KR102389523B1 - Hydrophilic fine-pattern stamp and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a hydrophilic micro-stamp, and more particularly, to a hydrophilic micro-stamp capable of forming a reliable hydrophilic micro-pattern.
The hydrophilic micro-stamp of the present invention includes a hydrophilic micro-pattern including a hydrophilic polymer containing a structural unit derived from a polyfunctional water-soluble monomer and an elastic substrate containing a silicone-based elastomer positioned on the upper surface of the hydrophilic micro-pattern, The hydrophilic micropattern and the elastic substrate are coupled to each other to impart elasticity to the hydrophilic micropattern.

Description

Hydrophilic fine-pattern stamp and manufacturing method thereof

The present invention relates to a hydrophilic micro-stamp, and more particularly, to a hydrophilic micro-stamp capable of forming a reliable hydrophilic micro-pattern.

In general, the micro-pattern forming process applied to data storage, small sensors, photonic crystals and optical devices, micro-electromechanical devices, display devices, displays, and semiconductors uses a photolithography process to form micro-patterns using light. am. However, as LCD substrates become larger, pattern sizes are miniaturized, and price competitiveness in each field is intensifying, the need for a lithography process of an innovative new concept has emerged rather than the existing photolithography process.

That is, in the conventional photolithography process, exposure, post-exposure bake, development, post-development bake, etching process, cleaning process, etc. must be performed every time a pattern is formed, so the process takes a long time, and the photo process is repeated a number of times. There is a problem in that productivity is lowered because it has to be done. In addition, it is difficult to manufacture a fine linear pattern because the resolution limit due to the diffraction phenomenon of light occurs. Accordingly, various lithography technologies, such as electron beam lithography, X-ray lithography, and focused ion beam, have been studied, but these technologies require expensive equipment and complicated processes, so there is a problem in commercialization.

Due to these problems, an imprint lithography process has recently been attracting attention. Imprint lithography is a method first developed by Stephen Chou of Princeton University, USA to imprint nanoscale, and the shape (pattern) required on the surface of a stamp made of relatively strong inorganic or polymer. is to form a fine pattern by pre-fabricating and pressing a stamp on another material (resin) previously applied to form a pattern. Specifically, it is a method of forming a pattern in the curable composition by compressing it to a curable composition coated on a metal film or organic film using a stamp having a desired fine pattern formed in advance, and heat or photocuring it to simplify the process compared to the existing photolithography method and It has an advantage advantageous for forming a fine pattern.

However, since most of the stamps used in the imprint lithography process are hydrophobic materials, there is a problem in that it is difficult to form nano-scale fine patterns on hydrophilic materials (resins).

In order to solve this problem, a method of forming a micropattern on a hydrophilic resin after plasma-treating a stamp made of polydimethylsiloxane (PDMS) to modify the surface to be hydrophilic has been developed. However, the method has disadvantages in that the hydrophilicity of the PDMS stamp surface is easily lost, and thus a new plasma treatment is required repeatedly in order to re-modify to hydrophilicity, and cracks may occur in the PDMS during plasma treatment.

In addition, U.S. Patent No. 6596346 proposes a technique for making the surface of the stamp hydrophilic by grafting polyethylene glycol (PEG) on the surface of a polydimethylsiloxane (PDMS) stamp on which a pattern is formed. there is.

The stamp graft technology has the advantage of higher hydrophilicity than the plasma-treated stamp because PEG is grafted onto the stamp surface, but when the molecular weight of PEG has a certain level or more, the graft density is lowered. When the stamp is repeatedly used, there is a problem that the PEG bound to the stamp surface is bound to the hydrophilic resin and the PEG may be separated from the stamp.

Accordingly, the hydrophilicity of the stamp surface is not lost even if it is repeatedly compressed on the hydrophilic resin and the hydrophilic micro-pattern is transferred, and it is necessary to develop a reliable hydrophilic micro-stamp having the same mechanical properties as that of PDMS.

(Patent Document 1): US Patent No. 06596346

An object of the present invention is to provide a hydrophilic micro-stamp capable of producing a reliable hydrophilic pattern.

The hydrophilic micro-stamp according to the present invention includes a hydrophilic micro-pattern including a hydrophilic polymer containing a structural unit derived from a polyfunctional water-soluble monomer and an elastic substrate containing a silicone-based elastomer positioned on the upper surface of the hydrophilic micro-pattern, The hydrophilic micropattern and the elastic substrate are bonded to each other to impart elasticity to the hydrophilic micropattern.

The micro-stamp according to an embodiment of the present invention may further include a mixed layer positioned between the upper surface of the hydrophilic micro-pattern and the lower surface of the elastic substrate, in which the hydrophilic polymer and the silicone-based elastomer coexist.

In the micro-stamp according to an embodiment of the present invention, the ratio (d1/d2) of the thickness d1 of the hydrophilic micro-pattern to the thickness d2 of the elastic substrate may be 1:1 to 1:1,000.

In the micro-stamp according to an embodiment of the present invention, the hydrophilic polymer may be a non-swellable cross-linked polymer.

In the micro-stamp according to an embodiment of the present invention, the polyfunctional water-soluble monomer may be a polyethylene glycol-based polyfunctional monomer.

In the micro-stamp according to an embodiment of the present invention, the hydrophilic polymer has a weight average molecular weight of 100 to 20,000 g/mol, and may be liquid at room temperature.

In the micro-stamp according to an embodiment of the present invention, the silicone-based elastomer may be a polydimethylsiloxane-based elastomer.

In the fine stamp according to an embodiment of the present invention, the fine stamp may have a Young's modulus of 0.5 to 10 MPa.

The method for producing a hydrophilic micro-stamp according to the present invention comprises the steps of (S1) applying a polymerizable solution containing a polyfunctional water-soluble monomer and a photoinitiator to a substrate including a pattern on the surface; (S2) photocuring the applied polymerizable solution to form a hydrophilic fine pattern; (S3) applying a silicone-based prepolymer solution to the upper surface of the hydrophilic micropattern; (S4) curing the silicone-based prepolymer solution; includes.

In the method of manufacturing a fine stamp according to an embodiment of the present invention, after step (S1), before step (S2), applying a silicone-based polymerizable solution on top of the applied polymerizable solution; may further include .

In the method for manufacturing a hydrophilic fine stamp according to an embodiment of the present invention, in step (S4), the silicone-based prepolymer solution may be thermosetting.

In the method of manufacturing a hydrophilic fine stamp according to an embodiment of the present invention, thermal curing may be performed at a temperature range of 25° C. to 150° C. for 10 minutes to 48 hours.

In the method of manufacturing a hydrophilic fine stamp according to an embodiment of the present invention, the silicone-based prepolymer solution may include a polydimethylsiloxane-based polymer including a vinyl group.

In the method of manufacturing a hydrophilic micro-stamp according to an embodiment of the present invention, after step (S4), the step of separating the hydrophilic micro-stamp from the substrate may be further included.

The method for producing a hydrophilic fine pattern according to the present invention comprises the steps of (A1) applying a hydrophilic solution containing a polyfunctional water-soluble monomer and a photoinitiator to the surface to form a hydrophilic coating layer; (A2) pressing the hydrophilic fine stamp according to any one of claims 1 to 8 on the hydrophilic coating layer; (A3) photo-curing the pressed hydrophilic coating layer; and (A4) separating the hydrophilic fine stamp.

In the method for producing a hydrophilic micropattern according to an embodiment of the present invention, the polyfunctional water-soluble monomer may be a polyethylene glycol-based polyfunctional monomer.

In the method for producing a hydrophilic fine pattern according to an embodiment of the present invention, the polymerizable solution may further include a monofunctional monomer.

The hydrophilic micropattern according to the present invention is manufactured by the method of claim 14 .

In the hydrophilic micro-stamp according to the present invention, the part on which the micro-pattern is formed and the part of the elastic base that imparts elasticity to the stamp are coupled to each other, so that a reliable micro-pattern can be repeatedly manufactured.

In addition, the hydrophilic micro-stamp according to the present invention can form micro/nano-sized micro-patterns on a biocompatible resin having a hydrophilic surface, including hydrophilic micro-patterns.

1 is a method of manufacturing a hydrophilic fine stamp according to an embodiment of the present invention,
2 is a method of manufacturing a hydrophilic fine pattern according to an embodiment of the present invention,
3 is a scanning electron microscope photograph showing the hydrophilic micro-pattern of the hydrophilic micro-stamp according to the present invention;
4 to 16 are scanning electron microscope photographs showing a hydrophilic micropattern (linear) according to the present invention;
17 is a photograph showing a hydrophilic micropattern (hole) according to the present invention and a photograph of a scanning electron microscope.

Unless otherwise defined in technical terms and scientific terms used in this specification, those of ordinary skill in the art to which this invention belongs have the meanings commonly understood, and in the following description and accompanying drawings, the subject matter of the present invention Descriptions of known functions and configurations that may unnecessarily obscure will be omitted.

Also, the singular form used herein may be intended to include the plural form as well, unless the context specifically dictates otherwise.

In addition, in the present specification, the unit used without special mention is based on the weight, for example, the unit of % or ratio means weight % or weight ratio, and the weight % means any one component of the entire composition unless otherwise defined. It means the weight % occupied in the composition.

In addition, the numerical range used herein includes the lower limit and upper limit and all values within the range, increments logically derived from the form and width of the defined range, all values defined therein, and the upper limit of the numerical range defined in different forms. and all possible combinations of lower limits. Unless otherwise defined in the specification of the present invention, values outside the numerical range that may occur due to experimental errors or rounding of values are also included in the defined numerical range.

As used herein, the term 'comprising' is an open-ended description having an equivalent meaning to expressions such as 'comprising', 'containing', 'having' or 'characterized', and elements not listed in addition; Materials or processes are not excluded.

In this specification, when it is said that a part of a film (layer), region, component, etc. is on or on another part, not only the case where it is directly on top in contact with another part, but also another film (layer), another region, etc. in the middle; The case in which other components etc. are interposed is also included.

As used herein, the term “master stamp” is for forming a fine pattern on the stamp of the present invention, and a fine pattern corresponding to the stamp of the present invention is formed. Specifically, when an embossed pattern is formed on the master stamp of the present invention, a corresponding engraved pattern is formed on the stamp of the present invention. On the contrary, when the engraved pattern is formed on the master stamp of the present invention, the corresponding embossed pattern is formed on the stamp of the present invention. The master stamp may use a master stamp of a conventional imprint lithography process capable of forming an embossed or engraved pattern on the stamp of the present invention. Specifically, it may be a silicon wafer having an embossed or engraved pattern formed through photolithography or electron beam lithography.

As used herein, the term “polymer” refers to a polymerization product of one or more monomers (monomers) and can be used in the same meaning as a polymer, and unless otherwise defined, homopolymer, interpolymer, copolymer, terpolymer and the like, and any combination or modification of the above, including block, graft, addition or condensation of polymers.

Conventionally, a hydrophilic fine pattern manufacturing method through an imprint lithography process uses a polydimethylsiloxane (PDMS) stamp in which polyethylene glycol (PEG) is grafted onto the surface and becomes hydrophilic. However, since PEG is simply grafted onto the surface of the PDMS stamp, when the stamp is compressed on the hydrophilic resin, the hydrophilic resin and the PEG are bound to separate the PEG from the PDMS stamp. Accordingly, it is difficult to reliably manufacture the patterned hydrophilic resin, and the life of the stamp is also short. And in the case of such a stamp, after the pattern is formed on the PDMS, the PEG is grafted to make it hydrophilic, and thus the physical properties of the PDMS are affected during the pattern formation process. PDMS is a relatively soft polymer, and swelling may occur, which may change the pattern formed on the surface of the PDMS stamp. For this reason, it is difficult to actually apply the PDMS stamp as a stamp for forming a nano-sized pattern.

The present inventors conducted various studies on the material of the stamp to reliably form a pattern on the hydrophilic resin through the imprint lithography process. As a result, when the stamp is a hydrophilic polymer containing a structural unit derived from a polyfunctional water-soluble monomer, the It was confirmed that micro- and nano-sized precise patterns can be formed on the surface. However, as the above-described stamp has a lower elastic force compared to the conventional PDMS stamp, the adhesion between the stamp and the hydrophilic resin is lowered, so that a high defect rate occurs when forming a fine pattern, and rather reliability is lowered. As a result of in-depth research based on these findings, the present applicant was able to form a hydrophilic precise fine pattern through a hydrophilic polymer containing a structural unit derived from a polyfunctional water-soluble monomer, and at the same time, an elastic force on the top of the formed fine pattern. When manufacturing a stamp bonded with an elastic base having

Hereinafter, the hydrophilic micro-stamp of the present invention will be described in detail.

As described above, the hydrophilic micro-stamp of the present invention has a hydrophilic micro-pattern including a hydrophilic polymer containing a structural unit derived from a polyfunctional water-soluble monomer and an elastic substrate containing a silicone-based elastomer positioned on the upper surface of the hydrophilic micro-pattern. Including, the hydrophilic micro-pattern and the elastic substrate are bonded to each other to impart elasticity to the hydrophilic micro-pattern. Such a stamp can transfer the micropattern to the hydrophilic resin as the hydrophilic micropattern that can form a micropattern in contact with another material (resin) includes a hydrophilic polymer. In addition, since the hydrophilic micropattern and the elastic substrate are combined, separation is prevented, and as elastic force is given to the hydrophilic micropattern, the adhesion between the hydrophilic resin and the stamp can be increased, and a reliable micropattern can be repeatedly formed. there is. In particular, the stamp of the present invention can precisely and repeatedly form micro- and nano-sized patterns on most hydrophilic biocompatible materials, and it can be possible to manufacture bio devices such as DNA chips, protein chips, and cell chips.

Specifically, as the hydrophilic micropattern of the hydrophilic micro-stamp contains a hydrophilic polymer containing a structural unit derived from a polyfunctional water-soluble monomer, micro- and nano-sized micro-patterns are formed on the hydrophilic resin, unlike a stamp made of a hydrophobic polymer. can do.

According to an aspect of the present invention, the hydrophilic polymer of the stamp may be a polymer made of a polyfunctional water-soluble oligomeric monomer. In addition, according to an aspect of the present invention, it may be a combination of a polyfunctional water-soluble low molecular weight monomer and a monofunctional water-soluble low molecular weight monomer. The polyfunctional water-soluble oligomer-type monomer has a relatively low viscosity and high fluidity, so that it can be applied to the nano-sized pattern formed on the master stamp without a gap. Accordingly, it is possible to provide a stamp having micro- and nano-sized micro-patterns with high precision.

The polyfunctional water-soluble oligomeric monomer may preferably be a polyethylene glycol-based polyfunctional monomer. More preferably, the polyethylene glycol-based polyfunctional monomer may be polyethyleneglycol diacrylate (PEGDA) or polyethyleneglycol dimethacrylate (PEGDMA). The hydrophilic polymer formed of the structural unit derived from such a polyethylene glycol-based polyfunctional monomer may be a non-swellable cross-linked polymer as well as a hydrophilic and biocompatible polymer. Accordingly, the stamp containing the polyethylene glycol-based polyfunctional monomer is mostly compressed on a hydrophilic biocompatible resin, making it possible to manufacture bio devices such as DNA chips, protein chips, and cell chips. The number of functional groups of the polyethylene glycol-based polyfunctional monomer may be 2 to 6, preferably 2 to 4, and more preferably 2 to 3. The polyethylene glycol-based polyfunctional monomer having the number of functional groups in the above range may have a curing rate at which a hydrophilic polymer having a homogeneous density can be formed.

Such a polyfunctional water-soluble monomer may have a weight average molecular weight of 100 to 20,000 g/mol, preferably 100 to 10,000 g/mol, and most preferably 500 to 5,000 g/mol, and may be liquid at room temperature. In the above range, the polyfunctional water-soluble monomer may have an appropriate viscosity for forming a fine pattern. If the fluidity is too low because the viscosity of the polyfunctional water-soluble monomer is too low, it is difficult to apply it evenly on the surface of the master stamp, so that it is difficult to transfer the fine pattern into an accurate shape. Conversely, if the fluidity is too high due to the low viscosity, it is not possible to maintain an appropriate thickness for forming a fine pattern on the surface of the master stamp. In the above range, the multifunctional water-soluble monomer may have a suitable viscosity to form a fine pattern on the surface of the master stamp and at the same time form an appropriate thickness.

According to one aspect of the present invention, the hydrophilic polymer may be a non-swellable crosslinked polymer. The non-swellable cross-linked polymer does not swell like PDMS when it is cured in a liquid phase and changed to a solid phase. Accordingly, it is possible to prevent dimensional change due to hardening, so that a precise and reliable pattern can be formed on the stamp. In addition, it is possible to prevent swelling due to oil or moisture in the surrounding environment, thereby maintaining a precise pattern shape for a long time.

The elastic substrate of the present invention is for imparting elastic force to the hydrophilic micro-pattern, and is located on the upper surface of the hydrophilic micro-pattern. Here, the upper surface of the hydrophilic micropattern refers to a surface opposite to one side of the hydrophilic micropattern in contact with the master stamp. That is, the lower surface of the hydrophilic micropattern is in contact with the master stamp, and the upper surface is coupled to the elastic substrate. The elastic substrate has elasticity as it contains a silicone-based elastomer, and as an elastic force is applied to the stamp, the hydrophilic micropattern of the stamp is closely adhered to the hydrophilic resin to form the micropattern without space, and the micropattern is precisely formed on the hydrophilic resin. can be formed. That is, it is possible to reduce the defect rate of the fine pattern manufactured from the stamp.

At this time, the stamp of the present invention may have a Young's modulus of 0.5 to 10 MPa, preferably 1 to 7 MPa, more preferably 2 to 5 MPa. In the above range, the stamp of the present invention has an appropriate elastic force to form a fine pattern. When the Young's modulus is higher than the above range, the stamp is not in close contact with the hydrophilic resin, so the defect rate of the micropattern produced from the stamp is increased. can be

The Young's modulus, that is, the elastic force, of the stamp of the present invention can be controlled by the ratio (d1/d2) of the thickness (d1) of the hydrophilic micropattern to the thickness (d2) of the elastic substrate. Alternatively, the elastic force of the stamp can be adjusted through the intrinsic elastic force of the elastic substrate. Specifically, the ratio (d1/d2) of the thickness (d1) of the hydrophilic micropattern to the thickness (d2) of the elastic substrate is 1:1 to 1:1,000, preferably 1:2 to 1:100, more preferably It may be 1:5 to 1:50. In the thickness ratio (d1/d2) in the above range, the stamp forms an appropriate Young's modulus, and as a stamp, it is easy for a user to handle.

In contrast, the elastic force of the elastic substrate can be controlled through the physical properties of the silicone-based elastic polymer. For example, the elastic base material of the present invention may be any silicone-based elastic polymer having elasticity, but preferably a polydimethylsiloxane-based elastic polymer. The elastic force of the polydimethylsiloxane-based elastomer can be variously adjusted according to the content of the curing agent added during curing, so it is easy to provide the elastic force required by the stamp of the present invention. The polydimethylsiloxane-based elastomer may preferably be a polydimethylsiloxane-based polymer including a vinyl group, and more specifically, may be polydimethylsiloxane (PDMS). Polydimethylsiloxane is a non-toxic elastomer, which can be advantageously applied in the manufacture of bio devices. As described above, the silicone-based elastomer of the present invention may be a cross-linked elastomer prepared by curing a silicone-based prepolymer.

The elastic substrate is combined with the hydrophilic micro-pattern to impart elasticity to the hydrophilic micro-pattern. In this case, the hydrophilic micropattern and the elastic polymer are bonded to each other, and a mixed layer in which the hydrophilic polymer and the silicone-based elastomer coexist may be further included between the upper surface of the hydrophilic micropattern and the lower surface of the elastic substrate. By the mixed layer, the hydrophilic micro-pattern including the hydrophilic polymer and the elastic substrate including the silicone-based elastomer may be more strongly bonded to each other. Such, the stamp of the present invention can form a fine pattern repeatedly on the hydrophilic resin more reliably during the imprint process, and has a long lifespan. Accordingly, the industrial applicability is high by enabling mass production and repeated production.

The hydrophilic micro-stamp of the present invention described above includes a hydrophilic micro-pattern and an elastic substrate that is coupled thereto to impart elastic force to the hydrophilic micro-pattern, and a precise micro-pattern can be reliably and repeatedly formed on a hydrophilic resin. In particular, it is possible to stably form a fine pattern on a biocompatible material that is mostly hydrophilic.

1 shows a method of manufacturing a hydrophilic fine stamp according to an embodiment of the present invention. Hereinafter, with reference to FIG. 1, the manufacturing method of the hydrophilic fine stamp of the present invention will be described.

The method for producing a hydrophilic fine stamp of the present invention comprises the steps of (S1) applying a polymerizable solution containing a polyfunctional water-soluble monomer and a photoinitiator to a substrate including a pattern on the surface, (S2) photocuring the applied polymerizable solution forming a hydrophilic micropattern, (S3) applying a silicone-based prepolymer solution to the upper surface of the hydrophilic micropattern, (S4) curing the silicone-based prepolymer solution; may include. In this manufacturing method, as the silicone-based prepolymer solution is cured on the hydrophilic micropattern, an elastic substrate formed by curing the silicone-based prepolymer solution is formed on the hydrophilic micropattern. That is, the elastic substrate is coupled to the upper portion of the hydrophilic fine pattern. As the liquid silicone-based prepolymer solution is applied on the cured hydrophilic micropattern, the silicone-based prepolymer solution partially penetrates into the hydrophilic micropattern, and thereafter, the silicone-based prepolymer solution Upon curing, a mixed layer in which the hydrophilic micropattern and the elastic substrate coexist is formed between the hydrophilic micropattern and the elastic substrate. That is, the mixed layer can prevent the hydrophilic micropattern from being separated from the elastic substrate even when the imprint lithography process is repeatedly performed by increasing the bonding force between the hydrophilic fine pattern and the elastic substrate.

Specifically, step (S1) is a step of applying a polymerizable solution containing a polyfunctional water-soluble monomer and a photoinitiator to a substrate including a pattern on the surface. A substrate having a pattern on its surface refers to the master stamp of the impregnated lithography process. All general master stamps are applicable, and in general, it may be a silicon wafer on which an intaglio or embossed pattern is formed.

The polymerizable solution may be applied through spin coating, spray coating, knife coating, or roll coating, but is not limited thereto, and is uniformly applied to the substrate by a known coating method. It can be applied in one thickness. In step (S1), the polymerizable solution contains a polyfunctional water-soluble monomer and a photoinitiator, and can be cured when irradiated with ultraviolet light by the photoinitiator.

As the polymerizable solution contains a polyfunctional water-soluble monomer, it exhibits hydrophilicity after curing. The polyfunctional water-soluble monomer may preferably be a polyethylene glycol-based polyfunctional monomer. In this case, the functional group may be 2 to 10, preferably 2 to 8, more preferably 2 to 5. A polymerizable solution containing such a polyfunctional water-soluble monomer may exhibit biocompatibility as well as hydrophilicity after curing.

The photoinitiator has a characteristic that radicals are generated by light irradiation, and in particular, 320 nm to 380 nm in the ultraviolet wavelength region, for example 330 nm to 375 nm, specifically, radicals upon irradiation with light of 340 nm to 370 nm This can happen. When the light in the ultraviolet wavelength range is irradiated, a photocuring reaction in the polymerizable solution may be started. For example, the photoinitiator is anthraquinone, anthraquinone-2-sulfonic acid sodium salt monohydrate (anthraquinone-2-sulfonicacid, sodium salt monohydrate), (benzene) tricarbonylchromium [(benzene) tricarbonylchromium], benzyl ( benzil), benzoin ethyl ether, benzoin isobutyl ether, benzoin methyl ether, benzophenone, 4-benzoylbiphenyl , 4,4'-bis(diethylamino)benzophenone [4,4'-bis(diethylamino)benzophenone], 4,4'-bis(dimethylamino)benzophenone [4,4'-bis(dimethylamino)benzophenone ], dibenzosuberenone, 2,2-dimethoxy-2-phenylacetophenone (2,2-dimethoxy-2-phenylacetophenone), 3,4-dimethylbenzophenone (3,4-dimethylbenzophenone), 3 '-Hydroxyacetophenone (3'-hydroxyacetophenone), 2-hydroxy-2-methyl propiophenone (2-hydroxy-2-methyl propiophenone), 2-hydroxy-4'-(2-hydroxyethoxy )-2-methyl propiophenone [2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone], 1-hydroxycyclohexyphenyl ketone, methylbenzoyl formate ), diphenyl (2,4,6-trimethylbenzoyl)-phosphine oxide [diphenyl (2,4,6-trimethylbenzoyl)-phosphine oxide], phosphine oxide phenyl bis (2,4,6-trimethyl benzoyl) [ phosphine oxidephenyl bis (2,4,6-tri methyl benzoyl)], 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone {2-methyl-1-[4-(methylthio)phenyl] -2-(4-morpholinyl)-1-propanone}, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone {2-benzyl-2 -(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone}, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl- Phenyl)-butan-1-one] [2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one], bis(5-2 ,4-Cyclopentadien-1-yl)-bis(2,6-difluoro-3(1h-pyrrol-1yl)-phenyl)titanium [bis(.eta.5-2,4-cyclopentadien-1) -yl)-bis(2,6-difluoro-3(1h-pyrrol-1-yl)-

phenyl) titanium], 2-isopropyl thioxanthone, 2-ethylanthraquinone, 2,4-diethyl thioxanthone, benzyl dimethyl Ketal (benzil dimethylketal), benzophenone (benzophenone), 4-chloro benzophenone (4-chloro benzophenone), methyl-2-benzoyl benzoate (methyl-2-benzoylbenzoate), 4-phenyl benzophenone (4-phenyl benzophenone) , 2,2'-bis (2-chlorophenyl) -4,4'-5,5'-tetraphenyl-1,2'-bi-imidazole [2,2'-bis (2-chlorophenyl) -4 ,4',5,5'-tetraphenyl-1,2'-bi-imidazole], 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4' ,5'-diphenyl-1,1'-biimidazole [2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxypenly)-4',5'-diphenyl-1, 1'-biimidazole], 4-phenoxy-2',2'-dichloroacetophenone (4-phenoxy-2',2'-dichloro acetophenone), ethyl-4-(dimethylamino)benzoate [ethyl-4- (dimethylamino)benzoate], isoamyl 4-(dimethylamino)benzoate [isoamyl 4-(dimethylamino)benzoate], 2-ethyl hexyl-4-(dimethylamino)benzoate [2-ethyl hexyl-4-(dimethylamino) benzoate], 4,4'-bis(diethylamino)benzophenone [4,4'-bis(diethylamino)benzophenone],4-(4'-methylphenylthio)-benzophenone [4-(4'-methylphenylthio) -benzophenone],1,7-bis(9-acridinyl)heptane [1,7-bis(9-acridinyl)heptane], n-phenylglycine and 2-hydroxy-2 -Methylpropiophenone (2-hydroxy-2-methylpropiophenone) may be one or two or more selected from the group consisting of, but is not limited thereto, and all conventional photoinitiators that can be photocured by mixing with a polyfunctional water-soluble monomer are applicable Do.

The polymerizable solution of the present invention may contain 0.01 to 20 parts by weight of a photoinitiator, preferably 0.05 to 10 parts by weight, more preferably 1 to 5 parts by weight based on 100 parts by weight of the polyfunctional water-soluble monomer. In the above range, the photoinitiator may be mixed with the polyfunctional water-soluble monomer and cured, and the viscosity of the liquid polyfunctional water-soluble monomer does not significantly change.

Step (S2) is a step of photocuring the applied polymerizable solution to form a hydrophilic micropattern. The polymerizable solution can be cured when irradiated with ultraviolet light by a photoinitiator. The irradiated ultraviolet wavelength region may be 320 nm to 380 nm, preferably 330 nm to 375 nm, and more preferably 340 nm to 370 nm. In the above range, curing of the photoinitiator may occur to cure the polymerizable solution. In the case of photocuring, the light irradiation time may be 1 second to 30 minutes, preferably 30 seconds to 15 minutes, more preferably 1 minute to 10 minutes, but is not limited thereto, and the time sufficient to cure the polymerizable solution is not limited thereto. can be applied. As for the hydrophilic micropattern, a pattern corresponding to the substrate is formed. For example, when the engraved pattern is formed on the substrate, a embossed pattern is formed in the hydrophilic micropattern, whereas, when the embossed pattern is formed on the substrate, an engraved pattern is formed in the hydrophilic fine pattern.

And in one aspect of the present invention, it is possible to remove microbubbles of the applied polymerizable solution by inserting the applied polymerizable solution before the exposure (ultraviolet ray irradiation) in step (S2) into a vacuum chamber and forming a vacuum atmosphere. The polymeric solution from which the microbubbles are removed has a significantly lower defect rate due to microbubbles, and the polymerizable solution is quickly adhered to the nano-sized micropatterns formed on the surface of the substrate to quickly form a precise micropattern. At this time, the vacuum degree of the vacuum chamber may be a vacuum degree of 1×10 ° torr to 1×10 ^-3 torr, preferably 1×10 ^-1 torr to 1×10 ^-2 torr, and the vacuum degree maintaining time is 1 to 30 minutes. , preferably 5 to 10 minutes. In the above range, it is possible to remove microbubbles, and the polymerizable solution can be completely in close contact with the substrate.

Step (S3) is a step of applying a silicone-based prepolymer solution on the upper surface of the hydrophilic micropattern. In step (S3), as the liquid silicone-based prepolymer solution is applied to the upper surface of the hydrophilic micropattern, the silicone-based prepolymer solution partially penetrates the upper surface of the hydrophilic micropattern. The silicone prepolymer solution is intended to provide elasticity to the hydrophilic micropattern after curing, and specifically, may include a liquid silicone-based prepolymer and a curing agent (crosslinking agent).

The silicone-based prepolymer may be an addition-type silicone-based prepolymer capable of cross-linking and curing by addition reaction between the unsaturated group of the silicone-based prepolymer and the crosslinking agent in the presence of a catalyst. Specifically, the addition-type silicone-based prepolymer may be a siloxane-based prepolymer containing an ethylenically unsaturated group, and more specifically, may be a polydimethylsiloxane-based prepolymer containing a vinyl group. As a specific example, 2 to 20 vinyl groups may be included in one polydimethylsiloxane chain, but the present invention is not limited thereto. In the case of polydimethylsiloxane, the preferred range may include 2 to 4. Such a silicone prepolymer can control the elasticity in various ways according to the content of the curing agent added during curing, so it is easy to provide the elasticity required by the stamp of the present invention.

The curing agent may be used without particular limitation as long as it is a siloxane-based compound containing a Si-H bond. As a non-limiting example, it may be an aliphatic or aromatic polysiloxane containing a -(RaHSiO)-group. Ra may be an aliphatic group or an aromatic group, the aliphatic group may be a methyl group, an ethyl group, or a propyl group, and the aromatic group may be a phenyl group or a naphthyl group, and the substituent may be substituted with another substituent within the range that does not affect the crosslinking reaction, or Or it may be unsubstituted, but this is only an example and the number of carbon atoms and the type of substituent are not limited. In one non-limiting embodiment, polymethylhydrogensiloxane [(CH ₃ ) ₃ SiO(CH ₃ HSiO)xSi(CH ₃ ) ₃ ], polydimethylsiloxane [(CH ₃ ) ₂ HSiO((CH ₃ ) ₂ SiO )xSi(CH ₃ ) ₂ H], polyphenylhydrogensiloxane [(CH ₃ ) ₃ SiO(PhHSiO)xSi(CH ₃ ) ₃ ] or polydiphenylsiloxane [(CH ₃ ) ₂ HSiO((Ph) ₂ SiO )xSi(CH ₃ ) ₂ H] and the like, at this time, it is preferable to adjust the content of Si-H according to the number of vinyl groups contained in the addition-type silicone-based prepolymer, and for example, x may be 1 or more, and more Preferably, it may be 2 to 10, but is not limited thereto.

The silicone-based prepolymer solution may be applied through spin coating, spray coating, knife coating, or roll coating, but is not limited thereto, and may be applied to the substrate by a conventionally known coating method. It can be applied with a uniform thickness.

And in one aspect of the present invention, after step (S3) and before step (S4), it is possible to remove microbubbles of the silicone-based prepolymer solution applied by forming a vacuum atmosphere after insertion into the vacuum chamber. The silicone-based prepolymer solution from which micro-bubbles are removed has a significantly lower defect rate due to micro-bubbles, and a larger amount of silicone-based prepolymer solution than before vacuum atmosphere can penetrate the upper surface of the hydrophilic micro-pattern, and a more robust mixed layer can be formed. there is. At this time, the vacuum degree of the vacuum chamber may be a vacuum degree of 1×10° torr to 1×10 ^-3 torr, preferably 1×10 ^-1 torr to 1×10 ^-2 torr, and the vacuum degree maintaining time is 5 minutes to 1 time, preferably from 10 minutes to 30 minutes. In the above range, it is possible to remove microbubbles and form a solid mixed layer.

Step (S4) is a step of curing the silicone-based prepolymer solution. Curing of the silicone-based prepolymer solution may be thermosetting or photocuring depending on the type of the silicone-based prepolymer solution. Preferably, it may be thermally cured by using a silicone-based prepolymer solution containing a polydimethylsiloxane-based polymer including a vinyl group. Specifically, it can be cured by keeping it at room temperature, and alternatively, it can be put in an oven to be cured quickly at a temperature higher than room temperature. The curing temperature may be 25°C to 150°C, preferably 50°C to 120°C, and more preferably 80°C to 100°C. In the above range, the silicone-based prepolymer solution can be quickly and uniformly cured. When curing at a temperature higher than the above range, it can be cured more quickly, but the curing time is very fast, so there may be a problem that the silicone-based prepolymer solution does not sufficiently penetrate into the upper surface of the hydrophilic micropattern. On the other hand, when curing at a temperature lower than the above range, the curing time is too long and difficult to apply to the process. In the above temperature range, the curing time may be 1 to 30 minutes, more specifically 5 to 20 minutes, but is not limited thereto, and the time for the silicone-based prepolymer solution to be sufficiently cured in proportion to the applied silicone-based prepolymer solution is all applicable.

In one aspect of the present invention, after step (S4), the step of separating the hydrophilic micro-stamp from the substrate may be further included. For example, when a silicon wafer formed by etching a fine pattern by an electron beam or the like is used as a substrate, the hydrophilic fine stamp may be separated from the substrate by applying a physical force through a conventional separation device using suction force. On the other hand, when a silicon wafer having a pattern formed thereon by a photoresist is used as a substrate, the hydrophilic micro-stamp can be separated from the substrate by removing the photosensitive resin through a remover dedicated to the used photoresist. As such, the separation of the hydrophilic fine stamp from the substrate may be performed by various methods, and the present invention is not limited thereto, and any method for separating the stamp from the master stamp in the conventional imprint lithography process is applicable.

In one aspect of the present invention, after step (S1), before step (S2), it may further include the step of forming a film using a silicone-based prepolymer solution on top of the applied polymerizable solution. In the stamp manufactured by further including such a step, the film made of the silicone-based prepolymer solution is mixed with the polymerizable solution, and a more robust mixed layer is formed, so that it is possible to stably produce a hydrophilic fine stamp with improved reliability. Specifically, before the polymerizable solution is cured, a film may be formed by applying the silicone-based prepolymer solution to the surface of the polymerizable solution applied to the substrate. At this time, a mixed layer may be formed by mixing with each other at the interface of the applied polymerizable solution and the silicone-based prepolymer solution. Thereafter, through steps (S2) to (S4), the polymerizable solution and the silicone-based prepolymer solution are sequentially cured, respectively, and a mixed layer may be formed at the interface between the polymerizable solution and the silicone-based prepolymer solution. In step (S3), the thickness (T2) of the film formed in the step (S1) after step (S1) and before step (S2) may be the same or smaller than the thickness (T1) to which the silicone-based prepolymer solution is applied, preferably T1: T2 may be 1:0.01 to 1:0.5, more specifically 1:0.01 to 1:0.1. In the above range, the mixed layer may be firmly mixed. When the film is coated thicker than the above range, at the interface between the polymerizable solution and the silicone-based prepolymer solution, the silicone-based prepolymer solution penetrates excessively into the polymerizable solution, thereby preventing the polymerizable solution from forming a fine pattern. .

2 shows a method of manufacturing a hydrophilic micropattern through the above-described hydrophilic micro-stamp of the present invention. Hereinafter, a method of manufacturing a hydrophilic micropattern through the hydrophilic micro-stamp will be described with reference to FIG. 2 .

The method for producing a hydrophilic fine pattern of the present invention comprises the steps of (A1) forming a hydrophilic coating layer by applying a hydrophilic solution containing a polyfunctional water-soluble monomer and a photoinitiator to the surface, (A2) pressing the hydrophilic fine stamp on the hydrophilic coating layer and (A3) photocuring the compressed hydrophilic coating layer, and (A4) separating the hydrophilic fine stamp. Such a manufacturing method can simply manufacture a hydrophilic fine pattern through an already hydrophilic stamp, without the need to modify the surface of the stamp to be hydrophilic as in the prior art. In detail, since there is no need to treat the surface of the stamp with a hydroxyl group through plasma treatment as in the prior art, damage to the stamp by the plasma treatment can be prevented. In addition, the process is simple because a fine pattern can be manufactured only by applying, pressing, curing, and separating processes, and the hydrophilic stamp can be used repeatedly, which is advantageous for mass production.

As an example, the present invention may be a hydrophilic micropattern manufactured by the above method, and the hydrophilic micropattern manufactured in this way may be applied to a bio device such as a biochip. The hydrophilic micro-pattern is formed with a pattern corresponding to the pattern of the hydrophilic micro-stamp. Specifically, when an engraved pattern is formed on the hydrophilic micro-stamp, a embossed pattern corresponding to the manufactured micro-pattern may be formed. On the other hand, when an embossed pattern is formed on the hydrophilic micro-stamp, the manufactured micro-pattern may have an engraved pattern corresponding thereto.

In detail, step (A1) of the method for producing a hydrophilic fine pattern is a step of forming a hydrophilic coating layer by applying a hydrophilic solution containing a polyfunctional water-soluble monomer and a photoinitiator to the surface. In this case, the polymerizable coating layer may be formed on the upper surface of a substrate used in conventional imprint lithography, such as a silicon wafer or a polymethyl methacrylate (PMMA) substrate on which a pattern is not formed on the surface.

In step (A1) of the method for producing a hydrophilic fine pattern, the hydrophilic solution contains a polyfunctional water-soluble monomer and a photoinitiator, and can be cured when irradiated with ultraviolet light by the photoinitiator. The hydrophilic solution is applied to the substrate in a uniform thickness by conventionally known coating methods such as spin-coating, spray-coating, knife-coating, roll-coating, etc. layer can be formed. The hydrophilic coating layer preferably has a thickness equal to or greater than the thickness of the hydrophilic fine pattern formed on the hydrophilic stamp. When the thickness of the hydrophilic coating layer is smaller than the above range, it is difficult to properly transfer the fine pattern.

In one embodiment, the hydrophilic solution may contain a polyfunctional water-soluble monomer to exhibit hydrophilicity after curing. The polyfunctional water-soluble monomer may preferably be a polyethylene glycol-based polyfunctional monomer. The hydrophilic solution containing such a polyethylene glycol-based polyfunctional monomer may exhibit biocompatibility as well as hydrophilicity after curing. Accordingly, after the hydrophilic solution is cured, it may be used as a bio device such as a biochip, a DNA chip, or a protein chip.

Alternatively, the hydrophilic solution may further include a monofunctional monomer. When the hydrophilic solution further comprising a monofunctional monomer is applied to a substrate on which a fine pattern is formed, it has high fluidity and can be uniformly applied. Accordingly, a hydrophilic micropattern to which a nano-sized pattern is more precisely transferred can be manufactured. The monofunctional monomer may be an acrylate-based monomer, and specifically, ethylene glycol dimethacrylate, 2-hydroxyyethyl methacylate, and ethylene glycol dimethylacrylate ), 2-hydroxyethyl acrylate, methyl methacrylate, methacrylic acid, ethyl methacrylate, and thyl Acrylate can be The viscosity of the hydrophilic solution can be controlled by adjusting the content of the monofunctional monomer as described above in the hydrophilic solution.

The photoinitiator has a characteristic that radicals are generated by light irradiation, and in particular, 320 nm to 380 nm in the ultraviolet wavelength region, for example 330 nm to 375 nm, specifically, radicals upon irradiation with light of 340 nm to 370 nm This can happen. When the light in the ultraviolet wavelength range is irradiated, a photocuring reaction in the hydrophilic solution may be started. For example, the photoinitiator is anthraquinone, anthraquinone-2-sulfonic acid sodium salt monohydrate (anthraquinone-2-sulfonicacid, sodium salt monohydrate), (benzene) tricarbonylchromium [(benzene) tricarbonylchromium], benzyl ( benzil), benzoin ethyl ether, benzoin isobutyl ether, benzoin methyl ether, benzophenone, 4-benzoylbiphenyl , 4,4'-bis(diethylamino)benzophenone [4,4'-bis(diethylamino)benzophenone], 4,4'-bis(dimethylamino)benzophenone [4,4'-bis(dimethylamino)benzophenone ], dibenzosuberenone, 2,2-dimethoxy-2-phenylacetophenone (2,2-dimethoxy-2-phenylacetophenone), 3,4-dimethylbenzophenone (3,4-dimethylbenzophenone), 3 '-Hydroxyacetophenone (3'-hydroxyacetophenone), 2-hydroxy-2-methyl propiophenone (2-hydroxy-2-methyl propiophenone), 2-hydroxy-4'-(2-hydroxyethoxy )-2-methyl propiophenone [2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone], 1-hydroxycyclohexyphenyl ketone, methylbenzoyl formate ), diphenyl (2,4,6-trimethylbenzoyl)-phosphine oxide [diphenyl (2,4,6-trimethylbenzoyl)-phosphine oxide], phosphine oxide phenyl bis (2,4,6-trimethyl benzoyl) [ phosphine oxidephenyl bis (2,4,6-tri methyl benzoyl)], 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone {2-methyl-1-[4-(methylthio)phenyl] -2-(4-morpholinyl)-1-propanone}, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone {2-benzyl-2 -(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone}, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl- Phenyl)-butan-1-one] [2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one], bis(5-2 ,4-Cyclopentadien-1-yl)-bis(2,6-difluoro-3(1h-pyrrol-1yl)-phenyl)titanium [bis(.eta.5-2,4-cyclopentadien-1) -yl)-bis(2,6-difluoro-3(1h-pyrrol-1-yl)-

phenyl) titanium], 2-isopropyl thioxanthone, 2-ethylanthraquinone, 2,4-diethyl thioxanthone, benzyl dimethyl Ketal (benzil dimethylketal), benzophenone (benzophenone), 4-chloro benzophenone (4-chloro benzophenone), methyl-2-benzoyl benzoate (methyl-2-benzoylbenzoate), 4-phenyl benzophenone (4-phenyl benzophenone) , 2,2'-bis (2-chlorophenyl) -4,4'-5,5'-tetraphenyl-1,2'-bi-imidazole [2,2'-bis (2-chlorophenyl) -4 ,4',5,5'-tetraphenyl-1,2'-bi-imidazole], 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4' ,5'-diphenyl-1,1'-biimidazole [2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxypenly)-4',5'-diphenyl-1, 1'-biimidazole], 4-phenoxy-2',2'-dichloroacetophenone (4-phenoxy-2',2'-dichloro acetophenone), ethyl-4-(dimethylamino)benzoate [ethyl-4- (dimethylamino)benzoate], isoamyl 4-(dimethylamino)benzoate [isoamyl 4-(dimethylamino)benzoate], 2-ethyl hexyl-4-(dimethylamino)benzoate [2-ethyl hexyl-4-(dimethylamino) benzoate], 4,4'-bis(diethylamino)benzophenone [4,4'-bis(diethylamino)benzophenone],4-(4'-methylphenylthio)-benzophenone [4-(4'-methylphenylthio) -benzophenone],1,7-bis(9-acridinyl)heptane [1,7-bis(9-acridinyl)heptane], n-phenylglycine and 2-hydroxy-2 -Methylpropiophenone (2-hydroxy-2-methylpropiophenone) may be one or two or more selected from the group consisting of, but is not limited thereto, and all conventional photoinitiators that can be photocured by mixing with a polyfunctional water-soluble monomer are applicable Do.

The hydrophilic solution of the present invention may contain 0.01 to 20 parts by weight of a photoinitiator, preferably 0.05 to 10 parts by weight, more preferably 1 to 5 parts by weight based on 100 parts by weight of the polyfunctional water-soluble monomer. In the above range, the photoinitiator may be mixed with the polyfunctional water-soluble monomer and cured, and the viscosity of the liquid polyfunctional water-soluble monomer does not significantly change.

Step (A2) of the method for producing a hydrophilic fine pattern is a step of pressing the hydrophilic fine stamp of the present invention on the hydrophilic coating layer. In this case, the compression may be performed through a pressing device used in a conventional imprint lithography process. During compression, the upper surface of the hydrophilic coating layer and the lower surface of the hydrophilic fine pattern of the hydrophilic stamp of the present invention are in contact.

Step (A3) of the method for producing a hydrophilic fine pattern is a step of photocuring the pressed hydrophilic coating layer. The hydrophilic solution can be cured when irradiated with ultraviolet light by a photoinitiator. The irradiated ultraviolet wavelength region may be 320 nm to 380 nm, preferably 330 nm to 375 nm, and more preferably 340 nm to 370 nm. In the above range, curing of the photoinitiator may occur to cure the polymerizable solution. In the case of photocuring, the light irradiation time may be 1 second to 30 minutes, preferably 30 seconds to 15 minutes, more preferably 1 minute to 10 minutes, but is not limited thereto, and the time sufficient to harden the hydrophilic coating layer is not limited thereto. can be applied. At this time, the hydrophilic coating layer is cured and a pattern corresponding to the stamp is formed. For example, when the engraved pattern is formed on the stamp, an embossed hydrophilic pattern is formed, whereas when the embossed pattern is formed on the stamp, an engraved hydrophilic fine pattern is formed.

Step (A4) of the manufacturing method of the hydrophilic fine pattern is a step of separating the hydrophilic fine stamp. For example, the hydrophilic micro-stamp and the hydrophilic micro-pattern may be separated by applying a physical force through a conventional separation device using suction force. The present invention is not limited thereto, and all conventional methods for separating a fine pattern from a stamp in an imprint lithography process are applicable.

Hereinafter, the present invention will be described in detail by way of Examples, but these are for describing the present invention in more detail, and the scope of the present invention is not limited by the Examples below.

<Production of hydrophilic micro-stamp>

After preparing a 4-inch silicon wafer with a line pattern having a line width of 300 nm, an interval of 300 nm, and a height of 300 nm, 100 weight of polyethyleneglycol diacrylate (PEGDA, Sigma-Aldrich) having an average molecular weight of 575 on the upper surface of the silicon wafer Spin coating (10 ml, 500 rpm, 30 s) of a polymerizable solution containing 3 parts by weight of a 2-hydroxy-2-methylpropiophenone (HMPPP, Sigma-Aldrich) solution with respect to parts applied through. Thereafter, the polymerizable solution was cured by irradiating 350 nm ultraviolet light for 3 minutes to form a hydrophilic micropattern of the stamp, and then liquid polydimethylsiloxane (PDMS, Sylgard 184 elastomer, Dow) 100 was placed on the upper surface of the hydrophilic micropattern. A silicone-based prepolymer solution in which 10 parts by weight of a curing agent was mixed with respect to parts by weight was applied through spin coating (50 ml, 100 rpm, 1 min), and then cured at 90° C. for 15 minutes to form an elastic substrate. The silicone-based prepolymer solution was applied so that the ratio (d1:d2) of the thickness (d1) of the prepared hydrophilic micropattern to the thickness (d2) of the elastic substrate was 1:20.

Thereafter, after separating the hydrophilic micro-stamp from the silicon wafer, the hydrophilic micro-pattern of the hydrophilic micro-stamp was observed with a scanning electron microscope.

After preparing a 4-inch silicon wafer on which a line pattern having a line width of 300 nm, an interval of 300 nm, and a height of 300 nm was formed, polyethyleneglycol dimethacrylate (PEGDMA, Sigma-Aldrich) having an average molecular weight of 575 on the upper surface of the silicon wafer was prepared. A polymerizable solution containing 3 parts by weight of a 2-hydroxy-2-methylpropiophenone (HMPPP, Sigma-Aldrich) solution based on 100 parts by weight was spin-coated (10 ml, 500 rpm, 30 s). ) was applied through the Thereafter, the polymerizable solution was cured by irradiating 350 nm ultraviolet light for 3 minutes to form a hydrophilic micropattern of the stamp, and then liquid polydimethylsiloxane (PDMS, Sylgard 184 elastomer, Dow) 100 was placed on the upper surface of the hydrophilic micropattern. A silicone-based prepolymer solution in which 10 parts by weight of a curing agent was mixed with respect to parts by weight was applied through spin coating (50 ml, 100 rpm, 1 min), and then cured at 90° C. for 15 minutes. Thereafter, after separating the hydrophilic micro-stamp from the silicon wafer, the hydrophilic micro-pattern of the hydrophilic micro-stamp was observed with a scanning electron microscope.

<Production of hydrophilic micro-patterns through hydrophilic micro-stamps>

A hydrophilic micropattern was prepared through the stamp prepared in Example 1.

After preparing a 4 inch silicon wafer, 2-hydroxy-2-methylpropiophenone (2-hydroxy-2-methylpropiophenone) with respect to 100 parts by weight of polyethylene glycol diacrylate (PEGDA, Sigma-Aldrich) on the upper surface of the silicon wafer A hydrophilic solution containing 3 parts by weight of HMPPP, Sigma-Aldrich) and 150 parts by weight of distilled water was applied through spin coating (10 ml, 500 rpm, 30 s). Thereafter, after pressing the stamp prepared in Example 1, the hydrophilic solution was cured by irradiating 350 nm ultraviolet rays for 3 minutes. Thereafter, the hydrophilic micropattern in which the hydrophilic solution was cured was separated from the stamp.

The separated hydrophilic micropatterns were observed with a scanning electron microscope.

In the method of Example 3, 2-hydroxyethyl methacrylate (2-Hydroxyethyl Methacrylate; HEMA, Sigma-Aldrich) instead of 150 parts by weight of distilled water based on 100 parts by weight of polyethyleneglycol diacrylate (PEGDA) as a hydrophilic solution ) was carried out in the same manner as in Example 3, except that 10 parts by weight of the solution was mixed.

In the method of Example 3, instead of 150 parts by weight of distilled water based on 100 parts by weight of polyethyleneglycol diacrylate (PEGDA) as a hydrophilic solution, an ethylene glycol dimethacrylate (HGDMA, Sigma-Aldrich) solution Except for mixing 10 parts by weight, it was carried out in the same manner as in Example 3.

In the method of Example 3, 2-hydroxyethyl acrylate (2-Hydroxyethyl acrylate; HEA, Sigma-Aldrich) instead of 150 parts by weight of distilled water based on 100 parts by weight of polyethyleneglycol diacrylate (PEGDA) as a hydrophilic solution Except that 100 parts by weight of the solution was mixed, it was carried out in the same manner as in Example 3.

In the method of Example 3, 900 parts by weight of a methylmethacrylate (MMA, Sigma-Aldrich) solution instead of 150 parts by weight of distilled water with respect to 100 parts by weight of polyethyleneglycol diacrylate (PEGDA) as a hydrophilic solution was mixed. Except that, it was carried out in the same manner as in Example 3.

In the method of Example 3, 100 parts by weight of a methacrylic acid (MAA, Sigma-Aldrich) solution is mixed instead of 150 parts by weight of distilled water with respect to 100 parts by weight of polyethyleneglycol diacrylate (PEGDA) as a hydrophilic solution Except for the above, it was carried out in the same manner as in Example 3.

In the method of Example 3, 100 parts by weight of an ethyl methacrylate (EMA, Sigma-Aldrich) solution instead of 150 parts by weight of distilled water with respect to 100 parts by weight of polyethyleneglycol diacrylate (PEGDA) as a hydrophilic solution was mixed Except that, it was carried out in the same manner as in Example 3.

In the method of Example 3, 100 parts by weight of an ethyl acrylate (EA, Sigma-Aldrich) solution instead of 150 parts by weight of distilled water with respect to 100 parts by weight of polyethyleneglycol diacrylate (PEGDA) as a hydrophilic solution was mixed. Except that, it was carried out in the same manner as in Example 3.

A hydrophilic micropattern was prepared through the stamp prepared in Example 2.

After preparing a 4 inch silicon wafer, 2-hydroxy-2-methylpropiophenone (HMPPP, Sigma-Aldrich) with respect to 100 parts by weight of polyethylene glycol dimethacrylate (PEGDMA, Sigma-Aldrich) on the upper surface of the silicon wafer ) 3 parts by weight and a hydrophilic solution containing 100 parts by weight of distilled water was applied through spin coating (10 ml, 500 rpm, 30 s). Thereafter, after pressing the stamp prepared in Example 2, the hydrophilic solution was cured by irradiating 350 nm UV light for 3 minutes. Thereafter, the hydrophilic micropattern in which the hydrophilic solution was cured was separated from the stamp.

The separated hydrophilic micropatterns were observed with a scanning electron microscope.

In the method of Example 11, instead of 150 parts by weight of distilled water based on 100 parts by weight of polyethyleneglycol dimethacrylate (PEGDMA, Sigma-Aldrich) as a hydrophilic solution, a methylmethacrylate (Methylmethacrylate; MMA, Sigma-Aldrich) solution Except for mixing 100 parts by weight, it was carried out in the same manner as in Example 11.

In the method of Example 11, instead of 150 parts by weight of distilled water with respect to 100 parts by weight of polyethyleneglycol dimethacrylate (PEGDMA) as a hydrophilic solution, 10 parts by weight of a methacrylic acid (MAA) solution was mixed except that and carried out in the same manner as in Example 11.

In the method of Example 11, 100 parts by weight of an ethyl methacrylate (EMA, Sigma-Aldrich) solution instead of 150 parts by weight of distilled water with respect to 100 parts by weight of polyethyleneglycol dimethacrylate (PEGDMA) as a hydrophilic solution Except for mixing, it was carried out in the same manner as in Example 11.

In the method of Example 11, 100 parts by weight of an ethyl acrylate (EA, Sigma-Aldrich) solution instead of 150 parts by weight of distilled water with respect to 100 parts by weight of polyethyleneglycol dimethacrylate (PEGDMA) as a hydrophilic solution is mixed Except for the above, it was carried out in the same manner as in Example 11.

After preparing a 4-inch silicon wafer on which a hole pattern having a diameter of 200 nm, an interval of 400 nm, and a depth of 250 nm is formed, 2-hydroxyl based on 100 parts by weight of polyethyleneglycol diacrylate (PEGDA) on the upper surface of the silicon wafer A polymerizable solution containing 3 parts by weight of -2-methylpropiophenone (2-hydroxy-2-methylpropiophenone; HMPPP, Sigma-Aldrich) was applied through spin coating (10 ml, 500 rpm, 30 s). Thereafter, the polymerizable solution is cured by irradiating 350 nm ultraviolet light for 3 minutes to form a hydrophilic micropattern of the stamp, and then a curing agent 10 for 100 parts by weight of liquid polydimethylsiloxane (PDMS) on the upper surface of the hydrophilic micropattern. A silicone-based prepolymer solution mixed with parts by weight was applied through spin coating (50 ml, 100 rpm, 1 min), and then cured at 90° C. for 15 minutes. Thereafter, the hydrophilic micro-stamp was separated from the silicon wafer.

After that, 2-hydroxy-2-methylpropiophenone (2-hydroxy-2-methylpropiophenone, HMPPP) with respect to 100 parts by weight of polyethylene glycol diacrylate (PEGDA) on a genuine 4-inch silicon wafer without a pattern formed ) 3 parts by weight of a hydrophilic solution was applied through spin coating (10 ml, 500 rpm, 30 s). Thereafter, the polymerizable solution was transferred to the hydrophilic micro-stamp by contacting the hydrophilic micro-stamp on the upper surface of the hydrophilic solution. Thereafter, the hydrophilic micro-stamp was brought into contact with the polymethyl methacrylate (PMMA) substrate, and then the hydrophilic solution was cured by irradiating 350 nm UV light for 3 minutes. Thereafter, the hydrophilic micropattern in which the hydrophilic solution was cured was separated from the stamp.

The separated hydrophilic micropatterns were observed with a scanning electron microscope.

3 is a scanning electron microscope photograph of the hydrophilic micro-stamps prepared in Examples 1 to 2; Referring to FIG. 3 , in Examples 1 to 2, it was confirmed that a linear pattern having a width of about 300 nm was clearly formed.

4 to 16 are scanning electron micrographs of the hydrophilic micropatterns prepared in Examples 3 to 15 of the present invention. 4 to 16 , it was confirmed that, in all of Examples 3 to 15 of the present invention, a linear pattern having a width of about 300 nm was clearly formed. That is, it was confirmed that the hydrophilic micro-stamp of the present invention can not only precisely transfer nano-sized patterns, but also form nano-sized precise patterns on the hydrophilic resin.

17 is a photograph of the hydrophilic micropattern prepared in Example 16 of the present invention, and a scanning electron microscope photograph thereof. Referring to FIG. 17 , it could be confirmed that a non-linear, hole-shaped pattern could also be accurately transferred.

After preparing a 4-inch silicon wafer on which a line pattern having a line width of 300 nm, an interval of 300 nm, and a height of 300 nm is formed, on the upper surface of the silicon wafer, 2-hydroxy- A polymerizable solution containing 3 parts by weight of a 2-methylpropiophenone (2-hydroxy-2-methylpropiophenone, HMPPP) solution was applied through spin coating (10 ml, 500 rpm, 30 s). Thereafter, a silicone-based prepolymer solution in which 10 parts by weight of a curing agent is mixed with 100 parts by weight of liquid polydimethylsiloxane (PDMS) is applied to the upper surface of the applied polymerizable solution through spin coating (5 ml, 100 rpm, 1 min). did Then, the polymerizable solution is cured by irradiating 350 nm UV light for 3 minutes to form a hydrophilic micropattern of the stamp, and then a curing agent is applied to 100 parts by weight of a liquid polydimethylsiloxane (PDMS) polymer on the upper surface of the hydrophilic micropattern. A silicone-based prepolymer solution mixed with 10 parts by weight was applied through spin coating (50 ml, 100 rpm, 1 min), and then cured at 90° C. for 15 minutes to form an elastic substrate. The ratio (d1:d2) of the thickness (d1) of the prepared hydrophilic micropattern to the thickness (d2) of the elastic substrate was 1:20.

Thereafter, after separating the hydrophilic micro-stamp from the silicon wafer, a hydrophilic micro-pattern was prepared as follows.

After preparing a 4 inch silicon wafer, 2-hydroxy-2-methylpropiophenone (2-hydroxy-2-methylpropiophenone, HMPPP) 3 with respect to 100 parts by weight of polyethylene glycol diacrylate (PEGDA) on the upper surface of the silicon wafer A hydrophilic solution containing parts by weight was applied via spin coating (10 ml, 500 rpm, 30 s). Thereafter, after pressing the prepared stamp, the hydrophilic solution was cured by irradiating 350 nm ultraviolet rays for 3 minutes. Thereafter, the hydrophilic micropattern in which the hydrophilic solution was cured was separated from the stamp.

Through the same hydrophilic micro-stamp, the hydrophilic micro-pattern manufacturing method was repeated 10 times to prepare 10 hydrophilic micro-patterns. Reliability was determined by observing each surface of the prepared hydrophilic micropatterns. As a result of the observation, it was confirmed with the naked eye that precise patterns were formed in all ten hydrophilic micropatterns repeatedly manufactured through one hydrophilic micro-stamp. That is, it was confirmed that the hydrophilic micro-stamp of the present invention can repeatedly form a reliable hydrophilic micro-pattern.

As described above, the present invention has been described with specific details and limited examples and drawings, but these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention is not limited to the above embodiments. Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims described below, but also all of the claims and all equivalents or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (18)

delete delete delete delete delete delete delete delete (S1) applying a polymerizable solution containing a polyfunctional water-soluble monomer and a photoinitiator to a substrate including a pattern on the surface;
(S2) photocuring the applied polymerizable solution to form a hydrophilic fine pattern;
(S3) applying a silicone-based prepolymer solution to the opposite surface of one surface of the hydrophilic micro-pattern in contact with the substrate;
(S4) curing the silicone-based prepolymer solution;
A method for producing a hydrophilic fine stamp comprising a. 10. The method of claim 9,
In the step (S4), the silicone-based prepolymer solution is thermosetting, the method for producing a hydrophilic fine stamp. 11. The method of claim 10,
The thermosetting is carried out for 10 minutes to 48 hours at a temperature range of 25 ℃ to 150 ℃, a method for producing a hydrophilic fine stamp. 10. The method of claim 9,
The silicone-based prepolymer solution comprises a polydimethylsiloxane-based prepolymer including a vinyl group, a method for producing a hydrophilic fine stamp. 10. The method of claim 9,
After the step (S4), the method of manufacturing a hydrophilic micro-stamp further comprising the step of separating the hydrophilic micro-stamp from the substrate. 10. The method of claim 9,
After step (S1), before step (S2),
Forming a film with a silicone-based prepolymer solution on the applied polymeric solution; Method for producing a hydrophilic fine stamp further comprising a. delete delete delete delete

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