KR101357087B1 - Method for Manufacturing 3-dimensional Nanostructures by Imprint Lithography and 3-dimensional Nanostructures thereby - Google Patents

Abstract

The present invention relates to a method for manufacturing a three-dimensional nanostructure using imprint lithography and a three-dimensional nanostructure produced by the present invention, the method for manufacturing a three-dimensional nanostructure of the present invention is an imprint resin layer or photosensitive metal-organic on the substrate or thin film Forming a precursor layer, pressing the imprint resin layer or the photosensitive metal-organic precursor layer with a first imprint stamp having a first pattern formed thereon, and any one of heating or light irradiation methods or a combination thereof Forming a primary resin pattern layer or a primary metal oxide thin film pattern layer by a method; and forming the primary resin pattern layer or primary metal oxide thin film pattern layer with a second pattern different from the first imprint stamp. Pressurized with a heterogeneous second imprint stamp, and any of heating or light irradiation methods or a method in which these are mixed Forming a resin pattern layer or metal oxide thin film pattern layer having heterogeneous line widths and pattern shapes, including forming a secondary resin pattern layer or a secondary metal oxide thin film pattern layer with a plurality of imprint stamps, Various types of three-dimensional patterns can be formed, thereby making it easy to manufacture various three-dimensional nanostructures such as nano dots, nanotubes, nano-cones, etc. at low cost and large area.

Description

Method for manufacturing 3-dimensional nanostructures by using imprint lithography and manufactured by 3D nanostructures {Method for Manufacturing 3-dimensional Nanostructures by Imprint Lithography and 3-dimensional Nanostructures}

The present invention relates to a method for manufacturing a three-dimensional nanostructure using imprint lithography and to a three-dimensional nanostructure manufactured by the present invention. More specifically, a plurality of imprint stamps can be used to form various types of three-dimensional patterns, thereby making it inexpensive and expensive. The present invention relates to a three-dimensional nanostructure manufacturing method using imprint lithography that facilitates the production of various three-dimensional nanostructures, such as nano dots, nanotubes, nanocones, and the like, and to three-dimensional nanostructures produced thereby.

Nano Technology (NT) is a convergence of various scientific and technological fields such as physics, chemistry, biology, electronics, and materials engineering, overcoming the limitations of existing technologies, and inducing technological innovation in various industries. It is expected to dramatically improve the quality of life, and is attracting attention as a new paradigm technology that will lead industrial development in the 21st century along with Information Technology (IT) and Biotechnology (BT).

In addition, nanotechnology can be divided into a top-down approach and a bottom-up approach according to the approach.

A representative example of the approach from top to bottom is the optical lithography technique used in existing semiconductor device manufacturing processes.

However, optical lithography has a disadvantage in that it is difficult to fabricate a pitch of 100 nm or less due to the limitation of the line width of the laser, and thus, there have been many attempts to develop a process using nanoimprint technology.

Nanoimprint technology solves the low productivity problem of electron beam lithography by fabricating a stamp with a nanoscale pattern using electron beam lithography or other methods, imprinting the stamp on the polymer thin film to transfer the nanostructures, and using them repeatedly. do.

However, in the case of the nanoimprint process, there is a problem in that a residual layer remains between the pattern and the substrate fabricated after imprinting.

The residual layer is a layer in which the polymer layer does not penetrate between the empty spaces of the stamp, and the residual layer must be removed to obtain a pattern of a desired shape.

Accordingly, a subsequent process such as plasma etching is performed to remove the residual layer. As a prior art for easily removing the residual layer, Patent No. 10-0881233 removes the residual layer formed due to the uneven portion of the stamp between the patterns. To this end, after the stamp is separated from the polymer layer, an imprint lithography method comprising the step of etching to remove the residual layer on which the uneven portion is formed.

However, since the etching process is necessary after the imprint process in the related art, the process is complicated because the nanolithography and etching processes have to be repeated twice to form a nanostructure having a three-dimensional structure. .

In addition, there is a problem that the pattern is excessively etched during the etching process to reduce the height of the pattern, in order to prevent this, when the polymer layer is thinly applied, the polymer layer does not penetrate properly between the patterns of the stamp so that the proper height of the pattern There is a problem that can not be secured.

Therefore, a technique for simplifying the process has been required by omitting the etching process to solve the above-mentioned problems.

SUMMARY OF THE INVENTION The present invention has been made to meet the above requirements, and an object thereof is to provide a method for manufacturing a three-dimensional nanostructure using imprint lithography, which may simplify the process by omitting an etching process during an imprint process.

In addition, a method of manufacturing a three-dimensional nanostructure that can easily form a three-dimensional nanostructure by proceeding the imprint process in a multi-step by irradiating ultraviolet rays before and after the full curing dose value for the pattern formation of the imprint resin or photosensitive metal-organic precursor. The purpose is to provide.

In addition, a three-dimensional polymer nanostructure or a metal oxide nanostructure, such as a micro and nano hybrid pattern or a nano hybrid pattern or a micro hybrid pattern, may be formed by performing an imprint process in two steps using two or more stamps. The purpose is to provide a method for producing a nanostructure.

Another object of the present invention is to provide a three-dimensional nanostructure capable of forming a mixed three-dimensional pattern of various shapes such as nano-sized spheres, dots, tubes, cones, hemispheres, polygonal pyramids, and polygonal pillars using a plurality of imprint stamps.

In order to achieve the above object, in the present invention, forming an imprint resin layer or photosensitive metal-organic precursor layer on the substrate or the thin film, and the first pattern of the imprint resin layer or the photosensitive metal-organic precursor layer Pressing the formed first imprint stamp and forming a primary resin pattern layer or a primary metal oxide thin film pattern layer by any one of heating or light irradiation methods or a mixed method thereof; The primary resin pattern layer or the primary metal oxide thin film pattern layer is pressed with a heterogeneous second imprint stamp having a second pattern different from the first imprint stamp, and any of heating or light irradiation methods or a method in which these are mixed Forming a secondary resin pattern layer or a secondary metal oxide thin film pattern layer with a different line width and pattern form; Provided is a method of manufacturing a three-dimensional nanostructure, wherein the resin pattern layer or the metal oxide thin film pattern layer is formed.

In the present invention, the n-th resin pattern layer or the n-th metal oxide thin film pattern layer is pressed with an n + 1 imprint stamp having an n + 1 pattern different from the n-th imprint stamp, and during heating or light irradiation The method may further include forming an n + primary resin pattern layer or an n + primary metal oxide thin film pattern layer by using any one or a mixed method thereof.

Here, n is an integer of 2 or more.

In addition, the forming of the n + primary resin pattern layer or the n + primary metal oxide thin film pattern layer may be performed repeatedly.

In the present invention, the first pattern, the second pattern and the n + 1 pattern, at least one of the line width, spacing and depth is the same or different, it may be made of embossed or intaglio.

The first pattern, the second pattern, and the n + 1 pattern may be formed of any one selected from a micro pattern or a nano pattern, and the resin pattern layer or the metal oxide thin film pattern layer having the heterogeneous line width and pattern shape may be formed of micro and Nano hybrid pattern or nano hybrid pattern or micro hybrid pattern can be formed.

In the present invention, the step of forming the primary resin pattern layer or the primary metal oxide thin film pattern layer at the boundary point of the complete curing dose value for the pattern formation of the imprint resin layer or the photosensitive metal-organic precursor layer In the step of irradiating less than the complete curing dose value, and forming the secondary resin pattern layer or the secondary metal oxide thin film pattern layer may be irradiated more than the complete curing dose value.

In addition, the primary, secondary resin pattern layer or the primary, secondary metal oxide thin film pattern layer to form a boundary point of the complete curing dose value for the pattern formation of the imprint resin layer or the photosensitive metal-organic precursor layer In the step of irradiating less than the fully cured dose value, and in the step of forming the n + primary resin pattern layer or the n + primary metal oxide thin film pattern layer may be irradiated more than the full curing dose value.

Here, the substrate is an inorganic material including any one or more of silicon (Si), gallium arsenide (GaAs), gallium phosphide (GaP), gallium arsenide (GaAsP), SiC, GaN, ZnO, MgO, sapphire, quartz, glass Substrate or a polymer substrate comprising any one or more of polycarbonate, polyethylene naphthalate, polynorbornene, polyacrylate, polyvinyl alcohol, polyimide, polyethylene terephthalate, polyethersulfone.

In addition, the photosensitive metal-organic precursor layer is lithium (Li), beryllium (Be), boron (B), sodium (Na), magnesium (Mg), aluminum (Al), silicon (Si), indium (In) , Sulfur (S), potassium (K), calcium (Ca), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co) , Nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), rubidium (Rb), strontium (Sr), yttrium (Y ), Zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), indium (In), tin (Sn), tellurium (Te), antimony (Sb), barium At least one metal element selected from the group consisting of (Ba), hafnium (Hf), tantalum (Ta), tungsten (W), iridium (Ir), lead (Pb), bismuth (Bi), and polonium (Po) It may include.

The photosensitive metal-organic precursor layer is ethyl hexanoate, acetylacetonate, Acetylacetonate, Dialkyldithiocarbamates, Carboxylic acids, Carboxylates, Pyridine (Pyridine), Diamines, Arsines, Diarsines, Phosphines, Diphosphines, Butoxide, Isopropoxide, Ethoxide Ethoxide, Chloride, Acetate, Carbonyl, Carbonate, Hydroxide, Arenas, Beta-Diketonate, 2-nitrobenzaldehyde (2-Nitrobenzaldehyde), acetate dihydrate (Acetate Dihydrate) may be composed of any one or more of the organic ligand.

In the present invention, the photosensitive metal-organic precursor layer is hexane, 4-methyl-2-pentanone, ketone, methyl isobutyl ketone, methyl ethyl ketone, water, methanol, ethanol Propanol, isopropanol, butanol, pentanol, hexanol, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N-methylpyrrolidone, acetone, acetonitrile, tetrahydrofuran (Tetrahydrofuran: THF), tecan, nonane, octane, heptane, pentane, 2-methoxyethanol (E-Methoxyethanol) can be produced using at least one solvent selected from the group consisting of.

The first imprint stamp or the second imprint stamp may be made of any one of silicon (Si), silicon oxide (SiO ₂ ), quartz (Quartz), nickel (Ni), copper (Cu), polydimethylsiloxane (PDMS), Polymer stamps including any one or more of Polyurethane acrylate (PUA), Ethylene Tetrafluoroethylene (ETFE), Perfluoroalkyl acrylate (PFA), Perfluoropolyether (PFPE), and Polytetrafluoroethylene (PTFE) may be used.

When pressurized with the first imprint stamp or the second imprint stamp and irradiated with light, any one of ultraviolet rays, microwaves, X-rays, and gamma rays may be applied to the imprint resin layer or the like. Irradiating to the photosensitive metal-organic precursor layer, the irradiation time is characterized in that the irradiation time is 1 second to 5 hours.

When pressurized and heated with the first imprint stamp or the second imprint stamp, the heating temperature is in the range of 30 to 300 ° C., and the imprint resin layer for 1 second to 5 hours. Or the photosensitive metal-organic precursor layer may be heated.

In addition, in order to achieve the above object, the present invention provides a three-dimensional nanostructure in which a three-dimensional pattern of various forms is formed.

The pattern in the present invention may be made of any one or a mixture of spheres, points, tubes, cones, hemispheres, polygonal pyramids, polygonal cylinders and cylinders.

As described above, according to the present invention, the etching process may be omitted in the imprint process, thereby simplifying the process.

In addition, to form the imprint resin or the photosensitive metal-organic precursor by irradiating ultraviolet rays before and after the fully cured dose value in two steps (imprint process), the effect of being able to facilitate the formation of three-dimensional nanostructures There is.

In addition, by performing an imprint process in two steps using heterogeneous stamps, there is an effect that can form a three-dimensional polymer nanostructure or metal oxide nanostructures micro / nano hybrid.

In addition, various patterns such as nano-sized spheres, dots, tubes, cones, hemispheres, polygonal pyramids, and polygonal pillars may be formed by varying the pattern line width, spacing, and depth of a plurality of imprint stamps, or by using different patterns of embossed and engraved patterns. It is easy to form a three-dimensional nanostructure capable of forming a mixed three-dimensional pattern.

1A to 1F are perspective views showing step-by-step methods of manufacturing a three-dimensional nanostructure of the present invention.
2 is a SEM photograph of a three-dimensional nanostructure prepared according to an embodiment of the present invention.
3 is a graph showing ultraviolet sensitivity analysis of ZnO resins analyzed according to an embodiment of the present invention.
4 is a SEM photograph of a ZnO micro / nano-hybrid nanostructure formed in accordance with an embodiment of the present invention.
5 is an AFM photograph of a ZnO micro / nano-hybrid nanostructure formed in accordance with an embodiment of the present invention.
FIG. 6 is a graph illustrating nanostructure length analysis in FIG. 5.

Hereinafter, with reference to the accompanying drawings will be described in more detail an embodiment of a method for producing a three-dimensional nanostructure using the imprint lithography of the present invention and the three-dimensional nanostructure manufactured thereby.

1A to 1F are perspective views showing step-by-step methods of manufacturing a three-dimensional nanostructure of the present invention.

First, the method for manufacturing a three-dimensional nanostructure according to the present invention begins with forming an imprint resin layer 20 or a photosensitive metal-organic precursor layer on top of a substrate 10 or a thin film, as shown in FIG. 1A.

In an embodiment of the present invention to be described below, the imprint resin layer 20 is formed on the substrate 10.

However, the present invention is not limited thereto, and the thin film may be applied instead of the substrate 10 to manufacture the three-dimensional nanostructure of the present invention, and instead of the imprint resin layer 20, the substrate 10 or Forming a photosensitive metal-organic precursor layer on a thin film is, of course, included in the technical details of the present invention.

The substrate 10 used in this process may be any one of silicon (Si), gallium arsenide (GaAs), gallium phosphide (GaP), gallium arsenide (GaAsP), SiC, GaN, ZnO, MgO, sapphire, quartz, and glass. An inorganic substrate including one or more may be applied.

In addition, the substrate 10 may be made of a polymer substrate including any one or more of polycarbonate, polyethylene naphthalate, polynorbornene, polyacrylate, polyvinyl alcohol, polyimide, polyethylene terephthalate, polyethersulfone. .

In addition, in the present invention, the photosensitive metal-organic precursor layer formed on the substrate 10 or the thin film may include lithium (Li), beryllium (Be), boron (B), sodium (Na), magnesium (Mg), Aluminum (Al), Silicon (Si), Indium (In), Sulfur (S), Potassium (K), Calcium (Ca), Scandium (Sc), Titanium (Ti), Vanadium (V), Chromium (Cr), Manganese (Mn), Iron (Fe), Cobalt (Co), Nickel (Ni), Copper (Cu), Zinc (Zn), Gallium (Ga), Germanium (Ge), Arsenic (As), Selenium (Se) , Rubidium (Rb), strontium (Sr), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), indium (In), tin (Sn) ), Tellurium (Te), antimony (Sb), barium (Ba), hafnium (Hf), tantalum (Ta), tungsten (W), iridium (Ir), lead (Pb), bismuth (Bi), polonium ( Po) may include any one or more metal elements selected from the group consisting of.

In addition, the photosensitive metal-organic precursor layer may include ethyl hexanoate, acetylacetonate, dialkyldithiocarbamates, carboxylic acids, and carboxylates. ), Pyridine, Diamines, Arsines, Diarsines, Phosphines, Diphosphines, Butoxide, Butoxide, Isopropoxide, Ethoxide, Chloride, Acetate, Carbonyl, Carbonate, Hydroxide, Arenas, Beta-diketonate Diketonate), 2-nitrobenzaldehyde (2-Nitrobenzaldehyde), acetate dihydrate (Acetate Dihydrate) may be composed of any one or more of the organic ligand.

In the present invention, the photosensitive metal-organic precursor layer is hexane, 4-methyl-2-pentanone, ketone, methyl isobutyl ketone, methyl ethyl ketone, water, methanol, ethanol Propanol, isopropanol, butanol, pentanol, hexanol, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N-methylpyrrolidone, acetone, acetonitrile, tetrahydrofuran (Tetrahydrofuran: THF), tecan, nonane, octane, heptane, pentane, 2-methoxyethanol (E-Methoxyethanol) can be produced using at least one solvent selected from the group consisting of.

As such, the substrate 10 on which the imprint resin layer 20 or the photosensitive metal-organic precursor layer is formed is subjected to an imprint process.

That is, the imprint resin layer 20 or the photosensitive metal-organic precursor layer is pressed by the first imprint stamp 40 on which the first pattern 42 is formed.

Here, the first imprint stamp 40 is made of any one of silicon (Si), silicon oxide (SiO ₂ ), quartz (Quartz), nickel (Ni), copper (Cu), PDMS (Polydimethylsiloxane), PUA (Polyurethane acrylate), ETFE (Ethylene Tetrafluoroethylene), PFA (Perfluoroalkyl acrylate), PFPE (Perfluoropolyether), PTFE (Polytetrafluoroethylene) may be used a polymer stamp containing any one or more.

The first imprint stamp 40 may have a double structure, and a substrate 30 made of PET may be further provided on an upper surface of the first imprint stamp 40.

The first pattern 42 of the embodiment proposed by the present invention is a hole type pattern, and a micro pattern having a pattern size of micro units is applied.

As such, after pressing the imprint resin layer 20 or the photosensitive metal-organic precursor layer with the first imprint stamp 40 on which the first pattern 42 is formed, a heating or light irradiation method The imprint resin layer 20 or the photosensitive metal-organic precursor layer is cured in any one or in a mixed manner (FIG. 1b).

Here, when curing the imprint resin layer 20 or the photosensitive metal-organic precursor layer by irradiation with light, any one of ultraviolet rays, microwaves, X-rays and gamma rays to the imprint resin layer 20 or photosensitive Irradiating the metal-organic precursor layer, the irradiation time may be 1 second to 5 hours during the ultraviolet irradiation.

When the UV curing time is less than 1 second, the UV curing time is insufficient and pattern formation is not performed. When the UV curing time exceeds 5 hours, the deformation of the stamp for imprint occurs due to excessive UV irradiation time.

In addition, when curing the imprint resin layer 20 or the photosensitive metal-organic precursor layer by a heating method, the heating temperature is in the range of 30 ~ 300 ℃, the imprint resin layer 20 for 1 second to 5 hours ) Or the photosensitive metal-organic precursor layer can be heated.

When the curing time by the heating is less than 1 second, the pattern is not formed due to the lack of curing time due to heating. When the curing temperature is 5 hours at 300 ° C., the Si or metal oxide nano is pressed under the imprinting stamp. Aggregation of particles and formation of a crystalline phase of a metal oxide thin film cause cracks in the pattern layer, and deformation of the imprint stamp is not preferable.

Thereafter, the first imprint stamp 40 is removed to form a primary resin pattern layer 22 or a primary metal oxide thin film pattern layer (FIG. 1C).

Meanwhile, in the present invention, the primary resin pattern layer 22 or the primary metal oxide thin film pattern layer is formed based on a perfect curing dose value for patterning the imprint resin layer 20 or the photosensitive metal-organic precursor layer. In forming the step of irradiating less than the value of the full cure dose, there is a characteristic.

That is, the three-dimensional nanostructure manufacturing method of the present invention by performing a two-step (imprint) process of the imprint resin layer 20 or the photocurable metal-organic precursor layer to the boundary point of the fully cured dose value for the pattern formation To be able to easily form a three-dimensional nanostructure.

As such, after forming the primary resin pattern layer 22 or the primary metal oxide thin film pattern layer, the second imprint for heterogeneous second imprint having a second pattern 62 different from the first imprint stamp 40. The stamp 60 is prepared.

Here, the second imprint stamp 60 is made of any one of silicon (Si), silicon oxide (SiO ₂ ), quartz (Quartz), nickel (Ni), copper (Cu), PDMS (Polydimethylsiloxane), PUA (Polyurethane acrylate), ETFE (Ethylene Tetrafluoroethylene), PFA (Perfluoroalkyl acrylate), PFPE (Perfluoropolyether), PTFE (Polytetrafluoroethylene) may be used a polymer stamp containing any one or more.

The second imprint stamp 60 may have a double structure, and a substrate 50 made of PET may be further provided on an upper surface of the second imprint stamp 60.

The second pattern 62 of the embodiment proposed by the present invention is a pillar-type pattern, and a nano pattern having a pattern size of nano unit is applied.

As described above, the three-dimensional nanostructure manufactured according to the present invention may be formed in various shapes by using a plurality of imprint stamps, and the first pattern 42 and the second pattern 62 may have line widths, spacings, and the like. At least one of the depths may be the same or different.

In particular, the first pattern 42 is formed as a micro pattern, the second pattern 62 is formed as a nano pattern, the resin pattern layer or metal oxide thin film pattern layer prepared through the present invention is a micro and nano hybrid A pattern can be formed.

In addition, the first pattern 42 and the second pattern 62 may be formed of any one selected from a micro pattern or a nano pattern.

That is, the first pattern 42 is formed as a nano pattern, the second pattern 62 is formed as a micro pattern, and the resin pattern layer or metal oxide thin film pattern layer manufactured according to the present invention is nano / micro hybrid. A pattern can be formed.

In addition, both the first pattern 42 and the second pattern 62 may be formed as a nano pattern, or both the first pattern 42 and the second pattern 62 may be formed as a micro pattern.

In addition, the heterogeneous patterns 42 and 62 of the present invention may be embossed or engraved. That is, the first pattern 42 and the second pattern 62 may both be embossed or intaglio or a mixture of embossed and intaglio.

Thereafter, the first resin pattern layer 22 or the first metal oxide thin film pattern layer is pressed using the second imprint stamp 60 having the second pattern 62, and any of heating or light irradiation methods is used. One or a mixture thereof forms the secondary resin pattern layer 24 or the secondary metal oxide thin film pattern layer (FIG. 1F).

Here, in the step of forming the secondary resin pattern layer 24 or the secondary metal oxide thin film pattern layer, it is characterized in that to irradiate more than the complete curing dose value.

That is, in the present invention, the primary resin pattern layer 22 or the primary metal oxide thin film pattern layer based on a perfect curing dose value for pattern formation of the imprint resin layer 20 or the photosensitive metal-organic precursor layer. In the step of forming the irradiated less than the fully cured dose value, and in the step of forming the secondary resin pattern layer 24 or the secondary metal oxide thin film pattern layer is to irradiate more than the fully cured dose value.

Herein, when curing the primary resin pattern layer 22 or the primary metal oxide thin film pattern layer by irradiating light, one of ultraviolet rays, microwaves, X-rays, and gamma rays is irradiated, and the ultraviolet rays are irradiated. City survey time can be from 1 second to 5 hours.

When the UV curing time is less than 1 second, the UV curing time is insufficient and pattern formation is not performed. When the UV curing time exceeds 5 hours, the deformation of the stamp for imprint occurs due to excessive UV irradiation time.

In addition, when curing the primary resin pattern layer 22 or the primary metal oxide thin film pattern layer by a heating method, the heating temperature is in the range of 30 ~ 300 ℃, can be heated for 1 second to 5 hours. have.

When the curing time by the heating is less than 1 second, the pattern is not formed due to the lack of curing time due to heating. When the curing temperature is 5 hours at 300 ° C., the Si or metal oxide nano is pressed under the imprinting stamp. Aggregation of particles and formation of a crystalline phase of a metal oxide thin film cause cracks in the pattern layer, and deformation of the imprint stamp is not preferable.

2 is a SEM photograph of a three-dimensional nanostructure prepared according to an embodiment of the present invention.

As described above, the method of manufacturing a three-dimensional nanostructure of the present invention is performed by performing an imprint process in two steps by irradiating ultraviolet rays before and after a full curing dose value for pattern formation of an imprint resin or photosensitive metal-organic precursor. The nanostructure of the three-dimensional pattern can be prepared while omitting the etching process in.

In addition, the shape of the pattern may be in various forms such as spheres, points, tubes, cones, hemispheres, polygonal pyramids, polygonal cylinders, cylinders, and can also be a mixed shape thereof.

In addition, the three-dimensional nanostructure manufacturing method of the present invention can form a three-dimensional structure in a multi-step by using three or more imprint stamps of different patterns.

That is, the secondary resin pattern layer or the secondary metal oxide thin film pattern layer is pressed with a third imprint stamp having a third pattern different from the second imprint stamp, and any one of heating or light irradiation methods or these are mixed The method may further include forming the tertiary resin pattern layer or the tertiary metal oxide thin film pattern layer in a predetermined manner.

Here, the step of forming the tertiary resin pattern layer or the tertiary metal oxide thin film pattern layer in this way can be performed repeatedly, according to the manufacturing method of the three-dimensional nanostructure of the present invention, a variety of fourth, fifth or more It is possible to form a nanostructure in which the pattern of the form is formed.

In this case, the primary and secondary resin pattern layers or the primary and secondary metal oxide thin film pattern layers may be formed based on a perfect curing dose value for patterning the imprint resin layer or the photosensitive metal-organic precursor layer. In the step of irradiating less than the fully cured dose value, and in the step of forming the tertiary resin pattern layer or the tertiary metal oxide thin film pattern layer may be irradiated more than the full curing dose value.

≪ Example 1 >

Applicant has described Zinc acetate dihydrate (Sigma-Aldrich Co., USA), Monoethanolamine (Sigma-Aldrich Co., USA), 2-nitrobenzenaldehyde (Sigma-Aldrich Co., USA) to synthesize ZnO resin for the imprint process. And photosensitive ZnO resins were synthesized by mixing a certain amount of 2-methoxyethanol (Sigma-Aldrich Co., USA), and the primary micro stamp for imprint was a silicon master stamp (pillar-type having a 1 μm pillar line width and a 1.3 μm pillar height). After dropping PFPE (Perfluoropolyether) resin on the top of the Si Stamp, the PET (polyethylene-terephthalate) substrate was pressed, and then irradiated with ultraviolet rays for 3 minutes to produce a hole-type PFPE micro stamp.

In addition, as shown in Figure 3, for the ultraviolet sensitivity (D _1.0 ) curve analysis of the synthesized ZnO resin spin-coated the synthesized ZnO resin at 1000rpm, 60 seconds on the silicon substrate on top of the baking 80 ℃ 120 seconds 120 seconds After compressing the prepared hole-type PFPE micro stamp, UV, 2 minutes, 2.5 minutes, 3 minutes, 3.5 minutes, 4 minutes, 4.25 minutes, 4.5 minutes, 5 minutes, 5.5 minutes, 6 minutes, 7 minutes After 9 minutes and 11 minutes of irradiation, the PFPE stamps were separated (Demolding) to form ZnO patterns with Pillar-type and 1 μm pillar line width and 1.3 μm pillar height.

The ZnO resin synthesized was immersed in 2-methoxyethanol for 5 minutes using a Pillar-type ZnO sample formed according to various UV irradiation time for solvents for UV full curing dose analysis.

That is, the change in ZnO pattern height before and after solvent cleaning was analyzed by AFM measurement after soaking in 2-methoxyethanol. 3 shows a graph of normalized pattern height analysis based on a pattern depth of 1.3 μm of a hole-type PFPE stamp as 1 (100%).

The normalized pattern height value was 1, that is, the UV fully cured dose value of the synthesized ZnO resin was 8.25 J / cm ² . Therefore, in the first imprint process using a micro-patterned stamp, a UV pattern of 6.0 J / cm ² dose which is less than or equal to the full cure dose value was irradiated to form a micro-patterned ZnO pattern. The patterned Pillar-type PFPE stamp was pressed and additionally irradiated with 4.5 J / cm ² dose of ultraviolet light to fully cure the ZnO pattern to form a micro / nano-hybrid patterned ZnO structure.

The second nano stamp for imprint used is a drop of PFPE resin on top of a silicon master stamp (Hole-type Si Stamp having a 0.3 μm hole line width and a 0.2 μm hole depth) and a PET (polyethylene-terephthalate) substrate is pressed, followed by ultraviolet light. Was irradiated for 3 minutes to prepare a Pillar-type PFPE nano stamp.

4 is a SEM photograph of a ZnO micro / nano-hybrid nanostructure formed according to an embodiment of the present invention, FIG. 5 is an AFM photograph of a ZnO micro / nano-hybrid nanostructure formed according to an embodiment of the present invention. FIG. 6 is a graph illustrating nanostructure length analysis in FIG. 5.

That is, the first imprint process irradiates with ultraviolet rays less than the full cure dose, and the second imprint process irradiates with ultraviolet rays more than the full cure dose by imposing the fully cured dose value of the imprint resin. In this case, it can be seen that the three-dimensional nanostructures can be formed by a two-step imprint process.

The present invention as described above is not limited to the above-described embodiment and the accompanying drawings, it is possible that various forms of substitution, modification and change without departing from the spirit of the invention described in the claims It will be apparent to those of ordinary skill in the art.

10 substrate 20 imprint resin layer
22: primary resin pattern layer 24: secondary resin pattern layer
40: stamp for first imprint 42: first pattern
60: second imprint stamp 62: second pattern

Claims (16)

Forming an imprint resin layer or photosensitive metal-organic precursor layer on top of the substrate or thin film;
Pressing the imprint resin layer or the photosensitive metal-organic precursor layer with a first imprint stamp having a first pattern formed thereon, and the primary resin pattern layer by any one of heating or light irradiation methods or a mixture thereof. Or forming a primary metal oxide thin film pattern layer; And
The first resin pattern layer or the first metal oxide thin film pattern layer is pressed with a second imprint stamp having a second pattern different from the first imprint stamp, and any one of heating or light irradiation methods or a method in which these are mixed Forming a secondary resin pattern layer or a secondary metal oxide thin film pattern layer with a; Including,
A method of manufacturing a three-dimensional nanostructure, comprising forming a resin pattern layer or a metal oxide thin film pattern layer having a heterogeneous line width and a pattern form. The method according to claim 1,
Pressing the n-th resin pattern layer or the n-th metal oxide thin film pattern layer with an n + 1th imprint stamp having an n + 1th pattern different from the nth imprint stamp, and any one of heating or light irradiation methods or a mixture thereof Forming an n + 1st resin pattern layer or an n + 1st metal oxide thin film pattern layer in a conventional manner;
N is a three-dimensional nanostructure manufacturing method, characterized in that consisting of two or more integers. The method according to claim 2,
Forming the n + primary resin pattern layer or the n + primary metal oxide thin film pattern layer is a three-dimensional nanostructure manufacturing method, it characterized in that it can be performed repeatedly. The method according to claim 2 or 3, wherein the first pattern, the second pattern and the n + 1 pattern,
At least one of the line width, spacing, and depth is the same or different,
Method for producing a three-dimensional nanostructure, characterized in that the embossed or engraved. The method of claim 4,
The first pattern, the second pattern and the n + 1 pattern is formed of any one selected from a micro pattern or a nano pattern,
The resin pattern layer or the metal oxide thin film pattern layer having the heterogeneous line width and pattern form is a three-dimensional nanostructure manufacturing method characterized in that the micro and nano hybrid pattern or nano hybrid pattern or micro hybrid pattern is formed. The method according to claim 1,
As a boundary point, the fully cured dose value for patterning the imprint resin layer or the photosensitive metal-organic precursor layer is
In the step of forming the primary resin pattern layer or the primary metal oxide thin film pattern layer is irradiated less than the full curing dose value,
In the forming of the secondary resin pattern layer or the secondary metal oxide thin film pattern layer, the method of manufacturing a 3D nanostructure, characterized in that to irradiate more than the complete curing dose value. The method according to claim 2,
As a boundary point, the fully cured dose value for patterning the imprint resin layer or the photosensitive metal-organic precursor layer is
In the step of forming the primary, secondary resin pattern layer or the primary, secondary metal oxide thin film pattern layer is irradiated less than the value of the fully cured dose,
The forming of the n + primary resin pattern layer or the n + primary metal oxide thin film pattern layer in the step of producing a three-dimensional nanostructure, characterized in that to irradiate more than the value of the fully hardened dose. The method according to claim 1,
The substrate
Inorganic substrate or polycarbonate including any one or more of silicon (Si), gallium arsenide (GaAs), gallium phosphide (GaP), gallium arsenide (GaAsP), SiC, GaN, ZnO, MgO, sapphire, quartz, glass, Method for producing a three-dimensional nanostructure, characterized in that the polymer substrate comprising any one or more of polyethylene naphthalate, polynorbornene, polyacrylate, polyvinyl alcohol, polyimide, polyethylene terephthalate, polyether sulfone. The method according to claim 1, wherein the photosensitive metal-organic precursor layer,
Lithium (Li), beryllium (Be), boron (B), sodium (Na), magnesium (Mg), aluminum (Al), silicon (Si), indium (In), sulfur (S), potassium (K), Calcium (Ca), Scandium (Sc), Titanium (Ti), Vanadium (V), Chromium (Cr), Manganese (Mn), Iron (Fe), Cobalt (Co), Nickel (Ni), Copper (Cu), Zinc (Zn), Gallium (Ga), Germanium (Ge), Arsenic (As), Selenium (Se), Rubidium (Rb), Strontium (Sr), Yttrium (Y), Zirconium (Zr), Niobium (Nb) ), Molybdenum (Mo), ruthenium (Ru), rhodium (Rh), indium (In), tin (Sn), tellurium (Te), antimony (Sb), barium (Ba), hafnium (Hf), tantalum ( Ta), tungsten (W), iridium (Ir), lead (Pb), bismuth (Bi), polonium (Po) is a three-dimensional nanostructure fabrication comprising at least one metal element selected from the group consisting of Way. The method according to claim 1, wherein the photosensitive metal-organic precursor layer,
Ethylhexanoate, Acetylacetonate, Dialkyldithiocarbamates, Carboxylic acids, Carboxylates, Pyridine, Diamines, Arsines, Diarsines, Phosphines, Diphosphines, Butoxide, Isopropoxide, Ethoxide, Chloride, Acetate (Acetate), Carbonyl, Carbonate, Hydroxide, Arenas, Beta-Diketonate, 2-Nitrobenzaldihydr (2- Nitrobenzaldehyde), Acetate Dihydrate (Acetate Dihydrate) A method for producing a three-dimensional nanostructure, characterized in that consisting of at least one organic ligand. The method according to claim 1, wherein the photosensitive metal-organic precursor layer,
Hexane, 4-Methyl-2-pentanone, ketone, water, methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, dimethyl sulfoxide (DMSO), At least one selected from the group consisting of dimethylformamide (DMF), acetonitrile, tetrahydrofuran (THF), tecan, nonane, octane, heptane, pentane, and 2-methoxyethanol (E-Methoxyethanol) Method for producing a three-dimensional nanostructure, characterized in that produced using a solvent. The method of claim 1, wherein the first imprint stamp or the second imprint stamp is made of any one of silicon (Si), silicon oxide (SiO ₂ ), quartz (Quartz), nickel (Ni), copper (Cu), or PDMS ( Three-dimensional nanostructure, characterized in that using a polymer stamp comprising at least one of polydimethylsiloxane (PUA), polyurethane acrylate (PUA), ethylene tetrafluoroethylene (ETFE), perfluoroalkyl acrylate (PFA), perfluoropolyether (PFPE), polytetrafluoroethylene (PTFE) Manufacturing method. The method of claim 1, wherein when pressed with the first imprint stamp or the second imprint stamp and irradiated with light,
Any one of ultraviolet rays, microwaves, X-rays and gamma rays is irradiated to the imprint resin layer or the photosensitive metal-organic precursor layer, and the irradiation time is 3 seconds, characterized in that the irradiation time is 1 second to 5 hours. Nanostructure manufacturing method. The method of claim 1, wherein when pressurized and heated with the first imprint stamp or the second imprint stamp,
The heating temperature is in the range of 30 ~ 300 ℃, 3D nanostructure manufacturing method characterized in that for heating the imprint resin layer or photosensitive metal-organic precursor layer for 1 second to 5 hours. delete delete

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