KR101581437B1 - Fabrication method of asymmetric nanostructures for metal and metal oxide - Google Patents

Abstract

The present invention relates to a method of forming an asymmetric nanostructure, comprising a first step of forming an imprint layer on a substrate or a thin film, a step of positioning a variable imprint stamp on the imprint layer, A second step of pressing the variable imprint stamp in a pressure or direction for deforming and performing a hardening step to form an asymmetrical pattern layer; and a step of removing a residual film of the asymmetric pattern layer to expose a part of the substrate or the thin film A fourth step of depositing a metal or a metal oxide on the exposed substrate or thin film region and the asymmetric pattern layer; a step of removing the asymmetric pattern layer to form a metal or metal oxide pattern on the substrate or thin film; The method of claim 1, wherein the asymmetric metal or metal oxide nanostructure The castle way to a technical base. As a result, asymmetric metal or metal oxide nanostructures having a large area can be obtained by a simple process, and the degree of asymmetry of patterns can be adjusted according to the pressure or direction of the variable imprint stamp, have.

Description

[0001] The present invention relates to a method for forming asymmetric metal or metal oxide nanostructures,

The present invention relates to a method of forming an asymmetric nanostructure, and more particularly, to a method for forming an asymmetric patterned metal or metal oxide nanostructure by forming an asymmetric pattern layer using a variable imprint stamp, will be.

2. Description of the Related Art In recent years, studies on nanostructures and manufacturing methods thereof have been actively pursued in accordance with the trend toward higher integration and miniaturization of electronic devices. In general, nanostructures are composed of particles with a size of several nanometers and have optical, magnetic, and electrical properties, and exhibit different properties depending on the particle size.

Here, the nanostructure refers to a metal or a non-metal, a semiconductor, a magnetic material, or the like, and is formed of various materials depending on purposes and applications.

Particularly, in the present invention, metal nanostructures or metal oxide nanostructures are of interest. Metal oxide nanostructures are used in various electronic devices as insulators, dielectrics, and magnetic materials. In order to use such a nanostructure as an electronic device, a pattern is essential. In general, a pattern of a nanostructure is formed by deposition, patterning, and etching of a thin film.

Accordingly, Applicant has made various attempts to obtain nanostructures. Korean Patent Application No. 10-2008-0098598 (Method for forming metal nanostructure and metal nanostructure formed by the method), Application No. 10-2011- 0073391 (Aligned nanostructures with three-dimensional structure using imprint lithography and lift-off process and method for manufacturing the same), Application No. 10-2011-0117471 (Production of refractive index-controlled multilayer nanostructure using imprint lithography and lift- No. 10-2011-0135977 (a method for producing a three-dimensional nanostructure using imprint lithography and a three-dimensional nanostructure produced thereby), Application No. 10-2012-0152813 (Method for forming aligned metal oxide nanostructures) ).

However, although the above-described conventional techniques can be provided in a state where the nanostructure is aligned in a specific direction, application of the nanostructure to an area using anisotropic properties due to pattern asymmetry has been limited.

 Particularly, by using the anisotropy due to the asymmetry of the pattern of the nano structure, it is possible to detect the change of the magnetic field from the electric resistance change characteristic according to the intensity of the magnetic field, and thus, a very small, low power type high sensitivity magnetic field sensor, Direction sensors and the like.

For this purpose, there is a need for research into forming nano-structured patterns asymmetrically, and Highly Sensitive Biosensing Using Arrays of Plasmonic Au Nanorodisks Realized by Nanoimprint Lithography (VOL.5, NO.2, 897-904, 2011, ACS Nano) , Large Area Asymmetric Ferromagnetic Nanor Arrays Fabricated by Capillary Force Lithography ( Electronic Material Letters, Vol. 8, No. 1 (2012), pp. 71-74 ).

First, a resin is formed on a substrate, a pattern is formed by nano-imprint lithography, a residual layer is formed by tilted e-beam evaporation, And a metal is deposited by an electron beam evaporation method to form an elliptic metal nano structure.

The second technique is based on capillary force lithography. When a magnetic film is formed on a substrate, a diluted polymer layer is formed, and a stamp is placed on the polymer layer, a capillary force An asymmetric pattern is formed, and then an ion milling process is performed to obtain an asymmetric nanostructure.

However, these conventional techniques cause the asymmetric pattern itself to be formed immediately during the process, resulting in non-uniformity of the pattern and low reproducibility. In addition to the imprinting process, the electron beam deposition method and the capillary force lithography are used, The process is complicated and the cost is high.

In addition, it is difficult to realize a large area, and control of the degree of asymmetry of the pattern is not easy, and the utilization thereof is low.

In order to solve the above problems, the present invention relates to a method of forming an asymmetric nanostructure, and more particularly, to a method of forming an asymmetric pattern by using a stamp for variable imprint capable of deforming a pattern depending on a pressure, The object of the present invention is to provide a metal oxide nanostructure.

According to an aspect of the present invention, there is provided a method of manufacturing a variable imprint stamp, comprising the steps of: forming an imprint layer on a substrate or a thin film; placing a variable imprint stamp on the imprint layer; A third step of exposing a part of the substrate or thin film by removing a residual film of the asymmetric pattern layer; and a third step of exposing a part of the substrate or thin film by removing the remaining film of the asymmetric pattern layer, A fourth step of depositing a metal or a metal oxide on the exposed substrate or thin film region and the asymmetrical pattern layer, and a fifth step of forming the metal or metal oxide pattern on the substrate or thin film by removing the asymmetric pattern layer A method for forming an asymmetric metal or metal oxide nanostructure is provided. .

The substrate may be an inorganic substrate of any one of silicon (Si), gallium arsenide (GaAs), gallium arsenide (GaP), gallium arsenide (GaAsP), SiC, GaN, ZnO, MgO, sapphire, quartz, It is also possible to use polycarbonate (PC), polyethylene naphthalate (PEN), polynorbornene, polyacrylate, polyvinyl alcohol, polyimide, polyethylene terephthalate polyethylene terephthalate (PET), and polyethersulfone (PES).

It is preferable that the imprint layer of the first step is made of an imprint resin or a photosensitive metal-organic precursor, and the thickness of the imprint layer is relatively thinner than the pattern thickness of the variable imprint stamp. It is also preferable that the polymer layer is first formed on the substrate or thin film, and the imprint layer is formed.

The polymer layer is formed to have a thickness of 50 nm to 3000 nm and is made of polyvinyl chloride (PVC), neoprene, polyvinyl alcohol (PVA), poly methyl methacrylate (PMMA), polybenzyl methacrylate (PBMA) On glass, polydimethylsiloxane (PDMS), polyvinyl formal (PVFM), parylene, polyester, epoxy, polyether, polyimide and LOR (lift-off resist).

The stamp for the variable imprint of the second step may be formed of any one of PDMS (Polydimethylsiloxane), PUA (Polyurethane acrylate), ETFE (Ethylene Tetrafluoroethylene), PFA (Perfluoroalkyl acrylate), PFPE (Perfluoropolyether) and PTFE (Polytetrafluoroethylene) .

In the second step, it is preferable to press the variable imprint stamp at a pressure of 1.1 bar to 50 bar in order to deform the pattern of the variable imprint stamp. Further, in order to deform the pattern of the variable imprint stamp It is preferable to press the variable imprint stamp in a direction parallel to the interface between the imprint layer and the variable imprint stamp.

The curing step of the second step is carried out by photo-curing by ultraviolet light, and is performed by irradiating ultraviolet rays to the imprint layer for 1 second to 5 hours or by thermal curing by heat, To 300 < 0 > C for 1 second to 5 hours.

Further, the residual film removed in the third _{step, BCl 3, SiCl 4, Cl} 2, HBr, SF 6, CF 4, C 4 F 8, CH 4, CHF 3, NF 3, CFCs (chlorofluorocarbons), H 2 and O is done by the _second dry etching using at least any one or more gases selected from the group consisting of, preferably at least one for use by further comprising the inert gas is selected from the gases N _2, Ar and He.

Here, the deposition of the metal or metal oxide in the fourth step is performed by an electron beam evaporator, and the metal or metal oxide is preferably deposited to a thickness of 10 nm to 1000 nm, It is preferable to form a multi-layer structure by sequentially depositing a metal or a metal oxide.

The removal of the asymmetric pattern layer may be carried out in a solvent such as acetone, 4-methyl-2-pentanone, ketone, methyl isobutyl ketone, methyl ethyl ketone, water, methanol, ethanol, propanol, isopropanol Such as butanol, pentanol, hexanol, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N-methylpyrrolidone, acetone, acetonitrile, tetrahydrofuran It is preferable to perform the wet etching process using at least one solvent selected from the group consisting of methanol, ethanol, isopropanol, n-butanol, heptane, pentane and 2-methoxyethanol.

The asymmetrical metal or metal oxide nanostructure of large area can be obtained by a simple process and the degree of asymmetry of the pattern can be controlled by controlling the pressure, direction or thickness of the imprint layer of the variable imprint stamp There is an effect that can be utilized variously.

In addition, the present invention is not limited to forming asymmetric metal or metal oxides to form an asymmetric nanostructure, but may be formed by first forming an asymmetrical pattern layer by a stamp for variable imprint and then depositing metal or metal oxide, It is possible to prevent the deformation of the nanostructure, and as a result, it is possible to provide a high-quality nanostructure with excellent reproducibility.

It is also expected that various asymmetric metal or metal oxides can be easily produced by controlling the imprinting process conditions such as the pressing force and direction of the variable imprint stamp.

1 is a schematic diagram of a method for forming an asymmetric metal or metal oxide nanostructure according to the present invention.
Fig. 2 is a view showing data according to Embodiment 1 of the present invention; Fig.
3 is a view showing data according to Embodiment 2 of the present invention;

The present invention relates to a method of forming an asymmetric nanostructure, and more particularly, to a method for forming an asymmetric patterned metal or metal oxide nanostructure by forming an asymmetric pattern layer using a variable imprint stamp, will be.

As a result, by forming the asymmetrical pattern layer using the variable imprint stamp, it is possible to obtain a large area asymmetric metal or metal oxide nanostructure by a simple process, and the pressure or direction of the variable imprint stamp or the width of the imprint layer It is possible to control the degree of asymmetry of the pattern according to the thickness control and to utilize it variously.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. 1 is a schematic view of a method for forming an asymmetric metal or metal oxide nanostructure according to the present invention.

As shown in the figure, a method of forming an asymmetric metal or metal oxide nanostructure according to the present invention includes a first step of forming an imprint layer on a substrate or a thin film, a step of placing a variable imprint stamp on the imprint layer, A second step of pressing a variable imprint stamp in a pressure or direction for deforming the pattern of the variable imprint stamp and performing a hardening step to form an asymmetrical pattern layer; A third step of exposing a part of the thin film, a fourth step of depositing a metal or a metal oxide on the exposed substrate or the thin film region and the asymmetric pattern layer, and removing the asymmetric pattern layer to form a metal Or a fifth step of forming a metal oxide pattern.

First, in a first step for forming an asymmetric metal or metal oxide nanostructure according to the present invention, an imprint layer is formed on a substrate or a thin film. The imprint layer is imprinted by a variable imprint stamp, It is the part where the pattern is formed by the curing process.

The substrate may be any one of an inorganic substrate of silicon (Si), gallium arsenide (GaAs), gallium phosphide (GaP), gallium arsenide (GaAsP), SiC, GaN, ZnO, MgO, sapphire, quartz, polycarbonate, PC), polyethylene naphthalate (PEN), polynorbornene, polyacrylate, polyvinyl alcohol, polyimide, polyethylene terephthalate, PET, and polyethersulfone (PES).

The thin film is formed by forming a semiconductor thin film or the like according to an electronic device to be finally used in the upper layer of the substrate, and forming an imprint layer on the upper layer.

Here, the imprint layer is formed of an imprint resin or a photosensitive metal-organic precursor, and is subjected to photo-curing or thermal curing after imprinting.

The imprinted resin uses a crosslinkable monomer, an acrylic ester monomer, an aromatic vinyl monomer, an unsaturated monomer having a hydroxyl group, an unsaturated monomer having an acid group, a polymerization chain transfer agent, an oxidation stabilizer or a polymerization initiator.

In detail, the crosslinkable monomer may be at least one selected from the group consisting of N-methyl methacrylamide, methoxymethyl methacrylamide, N-ethoxymethyl methacrylamide, N-propoxymethyl methacrylamide, N-isopropoxymethyl methacrylamide , N-butoxymethyl methacrylamide, N-isobutoxymethyl methacrylamide or N-tertiary butoxymethyl methacrylamide, and the acrylic acid ester monomer is at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate , Propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, phenyl methacrylate, stearic methacrylate, cyclo Hexyl methacrylate, or lauryl methacrylate.

The aromatic vinyl-based monomer may be any one or more of styrene, trans-methylstyrene, metmethylstyrene, alpha-methylstyrene, betamethylstyrene, and 4-methylstyrene. The unsaturated monomer having a hydroxyl group may be beta-hydroxyethylmethacryl Hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, or hydroxyethyl methacrylate to which? -Caprolactone is added; and the unsaturated monomer having an acid group is at least one selected from the group consisting of acrylic acid, methacrylic acid, Maleic acid, fumaric acid or itaconic acid.

In addition, the photosensitive metal-organic precursor is provided as a metal-organic precursor sol in which nano-sized metal and organic ligands are well dispersed in a solvent.

The metal element constituting the metal-organic precursor may be lithium, beryllium, boron, sodium, magnesium, aluminum, silicon, indium, (S), potassium (K), calcium (Ca), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe) , Nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), rubidium (Rb), strontium ), Zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), indium (In), tin (Sn), tellurium (Te), antimony (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), gadolinium (Gd), hafnium (Hf), tantalum (Ta), tungsten (Ir), lead (Pb), bismuth (Bi), polonium (Po) and uranium (U).

The organic ligand constituting the metal-organic precursor may be selected from the group consisting of ethylhexanoate, acetylacetonate, dialkyldithiocarbamates, carboxylic acids, carboxylate but are not limited to, carboxylates, pyridines, diamines, arsines, diarsines, phosphines, diphosphines, butoxide, isopropoxide ), Ethoxide, chloride, acetate, carbonyl, carbonate, hydroxide, arenas, beta-diketonate beta-diketonate, 2-nitrobenzaldehyde, acetate dihydrate, monoethanolamine, and mixtures thereof. The term " monoethanolamine "

The solvent of the metal-organic precursor composition may be selected from the group consisting of hexane, 4-methyl-2-pentanone, ketone, methyl isobutyl ketone, methyl ethyl ketone, water, methanol, ethanol, propanol , Dimethylformamide (DMF), N-methylpyrrolidone, acetone, acetonitrile, tetrahydrofuran (THF), tetrahydrofuran (THF) , At least one selected from the group consisting of tecane, nonane, octane, heptane, pentane and e-methoxyethanol is used.

The imprint resin or the metal-organic precursor sol is coated on the substrate or thin film by a method such as spin coating to form an imprint layer.

In addition, the polymer layer may be formed before the imprint layer is formed on the substrate or the thin film.

The polymer layer is formed to have a thickness of 50 nm to 3000 nm and is made of polyvinyl chloride (PVC), neoprene, polyvinyl alcohol (PVA), poly methyl methacrylate (PMMA), polybenzyl methacrylate (PBMA), poly styrene, spin on glass , PDMS (Polydimethylsiloxane), PVFM (Polyvinyl formal), Parylene, Polyester, Epoxy, Polyether, Polyimide and LOR (Lift-off resist).

The polymer layer is formed between the imprint layer and the substrate or the thin film to improve the coating property and the film property of the imprint layer and has an etching resistance to a dry etching to be described later to help form a clear imprinting pattern .

Next, in the second step, a variable imprint stamp is placed on the imprint layer, a variable imprint stamp is pressed in a pressure or direction for deforming the pattern of the variable imprint stamp, and a hardening process is performed, Thereby forming a pattern layer.

That is, a flexible imprinting stamp is used to press the imprinting stamp at a constant force and direction to warp the pattern of the imprinting stamp to form an asymmetrical pattern layer.

The stamp for imprinting is preferably formed of a flexible material and may be formed of any material selected from the group consisting of PDMS (Polydimethylsiloxane), PUA (Polyurethane acrylate), ETFE (Ethylene Tetrafluoroethylene), PFA (Perfluoroalkyl acrylate), PFPE (Perfluoropolyether) Of a polymer material.

The stamp for imprinting has a predetermined pattern corresponding to the pattern of the asymmetric pattern layer and is placed in the imprint layer so as to pressurize the imprinting stamp in a specific direction or at a pressure capable of causing warping deformation of the pattern of the imprinting stamp .

Further, it is preferable to press the variable imprint stamp at a pressure of 1.1 bar to 50 bar to deform the pattern of the variable imprint stamp. The pattern of the variable imprint stamp can not be deformed. If it is higher than this, the asymmetric pattern layer may not be formed properly or adhesion between adjacent patterns may occur.

In order to deform the pattern of the variable imprint stamp, the variable imprint stamp is pressed in a direction parallel to the interface between the imprint layer and the variable imprint stamp, so that the pattern of the variable imprint stamp is deformed in a predetermined direction The uniformity of the pattern of the asymmetric nanostructure is achieved.

Meanwhile, in order to more easily control the shape and size of the asymmetric pattern layer, to further improve the uniformity of the non-birefringent pattern layer and to be formed close to the design value, the thickness of the imprint layer It is preferable that the thickness is relatively thinner than the pattern thickness.

If the thickness of the imprint layer is thicker than the thickness of the stamp pattern for the variable imprint, the stamp pattern for the variable imprint is not easily deformed even if the pressure and the direction are applied, so that there is a high possibility that the asymmetric pattern layer is not formed.

That is, when filling the imprint layer with the variable imprint stamp, the imprint layer is not completely filled between the stamp patterns for the variable imprint (pattern and pattern space [Void]), The deformation of the stamp pattern for the variable imprint is more likely to occur, and the formation of the asymmetric pattern layer is more easily achieved.

Therefore, by adjusting the thickness of the imprint layer, the degree of deformation of the variable imprint stamp pattern can be easily controlled, and the shape of the asymmetric pattern layer can be easily controlled.

Then, the curing process is performed in a state of being pressurized by the variable imprint stamp. Here, the curing process may be a combination of the two processes depending on the necessity of either light curing by ultraviolet light or heat curing by heat.

In the photo-curing process by ultraviolet rays, an asymmetric pattern layer is formed by irradiating the imprint layer with ultraviolet rays for 1 second to 5 hours to cure the imprint layer and remove the stamp for variable imprint.

In the thermal curing step by heat, the asymmetric pattern layer is formed by heating the imprint layer at 30 to 300 DEG C for 1 second to 5 hours to cure the imprint layer and removing the variable imprint stamp .

Further, according to the material of the variable imprint stamp or according to the material of the imprint layer and the polymer layer, the variable imprint stamp is removed after the soft curing process (the ultraviolet irradiation time is short or the heat curing temperature is low) ) Curing process may be performed.

The curing of the imprint layer as described above can be realized by ultraviolet irradiation or heating. That is, the ultraviolet ray irradiation and the heating process can be carried out alternately or alternately if necessary, and the asymmetric pattern layer is formed on the substrate or the thin film by removing the stamp for the variable imprint.

Here, the asymmetric pattern layer may be formed in various shapes depending on the pressure and direction of the variable imprint stamp pattern or the variable imprint stamp, and an elliptical shape is most preferable.

Then, the third step is to remove the residual film of the asymmetric pattern layer to expose a part of the substrate or thin film. In general, due to the nature of the imprinting process, the substrate or the thin film is not completely exposed and a residual film remains with a predetermined pattern.

The remaining thin film remaining by the imprinting and curing process of the imprint layer is removed to expose a part of the substrate or the thin film (area where the remaining film is formed) to form an asymmetric pattern layer from which the remaining film is removed.

The asymmetric pattern layer prevents deformation of an asymmetric nanostructure to be described later, and an asymmetric nanostructure is formed according to an asymmetric pattern layer, so that the reproducibility is excellent and a high-quality nanostructure can be provided. This is completely different from the prior art in which metal or metal oxide is formed asymmetrically from the beginning to form an asymmetric nanostructure, and the conventional technique has remarkably low reproducibility in accordance with the process.

The remnant film removal is performed by a dry etching process and is carried out by a dry etching process using BCl ₃ , SiCl ₄ , Cl ₂ , HBr, SF ₆ , CF ₄ , C ₄ F ₈ , CH ₄ , CHF ₃ , NF ₃ , CFCs chlorofluorocarbons), H _2, and O ₂ . At least one inert gas selected from N ₂ , Ar, and He may be further included in the gas during dry etching.

In the fourth step, a metal or a metal oxide is deposited on the exposed substrate or thin film region and the asymmetric pattern layer by an electron beam evaporator, and the thickness of the metal or metal oxide is about 10 nm to 1000 nm.

Particularly, in the electron beam deposition, the metal or the metal oxide is made to deposit a different kind of metal or metal oxide sequentially so as to form a multi-layer structure. For example, a material for improving adhesion between a substrate or a thin film and a metal or a metal oxide is deposited directly on a substrate or a thin film, and a metal or a metal, And a metal oxide is selected to form a multi-layer structure.

Next, in the fifth step, the asymmetric pattern layer is removed to form a metal or metal oxide pattern on the substrate or the thin film. Here, when the polymer layer is formed, the polymer layer is removed together with the asymmetric pattern layer.

The removal of the asymmetric pattern layer may be carried out in a solvent such as acetone, 4-methyl-2-pentanone, ketone, methyl isobutyl ketone, methyl ethyl ketone, water, methanol, ethanol, propanol, isopropanol, , Dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N-methylpyrrolidone, acetone, acetonitrile, tetrahydrofuran (THF) , Wet etching using at least one solvent selected from the group consisting of hexane, heptane, pentane, and 2-methoxyethanol.

As described above, the present invention relates to an asymmetric metal or metal oxide nanostructure, and more particularly, to an asymmetrical pattern layer using a variable imprint stamp capable of deforming a pattern in accordance with a pressure, Or a metal oxide nanostructure.

As a result, by forming the asymmetrical pattern layer using the variable imprint stamp, it is possible to obtain an asymmetric metal or metal oxide nanostructure having a large area by a simple process with uniform patterns and excellent reproducibility, It is possible to control the degree of asymmetry of the pattern by controlling the pressure, direction or the thickness of the imprint layer of the stamp for imprint,

Hereinafter, embodiments of the present invention will be described.

Example 1

  (Example of formation of asymmetric Au nanostructure using imprint resin)

950PMMA A7 (Micro Chem Co., USA) was spin-coated on the top of the silicon substrate at 3000 rpm and baked at 170 占 폚 for 300 seconds. The variable imprint stamp is made by stamping a PFPE resin on the top of a silicon-master stamp (Hole-patterned Si Stamp), pressing a PET (polyethylene-terephthalate) substrate and irradiating with ultraviolet light for 3 minutes to produce a pillar-patterned PFPE variable imprint stamp Respectively.

The imprinted NFP-SC28LV400 (Chem. Optics, Korea) was spin-coated on the top of the PMMA layer at 3500 rpm for 60 seconds. The prepared pillar-patterned PFPE variable imprint stamp was pressed at 20 bar, irradiated with ultraviolet rays for 2 minutes, The variable imprint stamp was relieved to form a nano-patterned asymmetric pattern layer on top of the 500 nm thick PMMA layer.

Thereafter, the residual film included in the asymmetric pattern layer and the lower 500 nm-thick PMMA layer were dry etched (FIG. 2 (a)). E-beam evaporator was fabricated by using UEE-1 (Ultech Co., Korea) equipment. Ti film was deposited at 10 nm at 2 Å / s and Au film was deposited at 200 nm at 2 Å / s. Is shown in FIG. 2 (b). As shown in FIG. 2 (c), an asymmetric Au nanostructure is formed by immersing in an acetone bath for 60 seconds and blowing with nitrogen gas.

Example 2

(Examples for forming an asymmetric Au nanostructure using photosensitive metal-organic precursors [Ti-organic precursors, Sn-organic precursors and Zr-organic precursors)

Titanium (VI) to synthesize a photosensitive Ti- organic precursor solution (n-butoxide) ₂ (2-ethylhexanoate) ₂ [Ti (VI) (n-butoxide) ₂ (2-ethylhexanoate) _2, synthesis; And 5.00 g of hexane (Hexane, Aldrich Co., USA) were mixed and stirred for 24 hours to prepare a 0.27 molar concentration.

Here, titanium (VI) (n-butoxide) ₂ (2-ethylhexanoate) ₂ [Ti (VI), (n-butoxide) ₂ (2-ethylhexanoate) _2] in order to synthesize a titanium (VI) (n 10.5266g of [Ti (VI) (n-butoxide) ₄ , Aldrich Co., USA], 8.7400g of 2-ethylhexanoic acid, Aldrich Co., USA, 15.000g Titanium (VI) (normal-butoxide) ₂ (2-ethylhexanoate) ₂ was synthesized by evaporating and condensing the mixture for 72 hours using a rotary evaporator in a round flask.

The synthesized photosensitive Ti-organic precursor solution was spin-coated on the 500 nm-thick upper part of the PMMA at 3000 rpm. The pillar-type PFPE variable imprint stamp was pressed at 20 bar, irradiated with ultraviolet rays for 20 minutes, TiO ₂ as a pattern layer was formed, and the result is shown in FIG. 3 (a).

The TiO ₂ asymmetric pattern layer (including the residual film) and the underlying 500 nm-thick PMMA were dry-etched, and then 10 nm of Ti and 200 nm of Au were deposited in the same manner as in Example 1. After immersing in an acetone bath for 60 seconds, Thereby forming an asymmetric Au nanostructure as shown in FIG. 3 (a).

Further, in order to use various photosensitive metal-organic precursors, a photosensitive Sn-organic precursor solution was synthesized. (VI) 2-ethylhexanoate (Sn (II) 2-ethylhexanoate, Alfa Aesar Co., USA) and hexane (Hexanes, Aldrich Co., USA) 6.000 g, and the mixture was stirred for 24 hours to prepare a 0.21 molar concentration.

The synthesized photosensitive Sn-organic precursor solution was spin-coated on the 500 nm-thick upper part of the PMMA at 4500 rpm. The pillar-type PFPE variable imprint stamp was pressed at 20 bar, irradiated with ultraviolet rays for 40 minutes, A SnO ₂ thin film pattern as an asymmetric pattern layer was formed, and the result is shown in FIG. 3 (b).

The SnO ₂ asymmetric pattern layer (including the residual film) and the lower 500 nm-thick PMMA were dry-etched and then 10 nm of Ti and 200 nm of Au were deposited in the same manner as in Example 1. After immersing in an acetone bath for 60 seconds, As shown in FIG. 3 (b), an asymmetric Au nanostructure was formed.

Also, in order to use various photosensitive metal-organic precursors, a photosensitive Zr-organic precursor solution was synthesized. To prepare a photosensitive Zr-organic precursor solution, 1.6893 g of zirconium (VI) 2-ethylhexanoate [Zr (VI) 2-ethylhexanoate, Strem Co., USA) and 10.6749 g of hexane (Aldrich Co., USA) Were mixed and stirred for 24 hours to prepare a 0.063 molar concentration.

The synthesized photosensitive Zr-organic precursor solution was spin-coated on the 500 nm-thick upper part of the PMMA at 6000 rpm. The pillar-type PFPE variable imprint stamp was pressed at 20 bar, irradiated with ultraviolet rays for 50 minutes, and then stamped for variable imprint To form a ZrO ₂ asymmetric pattern layer, and the result is shown in FIG. 3 (c).

The ZrO ₂ asymmetric pattern layer (including the residual film) and the lower 500 nm-thick PMMA were dry-etched. Then, 10 nm of Ti and 200 nm of Au were deposited in the same manner as in Example 1, immersed in an acetone bath for 60 seconds, An asymmetric Au nanostructure was formed as shown in FIG. 3 (c).

As shown in Example 1 and Example 2, various types of asymmetric metal nanostructures can be formed by controlling imprint process conditions using imprint resins and various photosensitive metal-organic precursors.

As described above, the present invention relates to a method of forming an asymmetric nanostructure, and more particularly, to a method of forming an asymmetric patterned layer using a variable imprint stamp capable of deforming a pattern in accordance with a pressure, .

As a result, by forming the asymmetrical pattern layer using the variable imprint stamp, it is possible to obtain a large area asymmetric metal or metal oxide nanostructure by a simple process, and the pressure or direction of the variable imprint stamp or the It is possible to control the degree of asymmetry of the pattern according to the thickness control and to utilize it variously.

In addition, the present invention is not limited to forming asymmetric metal or metal oxides to form an asymmetric nanostructure, but may be formed by first forming an asymmetrical pattern layer by a stamp for variable imprint and then depositing metal or metal oxide, It is possible to prevent deformation of the nanostructure and to provide a high-quality nanostructure with excellent reproducibility.

In addition, it is easy to fabricate asymmetric metal or metal oxide having various shapes by controlling the imprint process conditions such as the pressing force and direction of the variable imprint stamp.

Claims (17)

A first step of forming an imprint layer on a substrate or a thin film;
A variable imprinting stamp made of a flexible material is placed on the imprinting layer so as to press the variable imprinting stamp in a pressure or direction in which the pattern of the variable imprinting stamp causes warping deformation, A second step of forming a second electrode layer;
A third step of removing the remaining film of the asymmetric pattern layer to expose a part of the substrate or the thin film;
A fourth step of depositing a metal or a metal oxide on the exposed substrate or thin film region and the asymmetric pattern layer;
And removing the asymmetric pattern layer to form a metal or metal oxide pattern on the substrate or the thin film,
The thickness of the imprint layer in the first step may be,
Wherein when the imprint layer is pressed by the variable imprint stamp, the imprint layer is formed to be thinner than a thickness of the variable imprint stamp pattern so that the imprint layer is not completely filled between the variable imprint stamp patterns,
The second step comprises:
The variable imprint stamp is pressed at a pressure of 1.1 bar to 50 bar to deform the pattern of the variable imprint stamp,
Alternatively, the variable imprinting stamp may be pressed in a direction parallel to the interface between the imprint layer and the variable imprinting stamp in order to deform the pattern of the variable imprinting stamp. Way. The substrate processing apparatus according to claim 1,
A substrate made of an inorganic material such as silicon (Si), gallium arsenide (GaAs), gallium arsenide (GaP), gallium arsenide (GaAsP), SiC, GaN, ZnO, MgO, sapphire, quartz, ), Polyethylene naphthalate (PEN), polynorbornene, polyacrylate, polyvinyl alcohol, polyimide, polyethylene terephthalate (PET), polyethylene terephthalate A method for forming an asymmetric metal or metal oxide nanostructure, which is a polymer substrate of any one of polyethersulfone (PES). delete The method according to claim 1, wherein the imprinting layer of the first step comprises:
An imprint resin or a photosensitive metal-organic precursor. ≪ RTI ID = 0.0 > 11. < / RTI > 5. The method according to claim 4,
A method for forming an asymmetric metal or metal oxide nanostructure, wherein a polymer layer is first formed on a substrate or a thin film, and the imprint layer is formed. 6. The polymer electrolyte fuel cell according to claim 5,
A thickness of 50 nm to 3000 nm,
Polyvinyl Chloride (PVC), Neoprene, PVA (Polyvinyl Alcohol), PMMA (Poly Methyl Meta Acrylate), PBMA (Poly Benzyl Meta Acrylate), PolyStylene, SOG (Spin On Glass), PDMS (Polydimethylsiloxane) , Parylene, polyester, epoxy, polyether, polyimide, and lift-off resist (LOR). The method according to claim 1, wherein the second imprint stamp for imprinting comprises:
Wherein the asymmetric metal or metal oxide nanostructure is formed by one of PDMS (Polydimethylsiloxane), PUA (Polyurethane acrylate), ETFE (Ethylene Tetrafluoroethylene), PFA (Perfluoroalkyl acrylate), PFPE (Perfluoropolyether) and PTFE / RTI > delete delete The method according to claim 1, wherein the curing step of the second step comprises:
And irradiating the imprint layer with ultraviolet light for 1 second to 5 hours. The method for forming an asymmetric metal or metal oxide nanostructure according to claim 1, The method according to claim 1, wherein the curing step of the second step comprises:
And heat is applied to the imprint layer at 30 ° C to 300 ° C for 1 second to 5 hours to form an asymmetric metal or metal oxide nanostructure. 2. The method according to claim 1,
_{BCl 3, SiCl 4, Cl 2} , HBr, SF 6, CF 4, C 4 F 8, CH 4, CHF 3, NF 3, CFCs (chlorofluorocarbons), at least one selected from the group consisting of H ₂ and O ₂ Wherein the metal oxide or metal oxide nanostructure is formed by dry etching using a gas. 13. The method of claim 12,
Wherein at least one inert gas selected from the group consisting of N ₂ , Ar, and He is further added to the gas for use in forming the asymmetric metal or metal oxide nanostructure. 14. The method according to any one of claims 1, 2, 4, 7, and 10 to 13, wherein the deposition of the metal or metal oxide in the fourth step comprises:
Wherein an electron beam evaporator is used. 15. The method of claim 14, wherein the metal or metal oxide is deposited to a thickness of 10 nm to 1000 nm. 15. The method of claim 14,
Wherein the metal or metal oxide nanostructure is formed by sequentially depositing a heterogeneous metal or a metal oxide to form a multi-layered structure. 15. The method of claim 14, wherein removing the asymmetric pattern layer comprises:
Acetone, 4-methyl-2-pentanone, ketone, methyl isobutyl ketone, methyl ethyl ketone, water, methanol, ethanol, propanol, isopropanol, butanol, pentanol, Dimethylformamide (DMF), N-methylpyrrolidone, acetone, acetonitrile, tetrahydrofuran (THF), tecane, nonane, octane, heptane, pentane and 2 Wherein the wet etching step is performed by at least one solvent selected from the group consisting of e-methoxyethanol.

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