KR20100080336A - Method of manufacturing nano structure and method of manufacturing a pattern using the method - Google Patents

Abstract

PURPOSE: A method for manufacturing a nanostructure is provided to easily form the nanostructure which is successively arranged on a substrate using a block copolymer and to improve the productivity of the nanostructure and a polarizing plate. CONSTITUTION: A method for manufacturing a nanostructure comprises the following steps: forming a photoresist pattern on a substrate(110) including a neutral layer; forming a sacrificial structure including a first sacrificial block and a second sacrificial block using a first thin film including a first block copolymer; eliminating the first sacrificial block from the sacrificial structure; forming a chemical pattern(122) by oxidizing the neutral layer using the second sacrificial block as a mask; removing the second sacrificial block and the photoresist pattern from the substrate including the chemical pattern; and forming the nanostructure which is extensively arranged on the substrate using a second thin film including the second block copolymer.

Description

Method of manufacturing nanostructures and pattern manufacturing using the same TECHNICAL FIELD

The present invention relates to a method for producing a nanostructure and a method for producing a pattern using the same, and more particularly, to a method for producing a nanostructure using a block copolymer and a method for producing a pattern using the same.

In the natural world, self-assembled organisms have been found to have hierarchiral structures. Relevant researches for reproducing the chemical production method of the nanostructures formed from the organisms and applying them academically and commercially have attracted attention. This and self-assembly is also found in block copolymers, one of the polymers that can be synthesized organic chemically.

The block copolymer is a kind of polymer material, in which two or more polymers are connected to each other by covalent bonds. The diblock copolymer, which is the simplest structure of the block copolymer, has two polymers having different inclinations connected to each other to form one polymer. The two polymers connected to each other are easily phase separated due to different material properties, and finally the block copolymer may self-assemble to form nanostructures.

In order to broaden the practical application range of the nanostructures prepared using the block copolymer, it is important to form a thin film on a substrate and then induce stable nanostructure formation therein. However, the block copolymer in the thin film state causes problems such as the formation of nanostructures different from the bulk phase or the nanostructures arranged in an undesired form due to the interaction between the self-assembled material and the substrate. In order to solve this problem, technologies for controlling the orientation and arrangement of nanostructures with respect to thin film samples have been developed. In general, in order to control the orientation or arrangement of the nanostructure, an electric field, epitaxial self-assembly, graphoepitaxy, or the like is used. However, even the technologies developed to date have limitations in uniformly forming nanostructures on large-area substrates.

On the other hand, as a representative example of the technology for manufacturing a nanostructure, Carnegie Mellon University of the technique for producing a nanostructured material is disclosed in US Patent No. 7,056,455. The registered patent relates to a method for producing carbon nanostructures such as carbon nanofibers, carbon nanotubes, carbon nanocylinders by pyrolyzing precursors including block copolymers.

In addition, a method of manufacturing a nanopattern using an inorganic or organic material containing a polymer is disclosed in US 2008-0070010. The disclosed patent relates to a method for producing nanopatterns, nanostructures and nanopatterned functional oxides, and patterning a resist-coated substrate using electron beam lithography and removing the resist to form a patterned resist-coated substrate. The present invention relates to a technique for manufacturing a nanopatterned structure by spin coating with a liquid precursor of an organic material including a polymer and removing the remaining resist, and still removing the resist used in the lithography process. There is an inevitable problem.

Accordingly, the technical problem of the present invention was conceived in this respect, and an object of the present invention is to provide a method for producing a nanostructure using a block copolymer.

Another object of the present invention is to provide a method for producing a pattern using a block copolymer.

In the method of manufacturing a nanostructure according to an embodiment for realizing the above object of the present invention, a neutral layer is formed on a substrate, and a photoresist pattern is formed on the substrate including the neutral layer. A first thin film including the first block copolymer is formed on the substrate including the photoresist pattern. The first thin film forms a sacrificial structure including a first sacrificial block and a second sacrificial block. After removing the first sacrificial block from the sacrificial structure, the neutral layer is oxidized using the second sacrificial block as a mask to form a chemical pattern. The second sacrificial block and the photoresist pattern are removed from the substrate including the chemical pattern. A second thin film including a second block copolymer is formed on the substrate including the chemical pattern to form a nanostructure disposed entirely on the substrate.

The first and second block copolymers are substantially identical to each other.

The first and second block copolymers may have a lamella or cylinder.

The photoresist pattern may include barrier rib portions extending in a first direction of the substrate and repeatedly arranged in a second direction different from the first direction, wherein the first thin film and the sacrificial structure are formed between adjacent barrier rib portions. Can be.

In the method of manufacturing a nanostructure according to another embodiment of the present invention, a photoresist pattern including a convex portion and a concave portion repeatedly arranged in a first direction and extending in a second direction different from the first direction on a substrate do. A neutral layer is formed on a substrate including the photoresist pattern, and a nanostructure is formed of a thin film including a block copolymer on the substrate on which the neutral layer is formed.

The epithelial photoresist pattern forms pillar patterns extending in the second direction and spaced apart from each other in the first direction on the substrate, and then applying the photoresist composition on the substrate including the pillar patterns to form the convex portions; The recess can be formed.

Alternatively, the photoresist pattern may be formed using a halftone mask including a light blocking portion disposed on the convex portion and a halftone portion disposed on the concave portion.

In the method of manufacturing a nanostructure according to another embodiment of the present invention, forming a photoresist pattern on a substrate, the buffer structure comprising a buffer layer comprising a cylindrical block copolymer formed on the substrate including the photoresist pattern Form. A thin film including a plate-shaped block copolymer is formed on a substrate including the buffer structure, and the nanostructure is formed on the buffer structure with the thin film.

The photoresist pattern may include barrier rib portions extending in a first direction of the substrate and repeatedly arranged in a second direction different from the first direction. The buffer structure includes nano cylinders, half-cylinders and a substrate. The nanocylinders extend in the first direction and are disposed in the second direction between partition walls adjacent to each other. The half cylinders extend in the first direction and are disposed in the second direction on a substrate including the partition portions and the nano cylinders. The substrate is disposed between the nanocylinders and the half-cylinders.

In the method of manufacturing a pattern according to an embodiment for realizing another object of the present invention described above, a first block copolymer is formed on a substrate on which a mother thin layer, a neutral layer, and a photoresist pattern are sequentially formed. A first thin film is formed. The first thin film forms a sacrificial structure including a first sacrificial block and a second sacrificial block. The first sacrificial block is removed from the sacrificial structure. The neutral layer is oxidized using the second sacrificial block as a mask to form a chemical pattern. The second sacrificial block and the photoresist pattern are removed from the substrate including the chemical pattern. A second thin film including a second block copolymer is formed on a substrate including the chemical pattern, and the second thin film forms a nanostructure including a first nano block and a second nano block on the substrate. do. Subsequently, the first nanoblock is removed, and the thin film is patterned using the second nanoblock as a mask to form a pattern.

The pattern may have a grid shape.

The pattern may have a cylindrical shape.

In the method of manufacturing a pattern according to another embodiment of the present invention, a photoresist pattern is formed on a substrate including a metal layer. A buffer layer including a cylindrical block copolymer is formed on a substrate including the photoresist pattern, and a buffer structure is formed using the buffer layer. A thin film including a plate-shaped block copolymer is formed on a substrate including the buffer structure, and the thin film forms a nanostructure including a first nano block and a second nano block on the buffer structure. The buffer structure disposed under the first nanoblock and the first nanoblock is removed. The remaining buffer structure and the metal layer exposed through the second nanoblock are patterned to form a grid pattern.

In the method of manufacturing a pattern according to still another embodiment of the present invention, a photoresist pattern extending in a first direction of the substrate and including convex portions and concave portions repeatedly arranged in a second direction different from the first direction is formed. do. The metal layer and the neutral layer are sequentially formed on the substrate including the photoresist pattern. A thin film including a block copolymer is formed on a substrate on which the neutral layer is formed, and the thin film forms a nanostructure including a first nano block and a second nano block. After removing the first nanoblock, the metal layer is patterned using the second nanoblock as a mask to form a grid pattern.

In the method of manufacturing a pattern according to another embodiment of the present invention, the metal layer formed on the substrate is patterned to form a metal pattern including a first thickness portion and a second thickness portion lower than the first thickness portion. A buffer layer including a cylindrical block copolymer is formed on a substrate including the metal pattern, and a buffer structure is formed from the buffer layer. A preliminary layer including a plate-shaped block copolymer is formed on a substrate including the buffer structure, and a nanostructure including a first nanoblock and a second nanoblock is formed on the buffer structure using the preliminary layer. The buffer structure formed under the first nanoblock and the first nanoblock is removed. The remaining buffer structure and the metal pattern exposed through the second block are patterned to form a grid pattern.

According to the nanostructure of the present invention, a method of manufacturing the same, and a method of manufacturing a pattern using the same, it is possible to easily form a nanostructure continuously arranged on a large area substrate using a block copolymer. Thereby, productivity and manufacturing reliability of a nanostructure and a polarizing plate can be improved.

As the inventive concept allows for various changes and numerous modifications, the embodiments will be described in detail in the text. However, this is not intended to limit the present invention to the specific form disclosed, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention. Like reference numerals are used for like elements in describing each drawing. The terms first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another. The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "consist of" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described on the specification, but one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art and shall not be construed in ideal or excessively formal meanings unless expressly defined in this application. Do not.

In the accompanying drawings, the dimensions of the substrate, layer (film) or patterns are shown to be larger than actual for clarity of the invention. In the present invention, each layer (film), pattern or structures is referred to as being formed on the substrate, each layer (film) or patterns "on", "upper" or "lower". ), Meaning that the pattern or structures are formed directly above or below the substrate, each layer (film) or patterns, or another layer (film), another pattern or other structures may be further formed on the substrate.

Hereinafter, with reference to the accompanying drawings, it will be described in detail a preferred embodiment of the present invention. First, various nanostructures of the block copolymer will be described first with reference to FIG. 1, and then a method of forming nanostructures including the nanostructures and a method of manufacturing a pattern using the same will be described. The nanostructures are disclosed in Korean Patent Application No. 10-2007-0051020 (Republic of Korea Patent Publication No. 10-2008-0103812) filed by Korea Advanced Institute of Science and Technology. Nanostructures disclosed in the published patent are as follows.

1A to 1C are conceptual views illustrating various nanostructures of a block copolymer formed according to a composition ratio of a polymer.

Specifically, FIG. 1A is a state diagram that predicts a self-assembled nanostructure of a double block copolymer according to self-consistent mean field theory, and FIG. 1B shows a self-assembled nano structure of a double block copolymer formed according to a relative composition ratio of two blocks. It is shown. 1C is a state diagram verifying the shape of the self-assembled nanostructure of the double block copolymer experimentally according to the embodiment of the present invention.

In FIG. 1A, the x-axis represents f _A and the y-axis represents χ _N. N (degree of polymerization) is the size of the polymer, χ (segment interaction) is the interaction between the two blocks. When A represents a first polymer block and B represents a second polymer block other than the first polymer comprising A-block-A, f _A is defined as the relative composition ratio of A. f _B is defined as representing the relative composition ratio of B. Examples of the material forming the first polymer block include poly (methylmethacrylate), PMMA, poly (ethylene oxide), poly (ethylene oxide), PEO, and poly (vinylpyridine). (vinyl pyridine), PVP], poly (ethylene-art-propylene), [poly (ethylene-alt-propylene), PEP], polyisoprene [polyisoprene, PI], etc. are mentioned. As an example of the material which forms the said 2nd polymer block, polystyrene is mentioned.

Referring to FIG. 1A, when χ _N <10, block copolymers are formed randomly, and when 10 <χ _N <100, f _A = N _A / (N _A + N _B ) ≤ about 0.18 to 0.23 days At this time, a body-centered cubic sphere surrounded by a B block substrate is formed. In addition, when f _A ≤ about 0.30 to 0.35, the nanodomains forming the sphere form hexagonal lattices to form a nanostructure of cylinders, and f _A is further increased to 0.35≤ f _A When ≤ 0.40, a nanostructure of a gyroid is formed in which the cylinder forms are successively connected two by one. Finally, at f _A ≒ 0.5, lamellar nanostructures are formed.

In this regard, when f _B = N _B / (N _A + N _B ) ≤ about 0.18 to 0.23, a nanostructure of body centered cubic spheres surrounded by an A block substrate is formed. In addition, when f _B ≤ about 0.30 to 0.35, the nanodomains forming the sphere form hexagonal lattices to form a nanostructure of cylinders, and f _B is further increased to 0.35≤ f _B When ≤ 0.40, a nanostructure of a gyroid is formed in which the cylinder forms are successively connected two by one. Finally, at f _B ≒ 0.5, lamellar nanostructures are formed.

Referring to FIG. 1C, the graph shown in FIG. 1C shows a form similar to the graph of FIG. 1A, and it can be confirmed from the viewpoint of those skilled in the art that the results of FIG. 1C are included in the results of FIG. 1A.

Example 1

Nano structure

2 is a perspective view of a nanostructure manufactured according to Example 1 of the present invention.

The first nanostructure NS1 illustrated in FIG. 2 includes first nano blocks NB1 and second nano blocks NB2 formed on the base substrate 110. Nanostructure according to this embodiment is disclosed in Korean Patent Application No. 10-2008-126655 filed jointly by the applicant and the Korea Institute of Science and Technology. The nanostructure according to the present embodiment has a plate shape shown in FIG.

The first nano blocks NB1 extend in a first direction D1 of the base substrate 110 and are spaced apart from each other in a second direction D2 different from the first direction D1. The second direction D1 may be perpendicular to the first direction D1. The second nano blocks NB2 extend in the first direction D1 and are spaced apart from each other in the second direction D2. Each of the second nanoblocks NB2 is disposed between the first nanoblocks NB1 adjacent to each other.

Specific examples of the material for forming the first nanoblocks NB1 include poly (methylmethacrylate), PMMA, poly (ethylene oxide), PEO, and poly ( Vinyl pyridine) [poly (vinyl pyridine), PVP], poly (ethylene-art-propylene), [poly (ethylene-alt-propylene), PEP], polyisoprene (polyisoprene, PI) and the like. Specific examples of the material for forming the second nanoblocks NB2 may include polystyrene. The first nanostructure NS1 may include a block copolymer in which a polymer constituting the first nanoblocks NB1 and a polystyrene constituting the second nanoblocks NB2 are mixed at a composition ratio of about 50:50. It can form using.

The first nanostructure NS1 may further include a chemical pattern layer 122 formed on the base substrate 110. The chemical pattern layer 122 includes a chemical pattern 122a having hydrophilicity or hydrophobicity and a neutral pattern 122b having neutrality that is neither hydrophilic nor hydrophobic. The first region A1 of the base substrate 110 includes the neutral pattern 122b, and the second region A2 adjacent to the first region A2 includes the chemical pattern 122a and the neutral. Pattern 122b. The first region A1 is a region in which the photoresist pattern 132 (see FIG. 2B) is formed in the process of forming the first nanostructure NS1, and the second region A2 is the photoresist pattern 132. ) Is not formed so that the neutral layer 120 (see FIG. 2A) is exposed. In the second area A2, the chemical pattern 122a and the neutral pattern 122b are alternately disposed along the second direction D2.

Manufacturing method of nano structure

3A to 3F are perspective views illustrating a method of manufacturing the nanostructure shown in FIG. 2.

Referring to FIG. 3A, a neutral layer 120 is formed on the base substrate 110.

The base substrate 110 may include a glass substrate.

The neutral layer 120 has the first and second nano blocks NB1. NB2 on the base substrate 110 and has a perpendicularity in a direction perpendicular to the surface of the base substrate 110. You can grow. The neutral layer 120 is chemically neutral having neither hydrophilicity nor hydrophobicity. The neutral layer 120 includes an organic self-assembled monolayer (SAM), a polymer brush (Polymer Brush) and a cross-linked random copolymer mat (MAT) or cross-linked random copolymer mat (MAT), etc. It contains a monolayer.

Specific examples of the material for forming the self-assembled monolayer are pentyl trichlorosilane (PETCS), phenyl trichlorosilane (Phenyltrichlorosilane: PTCS), benzyltrichlorosilane (BZTCS), and toltrichlorosilane (Tolyltrichlorosilane: TTCS), 2-[(trimethoxysilyl) ethyl] -2-pyridine (2-[(trimethoxysilyl) ethl] -2-pyridine (PYRTMS)), 4-biphenylyltrimethowysilane: BPTMS), octadecyltrichlorosilane (OTS), 1-naphthyltrimehtoxysilane (NAPTMS), 1-[(trimethoxysilyl) methyl] naphthalene (1-[(trimethoxysilyl) methyl] naphthalene: MNATMS), (9-methylanthracenyl) trimethoxysilane ((9-methylanthracenyl) trimethoxysilane: MANTMS}, and the like.

Specific examples of the polymer brush include polystyrene-random-poly (methylmethacrylate), PS-random-PMMA.

Specific examples of the MAT include benzocyclobutene-functionalized polystyrene-random-poly (methacrylate) copolymer [Benzocyclobutene-functionalized polystyrene-r-poly (methacrylate) copolymer, P (sr-BCB-r-MMA)] Can be.

Although not illustrated, the surface of the base substrate 110 may be pretreated by using an acid solution in the base substrate 110 before forming the neutral layer 120. By the pretreatment, the affinity between the base substrate 110 and the neutral layer 120 can be improved. Examples of the acidic solution include hydrofluoric acid (HF).

In an embodiment of the present invention, the neutral layer 120 includes PS-Random-PMMA.

Referring to FIG. 3B, a photoresist pattern 132 is formed on the base substrate 110 on which the neutral layer 120 is formed. The photoresist pattern 132 is formed in the first region A1. The photoresist pattern 132 includes a first partition 132a and a second partition 132b. The first partition 132a and the second partition 132b extend along the first direction D1 and are disposed adjacent to each other in the second direction D2. The neutral layer 129 of the second region A2 is exposed by the first and second partition walls 132a and 132b.

As a method of forming the photoresist pattern, a photolithography process, a soft lithography process, a nanoimprint process, a scanning probe lithography process, or the like can be used.

In the photolithography process, the photoresist pattern 132 may be formed by forming a photoresist film on the neutral layer 120 and then developing the photoresist film by irradiating light from an upper portion of the mask. For example, the light source providing the light may be a g-line with a wavelength of about 436 nm, an h-line with a wavelength of about 405 nm, an i-line with a wavelength of about 365 nm, a KrF laser having a wavelength of about 248 nm, ArF lasers having a wavelength of about 193 nm or Deep Ultraviolet (DUV) using an wavelength of about 157 nm, X-rays, electron beams, and extreme ultraviolet rays having a wavelength of about 13.5 nm.

In the soft lithography process, the photoresist is printed by printing an alkanethiol solution using an elastomeric poly (dimethylsiloxane) stamp or an elasstomaric PDMS stamp on the photoresist film. The pattern 132 may be formed.

In the nanoimprint process, the photoresist pattern 132 may be formed by physically pressing the mold on which the pattern is formed in contact with the photoresist film by heat-treating the photoresist film.

In the scanning probe lithography process, the photoresist film may be deformed by applying a physical force directly to the surface of the photoresist film by using a fine tip. Accordingly, the photoresist pattern 132 may be formed.

The photoresist film may be formed of a compound that is typically used in the manufacture of semiconductors or liquid crystal displays. However, in the process of removing the first sacrificial block 144a (see FIG. 2D) in a subsequent process, it should not be damaged or removed by a material for removing the first sacrificial block 144a. Specific examples of the material for forming the photoresist film, a novolak-based resin, polyvinylphenol (PVP), acrylate (acrylate), norbornene (Norbornene) polymer, polytetrafluoroethylene (PTFE), silsesquioxane (Silsesquioxane ) Polymer, polymethylmethacrylate (PMMA), Terpolymer, Poly (1-butene sulfone), PBS, Novolac-based Positive Electron Resist (Novolac based Positive) electron Resist (NPR), poly (methyl-a-chloroacrylate-co-a-methyl styrene], poly (glycidyl methacrylate-co -Ethyl acrylate [poly (glycidyl methacrylate-co-ethyl acrylate)], polychloromethylstyrene (PCMS), etc. The photoresist pattern 132 is formed of an inorganic compound as it is formed of an organic compound Compared to Relatively removed from the base substrate 110 may be easy.

When the light source is a g-line, h-line, or I-line, the photoresist film is preferably formed using Norvolac polymer. When the light source is a KrF laser, PVP is used, and when the light source is an ArF laser, acrylate or norbornene polymer is preferably used. When the light source is a DUV or excimer laser, it is preferable to use PTFE or silsesquioxane polymer. In addition, when the light source is electron beam, X-ray, extreme ultraviolet ray or ion beam, PMMA, terpolymer, PBS, NPR, poly (methyl-a-chloroacrylate-co-a-methyl styrene, poly (glycidyl methacryl) Preference is given to using rate-co-ethyl acrylate or PCMS.

The photoresist pattern 132 controls the orientation of the block copolymer. The larger the aspect ratio of the photoresist pattern 132, the longer the correlation length of the block copolymer is, so that the alignment of the block copolymer is easy, and even when a thick block copolymer is used, the outside of the base substrate 110 is increased. Don't overflow The thickness of the photoresist pattern 132 according to the present invention may be about 100nm to about 1㎛. In addition, the distance between the first and second partitions 132a and 132b may be about 1 nm to about 900 nm.

Referring to FIG. 3C, a first thin film 142 including a first block copolymer is formed on the base substrate 110 including the photoresist pattern 132.

The first thin film 142 is formed on the neutral layer 120 in the second region A2. The block copolymer is a polymer in which two different types of monomers are covalently bonded. Two different monomers have different physical and chemical properties. Accordingly, any one first monomer has a relatively hydrophilicity compared to the other second monomer, and the second monomer has a relatively hydrophobicity compared to the first monomer. The first block copolymer according to the present invention includes polystyrene and a polymer covalently bonded with the polystyrene.

Specific examples of the first block copolymer include polystyrene-block-poly (methylmethacrylate) [polystyrene-block-poly (methylmethacrylate), PS-b-PMMA], polystyrene-block-poly (ethylene oxide) [polystyrene- block-poly (ethylene oxide), PS-b-PEO], polystyrene-block-poly (vinylpyridine) [polystyrene-block-poly (vinyl pyridine), PS-b-PVP], polystyrene-block-poly (ethylene- Art-propylene), [polystyrene-block-poly (ethylene-alt-propylene), PS-b-PEP], polystyrene-block-polyisoprene, PS-b-PI, etc. may be mentioned. .

In an embodiment of the invention, the first block copolymer comprises PS-b-PMMA.

Subsequently, the base substrate 110 including the first thin film 142 is heat treated. The heat treatment process may be performed at about 200 ° C. to about 300 ° C. for about 40 hours to about 60 hours.

Referring to FIG. 3D, the first thin film 142 is converted into a sacrificial structure 144 including a first sacrificial block 144a and a second sacrificial block 144b by the heat treatment.

The first block copolymer of the first thin film 142 is aligned along the first direction D1, and phase-separated into the polystyrene and the polymer along the second direction D2. Accordingly, a first sacrificial block 144a extending along the first direction D1 is formed, and is separated from the first sacrificial block 144a to form the second sacrificial block 144a. The second sacrificial block 144b disposed in D2) is formed. In an embodiment of the present invention, the first sacrificial block 144a includes a PMMA and the second sacrificial block 144b includes a PS.

The first block copolymer has a different shape according to the composition ratio of the first and second monomers. When the composition ratio of the polystyrene and the PS is about 50:50, the block copolymer has a lamella shape.

Referring to FIG. 3E, the first sacrificial block 144a is removed from the sacrificial structure 144. Accordingly, the second sacrificial block 144b and the photoresist pattern 132 remain on the neutral layer 120.

The first sacrificial block 144a may be removed through wet etching. For example, when the base substrate 110 including the sacrificial structure 144 is immersed in a solution containing acetic acid and then sonicated, only the first sacrificial block 144a may selectively select the sacrificial structure 144. ). In contrast, the first sacrificial block 144a may be removed through dry etching. For example, after irradiating the sacrificial structure 144 with ultraviolet rays, only the first sacrificial block 144a is selectively removed by a difference in etching selectivity through reactive ion etching (RIE). can do.

Subsequently, the neutral layer 120 is oxidized using the photoresist pattern 132 and the second sacrificial block 144b as a mask. For example, the neutral layer 120 may be selectively ion-etched using an oxygen plasma or oxidized using an ultraviolet ozone. In contrast, the neutral layer 120 may be oxidized using X-rays.

Referring to FIG. 3F, the chemical layer 122a is formed in a part of the second region A2 by oxidizing the neutral layer 120, and the chemical region 122a is formed in the remaining region except for the region in which the chemical pattern 122a is formed. The neutral pattern 122b having the properties of the neutral layer 120 as it is is formed.

Next, the second sacrificial block 144b and the photoresist pattern 132 are removed. For example, the base substrate 110 including the second sacrificial block 144b and the photoresist pattern 132 is immersed in a solution containing toluene, and then ultrasonically decomposed to form the second sacrificial block 144b. And the photoresist pattern 132 may be removed.

A second thin film including a second block copolymer is formed on the base substrate 110 on which the chemical pattern 122a is formed. The second block copolymer constituting the second thin film is substantially the same as the first block copolymer constituting the first thin film 142. The base substrate 110 including the second thin film is heat treated.

By the heat treatment, the first nano block NB1 is formed on the chemical pattern 122a, and the second nano block NB2 is formed on the neutral pattern 122b. Accordingly, the first nanostructure NS1 is formed on the base substrate 110.

A polymer having relatively hydrophilicity is disposed among the polymers constituting the second block copolymer on the chemical pattern 122a, and a polymer having relatively hydrophobicity is disposed on the neutral pattern 122b of the second region A2. Can be deployed. By aligning the hydrophilic polymer on the chemical pattern 122a, coupling is induced on the neutral pattern 122b of the second region A2 by the influence of the hydrophilic polymer to spontaneously have the hydrophobic polymer. May be aligned in the same direction as the direction in which the chemical pattern 122a is formed.

At the same time, on the neutral pattern 122b of the first area A1, the first and second parts are arranged on the neutral pattern 122b and the chemical pattern 122a of the second area A2. Coupling is induced by the influence of the nano blocks NB1 and NB2 so that the first and second nano blocks NB1 spontaneously from the edge of the first area A1 toward the center of the first area A1. , NB2) can be formed.

According to an embodiment of the present invention, in the PS-b-PMMA, since the PMMA is relatively more hydrophilic than the PS, the PMMA is disposed on the chemical pattern 122a to form the first nano block NB1. PS is disposed on the neutral pattern 122b to form the second nanoblock NB2.

As time passes, the first and second nano blocks NB1 and NB2 are formed on the front surface of the base substrate 110, and thus the first nanostructure NS1 is substantially formed on the front surface of the base substrate 110. ) Is formed.

According to the present embodiment, the sacrificial structure 144 is easily formed by using the first block copolymer by the photoresist pattern 132, and the photoresist pattern 132 and the sacrificial structure 144 are formed. The chemical pattern 122a may be formed by using. Accordingly, the second block copolymer may be uniformly aligned on the base substrate 110 having a large area, thereby easily forming the first nanostructure NS1.

Manufacturing method of the pattern

4A is a perspective view of a pattern manufactured using the nanostructure shown in FIG. 2.

4B is a cross-sectional view taken along the line II ′ of FIG. 4A.

The pattern shown in FIGS. 4A and 4B is a metal pattern constituting the first polarizing plate PL1. The grid pattern includes a first line 210a and a second line 210b formed on the base substrate 110. And 210.

The first and second lines 210a and 210b extend in the first direction D1 of the base substrate 110. The second line 210b is disposed in a second direction D2 different from the first direction D1 of the first line 210a. The first and second lines 210a and 210b are formed by patterning a metal layer. The metal layer may include aluminum, silver, platinum, or the like.

5A to 5C are cross-sectional views illustrating a method of manufacturing the pattern shown in FIG. 4B.

Referring to FIG. 5A, a metal layer 200 is formed on the base substrate 110 as a mother thin layer. For example, the metal layer 200 may include aluminum.

The neutral layer 120 and the photoresist pattern 132 are sequentially formed on the base substrate 110 including the metal layer 200. The photoresist pattern 132 includes a first partition 132a and a second partition 132b formed in the first region A1 of the base substrate 110. The neutral layer 120 on the second area A2 is exposed by the first and second partition walls 132a and 132b. The process of forming the photoresist pattern 132 is substantially the same as the process described with reference to FIG. 3B.

A sacrificial structure 144 is formed on the base substrate 110 including the photoresist pattern 132. The sacrificial structure 144 may be formed in substantially the same process as described in FIGS. 3C and 3D. Therefore, redundant description is omitted.

Subsequently, the first sacrificial block 144a of the sacrificial structure 144 is removed, and the neutral layer 120 is oxidized using the photoresist pattern 132 and the second sacrificial block 144b as a mask.

Referring to FIG. 5B, a portion of the neutral layer 120 is oxidized to form a chemical pattern layer 122, and the second sacrificial block 144b and the photoresist pattern on the chemical pattern layer 122 are formed. 132). The chemical pattern layer 122 is substantially the same as the chemical pattern layer described with reference to FIG. 3F. Therefore, redundant description is omitted.

Subsequently, a thin film including a block copolymer is formed on the base substrate 110 including the chemical pattern layer 122 and heat-treated to form a thin film including first and second nano blocks NB1 and NB2. 1 to form a nanostructure (NS1). Since the first nanostructure NS1 is substantially the same as the nanostructure described with reference to FIG. 2, a detailed description thereof will be omitted.

Referring to FIG. 5C, a chemical pattern 122a of the chemical pattern layer! 22 formed under the first nano block NB1 and the first nano block NB1 from the first nanostructure NS1. Remove it. Accordingly, the neutral pattern (! 22b) of the second nanoblock NB2 and the chemical pattern layer 122 remains on the metal layer 200.

The wire layer pattern 210 is formed by etching the exposed metal layer 200 using the second nanoblock NB2 as a mask. The second nano block NB2 and the neutral pattern 122b are removed after forming the wire grid pattern 210.

According to the present exemplary embodiment, the first nanostructure NS1 is formed using a block copolymer, and the metal layer 200 is patterned using the first nanostructure NS1 to form the wire grid pattern 210. To form. Accordingly, the wire grid pattern 210 having a nano size may be formed on the base substrate 110 having a large area, thereby improving manufacturing reliability and productivity of the first polarizing plate PL1.

Example 2

Nano structure

6 is a perspective view of a nanostructure manufactured according to Example 2 of the present invention.

The second nanostructure NS2 illustrated in FIG. 6 includes a first nanoblock NB1 and a second nanoblock NB2. The second nanostructure NS2 may further include a chemical pattern layer 122. The second nanostructure NS2 according to the present embodiment has a cylindrical shape shown in FIG. 1.

The first nano block NB1 has a cylindrical shape having a bottom surface in contact with the chemical pattern layer 122, and the second nano block NB2 has the first nano blocks NB1 disposed adjacent to each other. It is disposed between and surrounds the periphery of the first nano block (NB1). The first nano block NB1 includes a PMMA, and the second nano block NB2 includes a PS. In another aspect, the second nanoblock NB2 is substantially a substrate surrounding the first nanoblock NB1.

The chemical pattern layer 122 is substantially the same as the chemical pattern layer shown in FIG. 2. Therefore, redundant description is omitted.

Manufacturing method of nano structure

FIG. 7A is a perspective view illustrating a method of manufacturing the nanostructure shown in FIG. 6.

Referring to FIG. 7A, the photoresist pattern 132 including the neutral layer 120 and the first and second partition portions 132a and 132b is sequentially formed on the base substrate 110. The neutral layer 120 and the photoresist pattern 132 are substantially the same as described with reference to FIGS. 3A and 3B. Therefore, redundant description is omitted.

Subsequently, a thin film including a block copolymer is formed on the base substrate 110 including the photoresist pattern 132. The thin film may include PS-b-PMMA, and a composition ratio of PS and PMMA may be about 65:35 to 60:40. Alternatively, the composition ratio of PS and PMMA may be about 35:65 to 40:60.

The sacrificial structure 144 is formed by heat treating the base substrate 110 including the thin film. The sacrificial structure 144 includes a first sacrificial block 144a and a second sacrificial block 144b. The first sacrificial block 144a has a cylindrical shape like the first nano block NB1.

Subsequently, the first sacrificial block 144b is removed from the sacrificial structure 144 and the neutral layer 120 is oxidized using the photoresist pattern 132 and the second sacrificial block 144b as a mask. The chemical pattern layer 122 is formed.

The second sacrificial block 144b and the photoresist pattern 132 are removed, and a thin film including the block copolymer is formed on the chemical pattern layer 122. The second nanostructure NS2 illustrated in FIG. 6 may be easily formed on the base substrate 110 having a large area by heat-treating the thin film.

Manufacturing method of the pattern

FIG. 7B is a perspective view illustrating a pattern manufactured by using the nanostructure illustrated in FIG. 7A.

The pattern 310 illustrated in FIG. 7B is formed on the base substrate 110. The pattern 310 has a cylindrical shape substantially the same as the shape of the first nanoblock 144a of the second nanostructure NS2.

FIG. 7C is a perspective view illustrating a method of manufacturing a pattern in FIG. 7B.

Referring to FIG. 7C, the organic layer 300 is formed as a thin film on the base substrate 110, and the second nanostructure NS2 is formed on the organic layer 300. The process of forming the second nanostructure NS2 is substantially the same as described with reference to FIG. 6. Therefore, redundant description is omitted.

The first nanoblock NB1 is selectively removed from the second nanostructure NS2, and the organic layer 300 is patterned using the second nanoblock NB2 as a mask. Accordingly, the pattern 310 may be formed on the base substrate 110.

According to the present exemplary embodiment, the pattern 310 having a nano size may be formed on the base substrate 110 having a large area.

Example 3

Nano structure

8 is a perspective view of a nanostructure manufactured according to Example 3 of the present invention.

The third nanostructure NS3 illustrated in FIG. 8 includes a first nanoblock NB1 and a second nanoblock NB2. The third nanostructure NS3 may further include a photoresist pattern 134 and a neutral layer 120 sequentially formed on the base substrate 110. The neutral layer 120 is substantially the same as the neutral layer described with reference to FIG. 3A. Therefore, redundant description is omitted.

The first and second nano blocks NB1 and NB2 extend in a first direction D1 of the base substrate 110 and are repeatedly in a second direction D2 different from the first direction D1. Are arranged. The second direction D2 may be perpendicular to the first direction D1. The third nanostructure NS3 is substantially the same as the first nanostructure NS1 described with reference to FIG. 2 except that the third nanostructure NS3 is formed on the photoresist pattern 134. Therefore, redundant description is omitted.

The photoresist pattern 134 may include a convex portion 134a and a concave portion 134b that are repeatedly arranged along the first direction D1 and extend in the second direction D2. The recess 134b has a curvature, specifically, a half pipe shape. The distance between the convex portions 134a adjacent to each other may be about 1 μm to about 100 μm. The concave portion 134b may have a tangent of the concave portion 134b of about 3 ° to about 90 ° based on the surface of the base substrate 110.

Manufacturing method of nano structure

9A and 9B are perspective views illustrating a method of manufacturing the nanostructure shown in FIG. 8.

Referring to FIG. 9A, pillar patterns 133 are formed on the base substrate 110. The pillar patterns 133 extend in the second direction D2 and are spaced apart from each other in the first direction D1. The pillar patterns 133 are formed in regions corresponding to the convex portions 134a of the photoresist pattern 134.

Referring to FIG. 9B, the convex portion 134a is formed in a region where the light pattern 133 is formed by applying a photoresist composition on the base substrate 110 including the light pattern 133. . At the same time, the concave portion 134b is formed between the convex portions 134a adjacent to each other by the photoresist composition. Accordingly, the photoresist pattern 134 is formed on the base substrate 110.

Although not illustrated, the photoresist pattern 134 may be formed using a halftone mask. For example, after the photoresist composition is coated on the base substrate 110 by a predetermined thickness to form a photoresist film, the halftone mask is disposed on the base substrate 110 including the photoresist film. The photoresist film may be formed using a negative photoresist composition. The halftone mask includes a light blocking portion disposed on a region corresponding to the convex portion 134a and a halftone portion disposed on a region corresponding to the concave portion 134b. The photoresist pattern 134 may be formed by irradiating light onto the photoresist film from the upper halftone mask and then developing the photoresist film.

Alternatively, the photoresist pattern 134 may be formed using a slit mask in which the halftone part is replaced with a slit part including a plurality of slits.

Referring to FIG. 9C, the neutral layer 120 is formed on the base substrate 110 including the photoresist pattern 134. A thin film 145 including a block copolymer is formed on the base substrate 110 including the neutral layer 120. The block copolymer may include PS-b-PMMA having a plate shape.

Subsequently, the base substrate 110 including the thin film 145 is heat-treated to form the third nanostructure NS3. The principle in which the first and second nano blocks NB1 and NB2 are arranged in the first direction D1 is based on a difference in extinction rate of defects according to the thickness of the thin film 145. Since the block copolymer is vertically oriented at the interface between the neutral layer 120 and the thin film 145 by the neutral layer 120, the form of defects appearing at the interface is the entire thickness of the thin film 145. Penetrate Accordingly, the defect energy increases with the thickness of the thin film 145, and the defect energy imposes a gradient of defect extinction rate according to a thickness gradient. As a result, the first and second nano blocks NB1 and NB2 are formed from a thick portion of the thin film 145, for example, from the center of the recess 134b, to the thickness gradient during the heat treatment. Propagates accordingly. At the same time, the block copolymer may be phase-separated from PS and PMMA by diffusing in the second direction D2. That is, the directional domain growth occurs from the center of the concave portion 134b toward the convex portion 134a and phase separation may be performed to form the first and second nano blocks NB1 and NB2. Regarding the formation of the first and second nano blocks NB1 and NB2 by the thickness gradient, Korean Patent Application No. 10-2007-0066688 filed jointly by the present applicant and the Korea Advanced Institute of Science and Technology 10-2009-0001371).

Accordingly, the third nanostructure NS3 according to the present embodiment may be formed.

According to the present exemplary embodiment, the third nanostructure NS3 is easily formed by the photoresist pattern 134 without forming the sacrificial structure 144 and oxidizing the neutral layer 120 shown in FIG. 3D. Can be formed. In addition, instead of providing a thickness gradient to the thin film 145 using an imprinter, the thickness gradient may be provided by the photoresist pattern 134, resulting in a thickness gradient due to damage of the imprinter and inflow of foreign matter in the process. Problems such as a decrease in reliability can be prevented in advance.

Manufacturing method of the pattern

The pattern produced according to this embodiment is substantially the same as the pattern shown in Figs. 4A and 4B. Therefore, redundant description is omitted.

FIG. 9D is a perspective view illustrating a method of manufacturing a pattern using the nanostructure shown in FIG. 8.

Referring to FIG. 9D, the metal layer 200 is formed as a thin film on the base substrate 110, and the third nanostructure NS3 is formed on the metal layer 200. The process of forming the third nanostructure NS3 is substantially the same as described with reference to FIGS. 9A to 9C. Therefore, redundant description is omitted.

The first nanoblock NB1 is selectively removed from the third nanostructure NS3, and the photoresist pattern 134, the neutral layer 120, and the second nanoblock NB2 are used as masks. The metal layer 200 is patterned. Accordingly, the wire grid pattern 210 may be formed on the base substrate 110. After the wire grid pattern 210 is formed, the photoresist pattern 134 and the neutral layer 120 remaining on the base substrate 110 are removed.

According to the present exemplary embodiment, the grid pattern 210 having a nano size may be formed on the base substrate 110 having a large area.

Example 4

Nanostructures and Methods for Manufacturing the Same

The nanostructure according to the present embodiment is substantially the same as the third nanostructure NS3 shown in FIG. 8, and the manufacturing method of the nanostructure is substantially the same as the method described with reference to FIGS. 9A to 9C. Therefore, redundant description is omitted.

Manufacturing method of the pattern

10 is a perspective view of a pattern made according to Example 4 of the present invention.

The pattern shown in FIG. 10 is a metal pattern constituting the second polarizing plate PL2, and includes a wire grid pattern 220 including a first line 220a and a second line 220b formed on the base substrate 110. It includes.

The second polarizing plate PL2 may further include a photoresist pattern 134 formed under the wire grid pattern 220. The photoresist pattern 134 is arranged in a first direction D1 and includes a convex portion 134a and a concave portion 134b extending in a second direction D2 different from the first direction D1. . The concave portion 134b has a curvature and specifically has a half pipe shape.

The grid pattern 220 is formed on the photoresist pattern 134. The grid pattern 220 includes a first line 220a and a second line 220b extending in the first direction D1 of the base substrate 110. The first and second lines 220a and 220b are disposed adjacent to each other in a second direction D2 different from the first direction D1. The wire grid pattern 220 is formed along a bend formed by the convex portion 134a and the concave portion 134b of the photoresist pattern 134.

Although not illustrated in the drawings, an overcoat layer may be further formed on the base substrate 110 including the wire grid pattern 220 to planarize and protect the second polarizing plate PL2.

FIG. 11 is a perspective view illustrating a method of manufacturing the pattern shown in FIG. 10.

Referring to FIG. 11, the photoresist pattern 134 is formed on the base substrate 110. The photoresist pattern 134 may be manufactured in substantially the same manner as the photoresist pattern described with reference to FIGS. 9A and 9B. Therefore, redundant description is omitted.

The metal layer 200 is formed on the base substrate 110 on which the photoresist pattern 134 is formed, and the neutral layer 120 is formed on the metal layer 200. The neutral layer 120 is substantially the same as the neutral layer described with reference to FIG. 3A. Therefore, duplicate descriptions are omitted.

A thin film 145 including a block copolymer is formed on the base substrate 110 including the neutral layer 120. The block copolymer may include PS-b-PMMA having a plate shape. The thin film 145 is heat-treated to form a nanostructure. The nanostructure according to the present embodiment is substantially the same as the third nanostructure NS3 illustrated in FIG. 8, and is formed in the same manner as the third nanostructure NS3. Therefore, redundant description is omitted.

Subsequently, the first nano block NB1 of the third nanostructure NS3 is removed, and only the second block NB2 is left on the metal layer 200. The wire grid pattern 220 is formed by etching the metal layer 200 using the second nanoblock NB2 as a mask. Accordingly, the second polarizing plate PL2 including the photoresist pattern 134 and the wire grid pattern 220 may be manufactured on the base substrate 110.

According to the present exemplary embodiment, the third nanostructure NS3 is easily formed by the photoresist pattern 134 without forming the sacrificial structure 144 and oxidizing the neutral layer 120 shown in FIG. 3D. Can be formed. Accordingly, the wire grid pattern 220 having a nano size may be formed on the base substrate 110 having a large area.

Example 5

Nanostructures and Methods for Manufacturing the Same

The nanostructure according to the present embodiment is substantially the same as the third nanostructure NS3 shown in FIG. 8, and the manufacturing method of the nanostructure is substantially the same as the method described with reference to FIGS. 9A to 9C. Therefore, redundant description is omitted.

Manufacturing method of the pattern

12A is a perspective view of a pattern made according to Example 5 of the present invention.

FIG. 12B is a cross-sectional view taken along the line II-II 'of FIG. 12A.

12A and 12B are metal patterns constituting the third polarizing plate PL3 and include a grid pattern including a first line 220a and a second line 220b formed on the base substrate 110. 220. The third polarizer PL3 may further include a photoresist pattern 134, a neutral layer 120, and a residual block 146. The third polarizer PL3 is substantially the same as the second polarizer PL2 illustrated in FIG. 10 except for the neutral layer 120 and the residual block 146. Therefore, redundant description is omitted.

The neutral layer 120 is formed on the base substrate 110 on which the photoresist pattern 134 is formed. The neutral layer 120 is substantially the same as the neutral layer described with reference to FIG. 3A. Therefore, redundant description is omitted.

The residual block 146 is a residue of the nanostructure formed in the process of forming the wire grid pattern 220. The residual block 146 may include, for example, a PS. The residual block 146 is formed between the first line 220a and the second line 220b disposed adjacent to each other of the wire grid pattern 220.

13A and 13B are cross-sectional views illustrating a method of manufacturing the pattern shown in FIG. 12B.

Referring to FIG. 13A, the photoresist pattern 134 is formed on the base substrate 110. The neutral layer 120 is formed on the base substrate 110 on which the photoresist pattern 134 is formed. A third nanostructure NS3 including a first nanoblock NB1 and a second nanoblock NB2 is formed on the base substrate 110 on which the neutral layer 120 is formed. The third nanostructure NS3 is formed in substantially the same manner as the nanostructure shown in FIG. 8 and substantially the same as a method of manufacturing the same. Therefore, redundant description is omitted.

Referring to FIG. 13B, the first nanoblock NB1 is removed from the third nanostructure NS3, and the second nanoblock NB2, the neutral layer 120, and the photoresist pattern 132 are removed. The metal layer 200 is formed on the base substrate 110. The metal layer 200 is formed on the second nanoblock NB2, and is formed on the neutral layer 120 between the second nanoblocks NB2 adjacent to each other.

Subsequently, the metal layer formed on the second nanoblock NB2 by removing a portion of the second nanoblock NB2 along the virtual cutting line CL crossing the upper end of the second nanoblock NB2. 200 is also removed. Accordingly, the metal layer 200 remains only on the neutral layer 120 between the second nano blocks NB2, so that the wire grid pattern 220 is formed. The second nano block NB2 remaining on the base substrate 110 is defined as the residual block 146 of the third polarizer PL3. A portion of the second nano block NB2 may be removed through dry etching.

Accordingly, the third polarizing plate PL3 according to the present exemplary embodiment may be manufactured.

In another embodiment, the second nanoblock NB2 may be removed to form the second polarizing plate PL2 illustrated in FIG. 10 using the method described with reference to FIG. 11.

Example 6

Nanostructures and Methods for Manufacturing the Same

The nanostructure according to the present embodiment is substantially the same as the third nanostructure NS3 shown in FIG. 8, and the manufacturing method of the nanostructure is substantially the same as the method described with reference to FIGS. 9A to 9C. Therefore, redundant description is omitted.

Manufacturing method of the pattern

14 is a sectional view of a pattern made according to Example 6 of the present invention.

The pattern illustrated in FIG. 14 is a metal pattern constituting the fourth polarizing plate PL4, and includes a wire grid pattern 230 including a first line 230a and a second line 230b formed on the base substrate 110. It includes. The fourth polarizing plate PL4 may further include a photoresist pattern 134, a neutral layer 120, and a residual structure 148. The fourth polarizer PL4 is substantially the same as the second polarizer PL2 shown in FIG. 10 except for the neutral layer 120 and the residual structure 148. Therefore, redundant description is omitted.

The residual structure 148 includes a first remaining portion 148a formed under the wire grid pattern 230 and a second remaining portion 148b formed on the neutral layer 148b. The wire grid pattern 230 is formed on the first residual portion 148a, and the second grid line 230 is disposed between the first and second lines 230a and 230b spaced apart from each other. The remaining portion 148b is disposed.

The height of the first remaining portion 148a is relatively lower than the height of the second remaining portion 148b based on a virtual parallel line connecting the convex portions 134a of the photoresist pattern 134. The heights of the first and second remaining portions 148a and 148b from the surface of the base substrate 110 to the parallel lines are substantially the same, but the degree of protruding from the parallel lines is extended to the first remaining portions 148a. In comparison, the second residual portion 148b is larger. The first remaining portion 148a preferably has a thickness substantially equal to a height of at least the surface of the base substrate 110 and the parallelism. Accordingly, the wire lattice pattern 230 in which the first residual portion 148a fills the recess 134b and is disposed on the recess 134b is substantially parallel to the surface of the base substrate 110. It shows the effect formed on one side.

15A, 15B, and 15C are cross-sectional views for describing a method of manufacturing the pattern shown in FIG. 14.

Referring to FIG. 15A, the photoresist pattern 134, the neutral layer 120, and the third nanostructure NS3 are sequentially formed on the base substrate 110. The photoresist pattern 134, the neutral layer 120, and the third nanostructure NS3 may be formed in substantially the same method as described with reference to FIG. 13A. Therefore, redundant description is omitted.

Referring to FIG. 15B, a portion of the first nano block NB1 is removed from the third nanostructure NS3. Accordingly, the first nano block NB1 is removed by a predetermined thickness to form the first residual part 148a.

Referring to FIG. 15C, a metal layer 200 is formed on the base substrate 110 including the first residue 148a and the second nanoblock NB2 of the third nanostructure NS3. The metal layer 200 is formed on the first residual part 148a and the second nano block NB2.

Subsequently, the metal layer formed on the second nanoblock NB2 by removing a portion of the second nanoblock NB2 along the virtual cutting line CL crossing the upper end of the second nanoblock NB2. 200 is also removed. Accordingly, the metal layer 200 remains only on the first remaining portion 148a, so that the wire grid pattern 220 is formed. The second nano block NB2 remaining on the base substrate 110 is defined as the second residual part 148b of the residual structure 148. A portion of the second nano block NB2 may be removed through dry etching.

Accordingly, the fourth polarizing plate PL4 according to the present exemplary embodiment may be manufactured.

According to the present exemplary embodiment, the third nanostructure NS3 is easily formed by the photoresist pattern 134 without forming the sacrificial structure 144 and oxidizing the neutral layer 120 shown in FIG. 3D. Can be formed. As the residual structure 148 is formed using the third nanostructure NS3, the wire grid pattern 220 may be formed on a surface parallel to the surface of the base substrate 110. Accordingly, it is possible to prevent the polarization reliability from being lowered due to the bending of the photoresist pattern 134. Accordingly, productivity and manufacturing reliability of the fourth polarizing plate PL4 can be improved.

Example 7

Nano structure

16 is a perspective view of a nanostructure manufactured according to Example 7 of the present invention.

The fourth nanostructure NS4 illustrated in FIG. 16 includes a first nanoblock NB1 and a second nanoblock NB2. The fourth nanostructure NS4 may further include a buffer structure 145 and a photoresist pattern 132 formed on the base substrate 110.

The first and second nano blocks NB1 and NB2 are substantially the same as the first nano structure NS1 illustrated in FIG. 2 except that the first and second nano blocks NB2 and NB2 are formed on the buffer structure 145. Therefore, redundant description is omitted.

The photoresist pattern 132 is formed between the buffer structure 145 and the base substrate 110. The photoresist pattern 132 is formed in the first area A1 of the base substrate 110 and exposes the second area A2 between the first areas A1 adjacent to each other.

The buffer structure 145 includes nano cylinders 145a, half cylinders 145c and a substrate 145b. The nano cylinders 145a and the half cylinders 145c extend in a first direction D1 of the base substrate 110 and are parallel to a second direction D2 different from the first direction D2. Is arranged.

The nano cylinders 145a are disposed in the second area A2. That is, the nanocylinders 145a are disposed between the first partition 132a and the second partition 132b disposed adjacent to each other of the photoresist pattern 132. The half cylinders 145c are disposed on the base substrate 110 including the photoresist pattern 132 and the nano cylinders 145a. The half cylinders 145c have a half shape of the nanocylinders 145a. The substrate 145b is disposed between the nanocylinders 145a and the half cylinders 145c to allow the buffer structure 145 to form one film.

Manufacturing method of nano structure

FIG. 17 is a cross-sectional view for describing a method of manufacturing the nanostructure illustrated in FIG. 16.

The photoresist pattern 132 is formed on the base substrate 110. The photoresist pattern 132 is formed in the first region A1. The photoresist pattern 132 may be formed in substantially the same manner as the photoresist pattern illustrated in FIG. 3C except that the photoresist pattern 132 is directly formed on the base substrate 110. Therefore, redundant description is omitted.

Meanwhile, the height of the photoresist pattern 132 may be about 1.5 times the distance between the center points of the nanocylinders 145a disposed adjacent to each other in the buffer structure 145. As a result, the half cylinders 145c may be disposed on the nanocylinders 145a.

Subsequently, a buffer layer including a cylindrical block copolymer is formed on the base substrate 110 on which the photoresist pattern 132 is formed. The buffer layer is heat-treated to form the buffer structure 145. The cylindrical block copolymer comprises PS-b-PMMA, the nanocylinder 145a and the half cylinder 145c comprise PMMA, and the substrate 145b comprises PS.

A thin film including a plate-shaped block copolymer is formed on the base substrate 110 including the buffer structure 145. The thin film is heat-treated to form the fourth nanostructure NS4 including the first and second nano blocks NB1 and NB2 in the buffer structure 145. The first nano block NB1 is formed on the substrate 145b, and the second nano block NB2 is formed on the half cylinder 145c.

Accordingly, the fourth nanostructure NS4 illustrated in FIG. 16 may be formed.

According to the present exemplary embodiment, the fourth nanostructure NS4 may be easily formed on the base substrate 110 by forming the buffer structure 145 without forming a neutral layer or a chemical pattern layer. . Since the cylindrical block copolymer has better mobility than the plate-shaped block copolymer, when the thin film including the plate-shaped block copolymer is formed within a short time after the buffer structure 145 is formed, the cylindrical block copolymer may be quickly formed. The fourth nanostructure NS4 may be formed.

Manufacturing method of the pattern

The pattern according to this embodiment is substantially the same as the pattern shown in Figs. 4A and 4B. Therefore, detailed description is omitted.

18A, 18B and 18C are cross-sectional views illustrating a method of manufacturing a pattern using the nanostructure shown in FIG. 16.

Referring to FIG. 18A, a metal layer 200 is formed on the base substrate 110, and a photoresist pattern 132 is formed on the metal layer 200. A buffer layer including a cylindrical block copolymer is formed on the base substrate 110 on which the photoresist pattern 132 is formed. The buffer layer is heat-treated to form the buffer structure 145. The buffer structure 145 is substantially the same as the buffer structure described with reference to FIG. 17. Therefore, redundant description is omitted.

Referring to FIG. 18B, a fourth nanostructure NS4 is formed on the base substrate 110 including the buffer structure 145. The fourth nanostructure NS4 is substantially the same as the nanostructure described with reference to FIG. 16. Therefore, redundant description is omitted.

Referring to FIG. 18C, the first nano block NB1 of the fourth nanostructure NS4, the substrate 145b disposed under the first nano block NB1, and the nano cylinder 145a are removed. For example, the first nano block NB1, a portion of the substrate 145b and the nano cylinder 145a may be removed using an oxygen plasma. Accordingly, a part of the substrate 145b, the half cylinder 145c and the second nano block NB2 remain on the metal layer 200. A portion of the metal layer 200 is exposed through the remaining fourth nanostructure NS4.

Subsequently, the metal layer 200 may be etched using the remaining fourth nanostructure NS4 as a mask to manufacture the pattern illustrated in FIGS. 4A and 4B.

According to the present exemplary embodiment, the fourth nanostructure NS4 is easily formed on the large sized base substrate 110 by forming the buffer structure 145 without forming a neutral layer or a chemical pattern layer. can do. Accordingly, productivity and manufacturing reliability of the first polarizing plate PL1 can be improved.

Example 8

Nanostructures and Methods for Manufacturing the Same

The nanostructure according to the present embodiment is substantially the same as the nanostructure shown in FIG. 16 except that the photoresist pattern 132 is not included. Therefore, redundant description is omitted.

Manufacturing method of the pattern

19A is a perspective view of a pattern made according to Example 8 of the present invention.

19B is a cross-sectional view taken along the line III-III ′ of FIG. 19A.

The pattern shown in FIGS. 19A and 19B is a metal pattern constituting the fifth polarizing plate PL5 and includes a first grid including first and second lines 230a and 230b formed on the base substrate 110. A second grid pattern 240 including a pattern 230 and third and fourth lines 240a and 240b may be included. The first wire grid pattern 230 has a first thickness a, and the second wire grid pattern 240 has a second thickness b. The second thickness b is relatively thin compared to the first thickness a.

20A to 20D are cross-sectional views for describing a method of manufacturing the pattern shown in FIG. 19B.

Referring to FIG. 20A, a metal pattern MP of the base substrate 110 is formed. The metal pattern MP includes a first thickness part TH1 having the first thickness a and a second thickness part TH2 having the second thickness b. The metal pattern MP may be formed by forming a metal layer and a photoresist pattern (not shown) on the base substrate 110 and etching the metal layer using the photoresist pattern as an etch stop layer.

Referring to FIG. 20B, a buffer layer (not shown) including a cylinder block copolymer is formed on the base substrate 110 including the metal pattern MP, and the buffer layer is heat-treated to form a buffer structure 145. To form. The buffer structure 145 is substantially the same as the buffer structure shown in FIG. 17. Therefore, redundant description is omitted.

Referring to FIG. 20C, a thin film including a plate-shaped block copolymer is formed on the base substrate 110 including the buffer structure 145. The thin film is heat-treated to form the fourth nanostructure NS4 including the first and second nano blocks NB1 and NB2 in the buffer structure 145. The first nano block NB1 is formed on the substrate 145b, and the second nano block NB2 is formed on the half cylinder 145c.

Referring to FIG. 20D, the first nano block NB1 and the buffer structure 145 formed under the first nano block NB1 are removed. Accordingly, the first nano block NB1 of the fourth nanostructure NS4, the substrate 145b disposed under the first nano block NB1, and the nano cylinder 145a are removed.

For example, the first nano block NB1, a portion of the substrate 145b and the nano cylinder 145a may be removed using an oxygen plasma. Accordingly, a part of the substrate 145b, the half cylinder 145c and the second nano block NB2 remain on the metal layer 200. The metal pattern MP is exposed through the remaining fourth nanostructure NS4.

Subsequently, the metal pattern MP is etched using the remaining fourth nanostructure NS4 as an etch stop layer, and the fourth nanostructure NS4 is removed. Accordingly, the fifth polarizing plate PL5 including the first and second wire grid patterns 230 and 240 may be manufactured.

Manufacturing Example-1

Hereinafter, an example of manufacturing a nanostructure according to the method of manufacturing a nanostructure according to Example 1 will be described.

First, the surface of the silicon substrate was cleaned using a pyranha treatment method. The piranha treatment method was carried out by immersing the silicon substrate in a mixed solution of sulfuric acid and hydrogen peroxide in a ratio of about 7: 3 and treating it at about 110 ° C. for 1 hour.

PS-r-PMMA was spincoated on the cleaned silicon substrate, heat treated at about 160 ° C. for about 48 hours, and then washed with toluene to form a neutral layer having a thickness of about 6 nm.

After spin coating a SU8 (trade name, MicroChem Corp., USA) photoresist composition on the silicon substrate including the neutral layer, the resultant was exposed using an I-line aligner (Midas, MDA-6000 DUV, Korea). A photoresist pattern about 300 nm high and about 300 to about 800 nm wide was formed.

On the substrate on which the photoresist pattern was formed, spin-coated PS-b-PMMA (polystyrene-b-poly methyl methacrylate), which is a block copolymer, was heat-treated at about 250 ° C. for about 48 hours to form a sacrificial structure. The ratio of the molecular weight of PS-b-PMMA was PS: PMMA = 52,000: 52,000, and fA of PMMA was about 0.5.

After selectively removing the PMMA from the sacrificial structure, the neutral layer was oxidized using the photoresist pattern and the PS as a mask. Thereafter, the silicon substrate including the photoresist pattern and the PS was immersed in toluene, and then sonicated. Subsequently, PS-b-PMMA having a plate shape on the silicon substrate was spin coated and heat treated at about 250 ° C. to form nanostructures.

As a result of observing the nanostructure, it was confirmed that hydrophilic PMMA is disposed on the oxidized neutral layer and relatively hydrophobic PS is disposed in the remaining portion. In addition, it was confirmed that the PMMA and the PS are aligned in one direction as shown in FIG. 3D on the silicon substrate.

Manufacturing Example-2

Hereinafter, an example of manufacturing a nanostructure according to the method of manufacturing a nanostructure according to Example 2 will be described.

First, the surface of the silicon substrate was cleaned using a pyranha treatment method. The piranha treatment method was carried out by immersing the silicon substrate in a mixed solution of sulfuric acid and hydrogen peroxide in a ratio of about 7: 3 and treating it at about 110 ° C. for 1 hour.

PS-r-PMMA was spincoated on the cleaned silicon substrate, heat treated at about 160 ° C. for about 48 hours, and then washed with toluene to form a neutral layer having a thickness of about 6 nm.

After spin coating a SU8 (trade name, MicroChem Corp., USA) photoresist composition on the silicon substrate including the neutral layer, the resultant was exposed using an I-line aligner (Midas, MDA-6000 DUV, Korea). A photoresist pattern about 300 nm high and about 300 to about 800 nm wide was formed.

On the substrate on which the photoresist pattern was formed, spin-coated PS-b-PMMA (polystyrene-b-poly methyl methacrylate), which is a block copolymer, was thermally treated at about 250 ° C. for about 48 hours to form a sacrificial structure. The ratio of the molecular weight of PS-b-PMMA was PS: PMMA = 46,000: 21,000, and fA of PMMA was about 0.31.

After selectively removing the PMMA from the sacrificial structure, the neutral layer was oxidized using the photoresist pattern and the PS as a mask. Thereafter, the silicon substrate including the photoresist pattern and the PS was immersed in toluene, and then sonicated. Subsequently, PS-b-PMMA having a plate shape on the silicon substrate was spin coated and heat treated at about 250 ° C. to form nanostructures.

As a result of observing the nanostructure, it was confirmed that hydrophilic PMMA is disposed on the oxidized neutral layer and relatively hydrophobic PS is disposed in the remaining portion. In addition, it was confirmed that the PMMA is aligned as shown in Figure 7a in the cylindrical form.

According to the present invention, a nanostructure can be easily formed using a block copolymer on a large-area substrate. The nanostructures can be used for the manufacture of polarizing plates including wire grids, the formation of reflective lenses in reflective liquid crystal displays, and the like.

In addition, the nanostructure is a nanowire transistor, a mold for manufacturing a memory, a mold for electrical and electronic components such as a nanostructure for nanoscale patterning of wire, a mold for etching a solar cell and a fuel cell, an etching mask And molds for manufacturing organic diode (OLED) cells and molds for manufacturing gas sensors.

Moreover, the manufacturing method of the said polarizing plate can be used not only for manufacture of the polarizing plate which is an independent member, but also for formation of the polarizing part integrated with a display panel. That is, it can use for the process of forming a polarizing part directly on the array substrate containing a thin film transistor, or a color filter substrate.

Although described with reference to the embodiments above, those skilled in the art will understand that the present invention can be variously modified and changed without departing from the spirit and scope of the invention as set forth in the claims below. Could be.

1A to 1C are conceptual views illustrating various nanostructures of a block copolymer formed according to a composition ratio of a polymer.

2 is a perspective view of a nanostructure manufactured according to Example 1 of the present invention.

3A to 3F are perspective views illustrating a method of manufacturing the nanostructure shown in FIG. 2.

4A is a perspective view of a pattern manufactured using the nanostructure shown in FIG. 2.

4B is a cross-sectional view taken along the line II ′ of FIG. 4A.

5A to 5C are cross-sectional views illustrating a method of manufacturing the pattern shown in FIG. 4B.

6 is a perspective view of a nanostructure manufactured according to Example 2 of the present invention.

FIG. 7A is a perspective view illustrating a method of manufacturing the nanostructure shown in FIG. 6.

FIG. 7B is a perspective view illustrating a pattern manufactured by using the nanostructure illustrated in FIG. 7A.

FIG. 7C is a perspective view illustrating a method of manufacturing a pattern in FIG. 7B.

8 is a perspective view of a nanostructure manufactured according to Example 3 of the present invention.

9A and 9B are perspective views illustrating a method of manufacturing the nanostructure shown in FIG. 8.

FIG. 9D is a perspective view illustrating a method of manufacturing a pattern using the nanostructure shown in FIG. 8.

10 is a perspective view of a pattern made according to Example 4 of the present invention.

FIG. 11 is a perspective view illustrating a method of manufacturing the pattern shown in FIG. 10.

12A is a perspective view of a pattern made according to Example 5 of the present invention.

FIG. 12B is a cross-sectional view taken along the line II-II 'of FIG. 12A.

13A and 13B are cross-sectional views illustrating a method of manufacturing the pattern shown in FIG. 12B.

14 is a sectional view of a pattern made according to Example 6 of the present invention.

15A, 15B, and 15C are cross-sectional views illustrating a method of manufacturing the pattern shown in FIG. 14.

16 is a perspective view of a nanostructure manufactured according to Example 7 of the present invention.

FIG. 17 is a cross-sectional view for describing a method of manufacturing the nanostructure illustrated in FIG. 16.

18A, 18B and 18C are cross-sectional views illustrating a method of manufacturing a pattern using the nanostructure shown in FIG. 16.

19A is a perspective view of a pattern made according to Example 8 of the present invention.

19B is a cross-sectional view taken along the line III-III ′ of FIG. 19A.

20A to 20D are cross-sectional views for describing a method of manufacturing the pattern shown in FIG. 19B.

<Explanation of symbols for the main parts of the drawings>

110: base substrate 120: neutral layer

NS1, NS2, NS3, NS4: First, Second, Third, and Fourth Nanostructures

144: sacrificial structure 122: chemical pattern layer

144a and 144b: first and second sacrificial blocks NB1 and NB2: first and second nanoblocks

132 and 134: photoresist patterns 132a and 132b: first and second partition walls

134a: convex portion 134b: concave portion

145: buffer structure 145a: nano cylinder

145b: substrate 145c: half cylinder

Claims (23)

Forming a photoresist pattern on the substrate including the neutral layer; Forming a sacrificial structure including a first sacrificial block and a second sacrificial block with a first thin film including a first block copolymer formed on a substrate including the photoresist pattern; Removing the first sacrificial block from the sacrificial structure; Oxidizing the neutral layer to form a chemical pattern using the second sacrificial block as a mask; Removing the second sacrificial block and the photoresist pattern from the substrate including the chemical pattern; And A second thin film comprising a second block copolymer formed on a substrate including the chemical pattern, the method of manufacturing a nanostructure comprising the step of forming a nanostructure disposed entirely on the substrate. The method of claim 1, wherein the first and second block copolymers have a lamellar. The method of claim 1, wherein the first and second block copolymers have a cylindrical shape. The photoresist pattern of claim 1, wherein the photoresist pattern includes partition walls extending in a first direction of the substrate and repeatedly arranged in a second direction different from the first direction. And the first thin film and the sacrificial structure are formed between adjacent partition walls. Forming a photoresist pattern on the substrate, the photoresist pattern including convex portions and concave portions repeatedly arranged in a first direction and extending in a second direction different from the first direction; Forming a neutral layer on the substrate including the photoresist pattern; And Method of manufacturing a nanostructure comprising the step of forming a nanostructure with a thin film comprising a block copolymer formed on the substrate on which the neutral layer is formed. The method of claim 5, wherein the forming of the photoresist pattern is performed. Forming pillar patterns extending in the second direction and spaced apart from each other in the first direction on the substrate; Forming a convex portion in a region where the pillar patterns are formed by applying a photoresist composition on a substrate including the pillar patterns; And A method of manufacturing a nanostructure, characterized in that it comprises forming a recess between the adjacent pillar pattern. The method of claim 5, wherein the photoresist pattern is And a halftone mask including a light blocking portion disposed on the convex portion and a halftone portion disposed on the concave portion. The method of claim 5, wherein the nanostructures The block copolymer is a method of manufacturing a nanostructure, characterized in that formed by spontaneous alignment by a thickness gradient (thickness gradient) by the photoresist pattern. The method of claim 5, wherein the nanostructure comprises a first nanoblock aligned in the second direction and a second nanoblock disposed in the first direction of the first nanoblock, And the first and second blocks are repeatedly arranged along the first direction. Forming a photoresist pattern on the substrate; Forming a buffer structure with a buffer layer including a cylindrical block copolymer formed on a substrate including the photoresist pattern; And Forming a nanostructure on the buffer structure with a thin film comprising a plate-shaped block copolymer formed on a substrate comprising the buffer structure. The method of claim 10, wherein the photoresist pattern is And a partition portion extending in a first direction of the substrate and repeatedly arranged in a second direction different from the first direction. The method of claim 11, wherein the buffer structure is Nano-cylinders extending in the first direction and disposed in the second direction between partition walls adjacent to each other; Half-cylinders extending in the first direction and disposed in the second direction on a substrate including the partition portions and the nanocylinders; And And a substrate disposed between the nanocylinders and the half-cylinders. The method of claim 12, wherein the nanostructures are And a first nanoblock and a second nanoblock extending in the first direction and corresponding to each of the half-cylinders and repeatedly arranged in the second direction. Forming a sacrificial structure including a first sacrificial block and a second sacrificial block from a first thin film including a first block copolymer formed on a substrate on which a thin film, a neutral layer, and a photoresist pattern are sequentially formed; Removing the first sacrificial block from the sacrificial structure; Oxidizing the neutral layer using the second sacrificial block as a mask to form a chemical pattern; Removing the second sacrificial block and the photoresist pattern from the substrate including the chemical pattern; Forming a nanostructure including a first nanoblock and a second nanoblock on the substrate using a second thin film including a second block copolymer formed on a substrate including the chemical pattern; Removing the first nanoblock; And And patterning the thin film using the second nanoblocks as a mask to form a pattern. Forming a photoresist pattern extending in a first direction of the substrate and including convex portions and concave portions repeatedly arranged in a second direction different from the first direction; Sequentially forming a thin film and a neutral layer on the substrate including the photoresist pattern; Forming a nanostructure including a first nanoblock and a second nanoblock as a thin film including a block copolymer formed on the substrate on which the neutral layer is formed; Removing the first nanoblock; And And patterning the thin film using the second nanoblock as a mask to form a pattern. Forming a photoresist pattern on the substrate, the photoresist pattern including a convex portion and a concave portion arranged in a first direction and extending in a second direction different from the first direction; Forming a neutral layer on the substrate including the photoresist pattern; Forming a nanostructure including a first nanoblock and a second nanoblock as a thin film including a block copolymer formed on the substrate on which the neutral layer is formed; Forming a thin film on the substrate from which a part of the nanostructure is removed; And Removing the thin film formed on the upper end of the second block and on the second block to form a pattern on the substrate. The method of claim 16, wherein forming the thin film The first nanoblocks are removed from the nanostructures to form the thin film on the substrate on which the second nanoblocks remain. The method of claim 16, wherein forming the thin film includes removing the portion of the nanostructure to form the thin film on a substrate including the remaining first nanoblock and the second nanoblock. and, And the pattern is formed on the remaining first nanoblocks. Forming a photoresist pattern on the substrate including the thin film; Forming a buffer structure with a buffer layer including a cylindrical block copolymer formed on a substrate including the photoresist pattern; Forming a nanostructure including a first nano block and a second nano block on the buffer structure using a thin film including a plate-shaped block copolymer formed on a substrate including the buffer structure; Removing the buffer structure disposed under the first nanoblock and the first nanoblock; And Patterning the remaining buffer structure and the thin film exposed through the second nanoblock to form a pattern. The method of claim 19, wherein the photoresist pattern is And partition walls which extend in a first direction of the substrate and are repeatedly arranged in a second direction different from the first direction. The method of claim 20, wherein the buffer structure is Nano-cylinders extending in the first direction and disposed in the second direction between partition walls adjacent to each other; Half-cylinders extending in the first direction and disposed in the second direction on a substrate including the partition portions and the nanocylinders; And And a substrate disposed between the nanocylinders and the half-cylinders. Patterning a thin film formed on the substrate to form a metal pattern including a first thickness portion and a second thickness portion lower than the first thickness portion; Forming a buffer structure with a buffer layer including a cylindrical block copolymer formed on a substrate including the metal pattern; Forming a nanostructure including a first nanoblock and a second nanoblock on the buffer structure with a preliminary layer including a plate-shaped block copolymer formed on a substrate including the buffer structure; Removing the first nanoblock and the buffer structure formed under the first nanoblock; And Patterning the remaining buffer structure and the metal pattern exposed through the second block to form a pattern. The method of claim 22, wherein the buffer structure Nanocylinders disposed on the second thickness portion; Half-cylinders disposed on the nanocylinders and the first thickness portion; And And a substrate disposed between the nanocylinders and the half-cylinders.

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