a nano pattern using an aluminum anodizing technique.
Meanwhile, the method of filling the micropores with ammonia gas may be performed by placing the mold in a closed container and evacuating it, exposing the ammonia liquid or connecting the gas ammonia bomb to the container to saturate it with ammonia gas It is preferable to fill it.
The present invention also provides a method of fabricating a microstructure, the method comprising: fabricating a microstructure that is repetitive using aluminum anodization techniques and whose size is controlled to a nanometer level; A method of inserting a viscous fluid into a mold having the above-mentioned nanometer-scale fine holes; Curing the filled viscous fluid; And separating the cured viscous fluid from the cured viscous fluid.
The method may further include modifying the microstructure to a hydrophobic surface, and adjusting the depth of the hole pattern of the microstructure through adjustment of the anodization time, And adjusting the width of the light emitting diode. The cured viscous fluid is preferably transferred to a substrate selected from the group consisting of a PS substrate, a PMMA substrate, a silicon wafer, a sapphire wafer, a glass substrate, and a quartz substrate.
According to the present invention, a desired material can be successfully filled in a recessed portion of a microstructure, which is a region where an artificial adjustment is not easy. As described in the embodiments of the present invention, various types of polymer precursors can be easily and quickly fabricated by filling various kinds of polymer precursors into microstructures without problems such as generation of bubbles and non-uniformity. And to provide an infrastructure technology that can be easily produced and used for further application research. When the present invention is applied, large-area nanopatterns can be accurately reproduced. This technique has a technical meaning that it is a simple way to control the phenomenon that occurs on the surface of a microstructure that is difficult to artificially control.
For better understanding, the present invention will be described by assuming ammonia gas specifically. In view of the fact that the ammonia gas is very soluble in water, the pattern substrate is sufficiently exposed to the ammonia gas to sufficiently fill the fine holes with the ammonia gas, and then exposed to the water to generate the instantaneous negative pressure effect The water was sucked into the micropores, and then the micropores were effectively filled into the micropores by stepwise exposure to solvents which are well mixed with water. Through this, it was possible to fabricate well - controlled polymer nanopatterns by overcoming the problems that have not been overcome by existing NIL technology such as occurrence of bubbles or non - uniformity of patterns in replicating large - area patterns ensuring the accuracy of nanometer level. 1 is a schematic diagram showing a schematic process of the present invention for selectively immobilizing an organic material on a patterned surface. Since
First, a
Hereinafter, the present invention will be described in more detail based on the following examples. It should be noted, however, that the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The present invention is not limited to the following examples. Will be apparent to those skilled in the art to which the present invention pertains.
An embodiment of the present invention will be described step by step.
Example 1. Hydrophilic P250 anodization pattern utilization 1
1) We fabricate microstructures that are repetitive and controlled to nanometer level using aluminum anodization technique.
- Aluminum substrate (2x5 cm 2 ) is put into a 25% perchloric acid ethanol solution and a potential of 20 V is applied for about 5 minutes. Keep the temperature at 7 ° C.
- 0.1M phosphoric acid solution for 10 hours at 0 ° C and 193V.
- Immerse in chromic acid solution for 12 hours at 65 ° C.
- 0.1M phosphoric acid solution for 5 hours at 0 ° C and 193V.
- phosphoric acid solution at 30 ° C for 2 1/2 hours.
FIG. 2 is a scanning electron microscope (SEM) image of the AAO template (P250) prepared by the above process. FIG. 3 is a graph showing the relationship between the depth of the hole pattern of the P250 fabricated under these conditions and the anodization time. It can be seen that the oxide film grows at a rate of 0.2 nm per second.
2) Put the microstructure of above 1) into a closed container with 25% ammonia solution and connect the rotary pump to the container to make vacuum. This state is maintained for 1 hour.
3) Alternatively, in addition to the methods described in 2) above, a gaseous ammonia bomb may be connected directly to the chamber to saturate the vessel with ammonia gas. This state is also maintained for 1 hour.
4) Remove the substrate exposed to ammonia gas by 2) or 3) above and immerse it in a 250-mL beaker containing ultra-pure water from which ions have been removed. This state is maintained for 1 hour
5) Remove the substrate made by 4) above and transfer to a 250 mL beaker containing 95% ethanol. This state is maintained for 1 hour. Remove the substrate from above 5), dry it with a weak flow of nitrogen gas, pour the UV curable polymer precursor in proper amount before the ethanol on the surface of the substrate is completely dried, and place the cleaned glass substrate thereon.
6) The substrate is exposed to ultraviolet rays and curing is progressed to a point at which the dose reaches 150 mJ cm -2 .
7) Finally, the AAO pattern is separated from the template. FIG. 4 shows a scanning electron microscope image of the final copied pattern in this manner.
Example 2. Hydrophilic O 65 Anodization Pattern Utilization 1
1) We fabricate microstructures that are repetitive and controlled to nanometer level using aluminum anodization technique.
- Aluminum substrate (2x5 cm 2 ) is put into a 25% perchloric acid ethanol solution and a potential of 20 V is applied for about 5 minutes. Keep the temperature at 7 ° C.
- Anodic oxidation in a 0.3M oxalic acid solution for 8 hours at 15 ° C, 40V.
- Immerse in chromic acid solution at 65 ° C for 3 hours or 4 hours.
- Anodic oxidation in a 0.3M oxalic acid solution for 3 minutes at 15 ° C, 40V.
- phosphoric acid solution at 30 ° C for 40 minutes.
FIG. 5 shows a scanning electron micrograph of the AAO template (O65) produced by such a process. Fig. 6 is a graph showing the relationship between the depth of the hole pattern of O65 and the anodic oxidation time, which were produced under these conditions. It can be seen that the oxide film grows at a rate of 1.5 nm per second. Based on this result, the anodic oxide fine pattern having a depth of about 120 nm was replicated by secondary anodization for 30 seconds in this embodiment.
2) Put the microstructure of above 1) into a closed container with 25% ammonia solution and connect the rotary pump to the container to make vacuum. This state is maintained for 1 hour.
3) Alternatively, in addition to the methods described in 2) above, a gaseous ammonia bomb may be connected directly to the chamber to saturate the vessel with ammonia gas. This state is also maintained for 1 hour.
4) Remove the substrate exposed to ammonia gas by 2) or 3) above and immerse it in a 250-mL beaker containing ultra-pure water from which ions have been removed. This state is maintained for 1 hour
5) Remove the substrate made by 4) above and transfer to a 250 mL beaker containing 95% ethanol. This state is maintained for 1 hour.
6) Remove the substrate prepared in step 5), dry it with a weak flow of nitrogen gas, pour an appropriate amount of ultraviolet curable polymer precursor before the ethanol on the surface of the substrate is completely dried, and place the cleaned glass substrate thereon.
7) The substrate is exposed to ultraviolet rays and curing is progressed to a point at which the dose reaches 150 mJ cm -2 .
8) Finally, the AAO pattern is separated from the template.
FIG. 7 shows a scanning electron microscope image of the final copied pattern in this manner.
Example 3. Hydrophilic P250 Anodization Pattern Utilization 2
1) We fabricate microstructures that are repetitive and controlled to nanometer level using aluminum anodization technique.
- Aluminum substrate (2x5 cm 2 ) is put into a 25% perchloric acid ethanol solution and a potential of 20 V is applied for about 5 minutes. Keep the temperature at 7 ° C.
- 0.1M phosphoric acid solution for 10 hours at 0 ° C and 193V.
- Immerse in chromic acid solution for 12 hours at 65 ° C.
- 0.1M phosphoric acid solution for 5 hours at 0 ° C and 193V.
- phosphoric acid solution at 30 ° C for 2 1/2 hours.
2) Pre-existing water is removed from the substrate made in 1) above.
- Rinse this substrate well with water and rinse it with methanol again.
- Rinse thoroughly and immerse in methanol solution for 30 minutes.
- Remove the substrate from the methanol solution and dry thoroughly with nitrogen gas.
- Put it in a desiccator and let it dry for an additional 10 minutes with a rotary pump.
3) Place the microstructure of above 2) in a closed container with 25% ammonia solution and connect the rotary pump to the container to make vacuum. This state is maintained for 1 hour.
4) Alternatively, in addition to the method described in 3) above, the gaseous ammonia bomb may be directly connected to the chamber to saturate the vessel with ammonia gas. This state is also maintained for 1 hour.
5) Take out the substrate which is sufficiently exposed to ammonia gas by 3) or 4) and immerse it in a 250 mL beaker containing ultra pure water from which ions have been removed. This state is maintained for 1 hour
6) Remove the substrate made by 5) above and transfer to a 250 mL beaker containing 95% ethanol. This state is maintained for 1 hour.
7) Remove the substrate prepared in step 6), dry it with a weak flow of nitrogen gas, pour an appropriate amount of ultraviolet curing type polymer precursor before the ethanol on the surface of the substrate is completely dried, and place the cleaned glass substrate thereon.
8) The substrate is exposed to ultraviolet rays and curing is progressed to a point at which the dose reaches 150 mJ cm -2 .
9) Finally, the AAO pattern is separated from the template.
FIG. 8 shows a scanning electron microscope image of the final copied pattern in this manner.
Example 4. Hydrophilic O65 Anodization Pattern Utilization 2
1) We fabricate microstructures that are repetitive and controlled to nanometer level using aluminum anodization technique.
- Aluminum substrate (2x5 cm 2 ) is put into a 25% perchloric acid ethanol solution and a potential of 20 V is applied for about 5 minutes. Keep the temperature at 7 ° C.
- Anodic oxidation in a 0.3M oxalic acid solution for 8 hours at 15 ° C, 40V.
- Immerse in chromic acid solution at 65 ° C for 3 hours or 4 hours.
- Anodic oxidation in a 0.3M oxalic acid solution for 3 minutes at 15 ° C, 40V.
- phosphoric acid solution at 30 ° C for 40 minutes.
2) Pre-existing water is removed from the substrate made in 1) above.
- Rinse this substrate well with water and rinse it with methanol again.
- Rinse thoroughly and immerse in methanol solution for 30 minutes.
- Remove the substrate from the methanol solution and dry thoroughly with nitrogen gas.
- Put it in a desiccator and let it dry for an additional 10 minutes with a rotary pump.
3) Place the microstructure of above 2) in a closed container with 25% ammonia solution and connect the rotary pump to the container to make vacuum. This state is maintained for 1 hour.
4) Alternatively, in addition to the method described in 3) above, the gaseous ammonia bomb may be directly connected to the chamber to saturate the vessel with ammonia gas. This state is also maintained for 1 hour.
5) Take out the substrate which is sufficiently exposed to ammonia gas by 3) or 4) and immerse it in a 250 mL beaker containing ultra pure water from which ions have been removed. This state is maintained for 1 hour
6) Remove the substrate made by 5) above and transfer to a 250 mL beaker containing 95% ethanol. This state is maintained for 1 hour.
7) Remove the substrate from above 6) and transfer it to a 250 mL beaker containing acetone. This state is maintained for 1 hour.
8) Remove the substrate from above 7), dry it with a weak flow of nitrogen gas, pour an appropriate amount of ultraviolet curing type polymer precursor before the ethanol on the surface of the substrate is completely dried, and place the cleaned glass substrate thereon.
9) The substrate is exposed to ultraviolet rays and curing is progressed to a point at which the dose reaches a specific dose (150 mJ cm -2 ).
10) Finally, the AAO pattern is separated from the template.
FIG. 9 shows a scanning electron microscope image of the final copied pattern in this manner.
Example 5. Utilizing hydrophobic P250 anodization pattern
1) We fabricate microstructures that are repetitive and controlled to nanometer level using aluminum anodization technique.
- Aluminum substrate (2x5 cm 2 ) is put into a 25% perchloric acid ethanol solution and a potential of 20 V is applied for about 5 minutes. Keep the temperature at 7 ° C.
- 0.1M phosphoric acid solution for 10 hours at 0 ° C and 193V.
- Immerse in chromic acid solution for 12 hours at 65 ° C.
- 0.1M phosphoric acid solution for 5 hours at 0 ° C and 193V.
- phosphoric acid solution at 30 ° C for 2 1/2 hours.
2) Pre-existing water is removed from the substrate made in 1) above.
- Rinse this substrate well with water and rinse it with methanol again.
- Rinse thoroughly and immerse in methanol solution for 30 minutes.
- Remove the substrate from the methanol solution and dry thoroughly with nitrogen gas.
- Put it in a desiccator and let it dry for an additional 10 minutes with a rotary pump.
3) The microstructure produced in 2) above is modified to a hydrophobic surface.
The well-dried microstructures are placed in a mixture of sulfuric acid and hydrogen peroxide (2: 1 by volume) and held for 1 minute.
- Remove the substrate, rinse well with water and dry it well with nitrogen gas.
- Place the substrate in a 250 mL solution containing normal hexane solution.
- Put this solution in a glove box, remove the moisture-containing air with a rotary pump, and fill it with high purity nitrogen (99.9% or more).
- Prepare 3mM HDFS solution as a normal hexane solvent and transfer the microstructure to this solution.
- After 10 minutes, transfer the microstructure back to the normal hexane solvent and take it out of the glove box.
- Transfer the substrate from the normal hexane solution to a beaker containing 3 M Novec HFE-7100 solution.
- Allow ultrasonic cleaning for 90 seconds.
4) Place the microstructure of above 3) in a closed container with 25% ammonia solution and connect the rotary pump to the container to make vacuum. This state is maintained for 1 hour.
5) Alternatively, in addition to the methods described in 4) above, a gaseous ammonia bomb may be connected directly to the chamber to saturate the vessel with ammonia gas. This state is also maintained for 1 hour.
6) Remove the substrate sufficiently exposed to ammonia gas by 4) or 5) above and immerse it in a 250 mL beaker containing deionized water. This state is maintained for 1 hour
7) Remove the substrate made by 6) above and transfer to a 250 mL beaker containing 95% ethanol. This state is maintained for 1 hour.
8) Remove the substrate from above 7), dry it with a weak flow of nitrogen gas, pour an appropriate amount of ultraviolet curing type polymer precursor before the ethanol on the surface of the substrate is completely dried, and place the cleaned glass substrate thereon.
9) The substrate is exposed to ultraviolet rays and curing is progressed to a point at which the dose reaches a specific dose (150 mJ cm -2 ).
10) Finally, the AAO pattern is separated from the template.
FIG. 10 shows a scanning electron microscope image of the final copied pattern in this manner.
Example 6. Utilizing hydrophobic O65 anodizing pattern
1) We fabricate microstructures that are repetitive and controlled to nanometer level using aluminum anodization technique.
- Aluminum substrate (2x5 cm 2 ) is put into a 25% perchloric acid ethanol solution and a potential of 20 V is applied for about 5 minutes. Keep the temperature at 7 ° C.
- Anodic oxidation in a 0.3M oxalic acid solution for 8 hours at 15 ° C, 40V.
- Immerse in chromic acid solution at 65 ° C for 3 hours or 4 hours.
- Anodic oxidation in a 0.3M oxalic acid solution for 3 minutes at 15 ° C, 40V.
- phosphoric acid solution at 30 ° C for 40 minutes.
2) Pre-existing water is removed from the substrate made in 1) above.
- Rinse this substrate well with water and rinse it with methanol again.
- Rinse thoroughly and immerse in methanol solution for 30 minutes.
- Remove the substrate from the methanol solution and dry thoroughly with nitrogen gas.
- Put it in a desiccator and let it dry for an additional 10 minutes with a rotary pump.
3) The microstructure produced in 2) above is modified to a hydrophobic surface.
The well-dried microstructures are placed in a mixture of sulfuric acid and hydrogen peroxide (2: 1 by volume) and held for 1 minute.
- Remove the substrate, rinse well with water and dry it well with nitrogen gas.
- Place the substrate in a 250 mL solution containing normal hexane solution.
- Put this solution in a glove box, remove the moisture-containing air with a rotary pump, and fill it with high purity nitrogen (99.9% or more).
- Prepare 3mM HDFS solution as a normal hexane solvent and transfer the microstructure to this solution.
- After 10 minutes, transfer the microstructure back to the normal hexane solvent and take it out of the glove box.
- Transfer the substrate from the normal hexane solution to a beaker containing 3 M Novec HFE-7100 solution.
- Allow ultrasonic cleaning for 90 seconds.
4) Place the microstructure of above 3) in a closed container with 25% ammonia solution and connect the rotary pump to the container to make vacuum. This state is maintained for 1 hour.
5) Alternatively, in addition to the methods described in 4) above, a gaseous ammonia bomb may be connected directly to the chamber to saturate the vessel with ammonia gas. This state is also maintained for 1 hour.
6) Remove the substrate sufficiently exposed to ammonia gas by 4) or 5) above and immerse it in a 250 mL beaker containing deionized water. This state is maintained for 1 hour
7) Remove the substrate made by 6) above and transfer to a 250 mL beaker containing 95% ethanol. This state is maintained for 1 hour.
8) Remove the substrate from above 7) and transfer to a 250-mL beaker containing acetone solution. This state is maintained for 1 hour.
9) Remove the substrate from 8) and dry it with a weak flow of nitrogen gas. Before the ethanol on the surface of the substrate is completely dried, pour an appropriate amount of ultraviolet curable polymer precursor, and place the cleaned glass substrate thereon.
10), the substrate is exposed to ultraviolet rays and cured until reaching a proper dose (150 mJ cm -2 ).
11) Finally, the AAO pattern is separated from the template.
FIG. 11 shows a scanning electron microscope image of the final copied pattern in this manner.
Example 7. Duplicate pattern over 3 micrometers deep
1) We fabricate microstructures that are repetitive and controlled to nanometer level using aluminum anodization technique.
- Aluminum substrate (2x5 cm 2 ) is put into a 25% perchloric acid ethanol solution and a potential of 20 V is applied for about 5 minutes. Keep the temperature at 7 ° C.
- 0.1M phosphoric acid solution for 10 hours at 0 ° C and 193V.
- Immerse in chromic acid solution for 12 hours at 65 ° C.
- 0.1M phosphoric acid solution for 5 hours at 0 ° C and 193V.
- phosphoric acid solution at 30 ° C for two and a half hours.
2) Pre-existing water is removed from the substrate made in 1) above.
- Rinse this substrate well with water and rinse it with methanol again.
- Rinse thoroughly and immerse in methanol solution for 30 minutes.
- Remove the substrate from the methanol solution and dry thoroughly with nitrogen gas.
- Put it in a desiccator and let it dry for an additional 10 minutes with a rotary pump.
3) The microstructure produced in 2) above is modified to a hydrophobic surface.
The well-dried microstructures are placed in a mixture of sulfuric acid and hydrogen peroxide (2: 1 by volume) and held for 1 minute.
- Remove the substrate, rinse well with water and dry it well with nitrogen gas.
- Place the substrate in a 250 mL solution containing normal hexane solution.
- Put this solution in a glove box, remove the moisture-containing air with a rotary pump, and fill it with high purity nitrogen (99.9% or more).
- Prepare 3mM HDFS solution as a normal hexane solvent and transfer the microstructure to this solution.
- After 10 minutes, transfer the microstructure back to the normal hexane solvent and take it out of the glove box.
- Transfer the substrate from the normal hexane solution to a beaker containing 3 M Novec HFE-7100 solution.
- Allow ultrasonic cleaning for 90 seconds.
4) Place the microstructure of above 3) in a closed container with 25% ammonia solution and connect the rotary pump to the container to make vacuum. This state is maintained for 1 hour.
5) Alternatively, in addition to the methods described in 4) above, a gaseous ammonia bomb may be connected directly to the chamber to saturate the vessel with ammonia gas. This state is also maintained for 1 hour.
6) Remove the substrate sufficiently exposed to ammonia gas by 4) or 5) above and immerse it in a 250 mL beaker containing deionized water. This state is maintained for 1 hour
7) Remove the substrate made by 6) above and transfer to a 250 mL beaker containing 95% ethanol. This state is maintained for 1 hour.
8) Remove the substrate prepared in step 7), dry it with a weak flow of nitrogen gas, pour an appropriate amount of UV-curable polymer precursor (PEG-DA) on the surface of the substrate before ethanol is completely dried, .
9) The substrate is exposed to ultraviolet rays and curing is progressed to a point at which the dose reaches a specific dose (150 mJ cm -2 ).
10) Finally, the AAO pattern is separated from the template.
FIG. 12 shows a scanning electron microscope image of the final copied pattern in this manner.
As described above, the technical structure of the present invention is based on the technical concept of the present invention or essential conditions, that is, the essential concept of effective filling using ammonia, so that the hydrophilic property, the hydrophobicity, Can be widely used for pattern replication techniques very effectively. In particular, it can be seen from the electron micrographs shown that the aluminum anodic oxidation pattern, which is the original of each replicate pattern, is exactly duplicated in size. For example, the hole depth of the O65 aluminum bipolar pattern is 70 nm, and this depth is accurately reflected in the height of the replica pattern (see FIGS. 5, 9 and 11) It can be seen that the replication pattern with the reflected height is created. (See Figs. 4, 8 and 10)
In addition, the present invention can be carried out in other specific forms while maintaining the core concept, and the depth can also be up to micrometers (see FIG. 12). In other words, it should be understood that the embodiments described in the present invention should be interpreted in all aspects as illustrative and not restrictive. FIG. 13 shows an example in which the selective modification is induced by another method using the technical core of the present invention. In the two embodiments of the present invention, the stepwise exchange phenomenon is induced in the ultraviolet curing
1 is a schematic diagram showing a schematic process of the present invention for selectively immobilizing an organic material on a patterned surface.
FIG. 2 is a scanning electron micrograph of the AAO template (P250) prepared in the same manner as in Example 1. FIG. 3 is a graph showing the relationship between the depth of the hole pattern of P250 produced by the process of Example 1 and the anodization time. It can be seen that the oxide film grows at a rate of 0.2 nm per second.
Fig. 4 shows a scanning electron microscope image of a replication pattern ultimately separated by Example 1. Fig.
FIG. 5A is a plane scanning electron micrograph of the O65 anodization pattern. FIG.
5B is a lateral scanning electron micrograph of the O65 anodization pattern.
FIG. 6 is a graph showing the rate of growth of the oxide film with respect to the O65 anodic oxidation pattern by time.
FIG. 7A is a plane scanning electron micrograph of a copy pattern replicated with O65 prepared in Example 2. FIG.
FIG. 7B is a lateral scanning electron micrograph of a copy pattern replicated with O65 prepared in Example 2. FIG.
FIG. 8A is a plane scanning electron micrograph of a duplicate pattern replicated with P250 produced in Example 3. FIG.
FIG. 8B is a side principal-prism micrograph of a copy pattern replicated with P250 produced in Example 3. FIG.
FIG. 9A is a plane scanning electron micrograph of a copy pattern replicated with O65 produced in Example 4. FIG.
FIG. 9B is a lateral scanning electron micrograph of a replica pattern replicated with O65 prepared in Example 4. FIG.
FIG. 10A is a plane scanning electron micrograph of a replica pattern replicated with P250 produced in Example 5. FIG.
10B is a lateral scanning electron micrograph of a replica pattern replicated with P250 produced in Example 5. Fig.
FIG. 11A is a planar scanning electron microscopic photograph of a replica pattern replicated with O65 prepared in Example 6. FIG.
11B is a lateral scanning electron micrograph of the replica pattern replicated with O65 prepared in Example 6. Fig.
12 is a scanning electron microscope (SEM) image of a depth of 3 micrometer duplicate pattern produced by Example 7. FIG.
FIG. 13 is a schematic diagram of another embodiment that can be applied using the core concept as it is similar to the embodiments of the present invention.
Claims (15)
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| PCT/KR2009/005739 WO2010041873A2 (en) | 2008-10-09 | 2009-10-08 | Method of insertion into nanopores of polymer precursor using vacuum effect and method for precision duplication of nanopattern using same |
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| JP2000108100A (en) | 1998-09-04 | 2000-04-18 | Nec Corp | Quantum dot solid and patterning method for conventional type solid |
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| JP5000112B2 (en) * | 2005-09-09 | 2012-08-15 | 東京応化工業株式会社 | Pattern formation method by nanoimprint lithography |
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