KR102308194B1 - Method for manufacturing block copolymer film - Google Patents

Abstract

The present invention easily controls the surface energy of a coated substrate using a polymer nanomosaic (PNM) coating layer formed by interfacial self-assembly (ISA) of a block copolymer. It is possible to provide a block copolymer film including vertically oriented block copolymer nanoregions. According to the manufacturing method, not only has excellent process economy, but also can be applied to various substrates without limitation on the size, shape and type of the substrate, and the self-assembled self-assembled with the desired orientation and pattern density by simply controlling the water surface area of the interfacial self-assembly. A block copolymer film can be prepared.

Description

Method for producing a block copolymer film {METHOD FOR MANUFACTURING BLOCK COPOLYMER FILM}

The present invention relates to a method for producing a block copolymer film using interfacial self-assembly (ISA) at an air/water interface.

Various nanopatterns fabricated using microphase separation based on the self-assembly of block copolymers (BCP) have made great strides in the application of nanotechnology for decades.

A block copolymer is a type of polymer material and represents a form in which two or more polymers are connected to each other through a covalent bond. In a diblock copolymer, which is the simplest structure of a block copolymer, two polymers with different tendencies are linked to each other to form a single polymer. The two polymers connected to each other are easily phase-separated due to different material properties, and finally, the block copolymer can be self-assembled to form a nanostructure.

According to the self-assembly of such block copolymers, phase separation occurs when sufficient energy is generally applied through heat to the block copolymer, resulting in sphere, cylinder, gyroid, and lamella. ) type can form a periodically arranged nanostructure, so the self-assembly of block copolymers is widely used in various application fields.

The most important issue in the practical application of the formation of various nanopatterns using block copolymers is to control the orientation of the block copolymer nanostructures in the thin film (or substrate). The orientation of the nanostructure may include a parallel orientation parallel to the substrate direction and a vertical orientation perpendicular to the substrate direction. In particular, among these two, vertical orientation has greater importance than horizontal orientation. A substrate (with neutral surface energy) should be used.

The most common method for obtaining such a chemically neutral substrate is to graft a brush/mat of a random copolymer onto the substrate. Here, the “brush” refers to a polymer brush, which means a polymer including a reactive functional group capable of reacting with a functional group on the surface of the substrate to form a layer of polymer chains attached to the substrate. The "mat" is a cross-linked random copolymer mat, in which a chain backbone can be horizontally aligned to a substrate.

In this regard, for example, Korean Patent Registration No. 0930966 discloses a nanostructure of a random copolymer having an accurate ratio of unit pairs and a method of manufacturing the random copolymer nanostructure through polymer brush growth. However, this method is not only complicated, but also has a problem in that a high temperature process must be performed under vacuum conditions for a long time to form a covalently bonded brush/mat, and there is a limitation in the applied substrate.

Republic of Korea Patent No. 0930966

The present invention is designed to solve the above conventional problems, and the first technical problem to be solved by the present invention is a polymer nanomosaic (PNM) coating layer formed by interfacial self-assembly (ISA) of a block copolymer at the air/water interface. To provide a method for easily controlling the surface energy of various substrates using

In addition, the second technical problem to be solved by the present invention is to provide a block copolymer film prepared by the above manufacturing method.

In order to achieve the above object, one embodiment provides an interfacial self-assembled product by 1) adding a solution containing the first block copolymer to water and interfacial self-assembling (ISA) of the first block copolymer at the air/water interface. Forming a 1-block copolymer layer; 2) transferring a part or all of the first block copolymer layer on a substrate to form a polymer nanomosaic (PNM) coating layer; And 3) coating a solution containing a second block copolymer on the polymer nano-mosaic coating layer and heat-treating to form a self-assembled second block copolymer layer, it provides a method for producing a block copolymer film .

In another embodiment, 1') a solution containing the first block copolymer is added to water, and the first block copolymer is interfacially self-assembled by interfacial self-assembly (ISA) at the air/water interface. forming a copolymer layer; 2') transferring a part or all of the first block copolymer layer onto a substrate to form a polymer nanomosaic (PNM) coating layer; 3') patterning the polymer nano-mosaic coating layer; and 4') coating a solution containing a second block copolymer on the patterned polymer nano-mosaic coating layer and heat-treating to form a self-assembled second block copolymer layer. Method of producing a block copolymer film provides

Another embodiment provides a block copolymer film prepared by the above manufacturing method.

According to the manufacturing method of the present invention, block copolymer nanoregions oriented perpendicular to the substrate are included by using a polymer nanomosaic (PNM) coating layer formed by interfacial self-assembly (ISA) of the block copolymer at the air/water interface. The block copolymer film can be prepared by a simple method for a short time even at room temperature and pressure conditions. As such, the block copolymer film manufacturing method of the present invention has excellent process economics compared to the prior art.

In addition, the manufacturing method of the present invention can be applied to various substrates without limitation on the size, shape, and type of the substrate.

Furthermore, according to the manufacturing method of the present invention, the substrate coated with PNM can be controlled to have a desired surface energy by simply controlling the water surface area, and a block copolymer film having a desired orientation and pattern density can be manufactured.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.
The meanings of the abbreviations described in the brief description of the drawings below are as defined in the specific embodiments.
1 is a schematic diagram illustrating a method of manufacturing a block copolymer film according to an embodiment of the present invention.
2 is (a) a schematic diagram of a nanostructure formed by interfacial self-assembly in a water tank according to an embodiment of the present invention, and (b) an SEM photograph showing various types of patterns that can be formed in the first block copolymer layer.
_{3 is (a) SEM photograph of the surface of the PNM 47nm} coating layer according to the surface pressure of the first block copolymer layer, (b) SEM of the block copolymer film surface of Example 1-1 according to the surface pressure of the first block copolymer layer Photograph, (c) SEM photograph of the block copolymer film surface of Example 1-2 according to the surface pressure of the first block copolymer layer, and (d) Example 1-3 according to the surface pressure of the first block copolymer layer It is a SEM photograph of the block copolymer film surface.
Figure 4 (a) PNM SEM picture of size distribution and PNM _47nm coating layer surface of the dot pattern formed on a _47nm coating layer, (b) PNM _58nm SEM picture of size distribution and PNM _58nm coating layer surface of the dot pattern formed on the coating layer, and (c ) is a SEM photograph of a size distribution and the surface of the coating layer PNM _{70nm 70nm} PNM dot pattern formed on the coating layer.
5 is (a) _{an expected cross-sectional photograph of a PS-b-PMMA nanoregion} (lamellar structure) formed vertically on a PNM 47nm coating layer, (b) Example 1-1 at various angles of incidence of 0.06 to 0.17°; Grazing Angle Incident Small Angle X-Ray Scattering (GISAXS) of Block Copolymer Films 2D data, (c) GISAXS 2D data of the block copolymer film of Examples 1-2 at various angles of incidence from 0.06 to 0.17°, (d) Block aerials of Examples 1-3 at various angles of incidence from 0.06 to 0.17° GISAXS 2D data of the copolymer film, (e) GISAXS 1D profile of the block copolymer film of Example 1-1 at various angles of incidence from 0.06 to 0.17°, (e) Example 1- at various angles of incidence from 0.06 to 0.17° GISAXS 1D profile of the block copolymer film of 2, and (f) GISAXS 1D profile of the block copolymer film of Examples 1-3 at various angles of incidence from 0.06 to 0.17°.
_{Figure 6a is (a) the surface SEM photograph (first row) of the PNM 58nm} coating layer (Examples 2-1 to 2-3) according to various surface pressures of the first block copolymer layer, the block copolymer film of Example 2-1 SEM photograph of the surface (second row), SEM photograph of the block copolymer film surface of Example 2-2 (third row), and SEM photograph of the block copolymer film surface of Example 2-3 (fourth row), (b ) _{GISAXS 1D data of the PNM 58nm} coating layer, (c) GISAXS 1D data of the block copolymer film of Example 2-2 at various incident angles of 0.06 to 0.17° at a surface pressure of 10 m/Nm, (d) first block copolymerization _{SEM photograph of the surface of the PNM 70nm} coating layer according to various surface pressures of the sieve layer (first row), SEM photograph of the surface of the block copolymer film of Example 3-1 (second row), the surface of the block copolymer film of Example 3-2 SEM photograph (third row), and SEM photograph of the block copolymer film surface of Example 3-3 (fourth row), (e) _{GISAXS 1D data of the PNM 70 nm} coating layer, (f) 0.06 to 0.06 at a surface pressure of 10 m/Nm GISAXS 1D data of the block copolymer film of Example 3-3 at various angles of incidence of 0.17°.
6b is a SEM photograph of the block copolymer film of Examples 1-5 in which PS-b-P2VP having a number average molecular weight of 45,000-b-49,000 g/mol is vertically oriented.
7 is (a) a graph showing the change in the water contact angle on the PNM coating layer according to the surface pressure of the first block copolymer layer, (b) the point formed on the PNM coating layer The diameter of the dot pattern (a) / The distance between the centers of the pattern ( d _cc ) is a graph showing the change in contact angle, and (c) a graph showing the relationship between the domain orientation of the PS-b-PMMA nano region (lamellar structure) and the domain spacing ratio of the PNM coating layer.
8 is (a) an SEM photograph of the surface of the block copolymer film of Examples 1-3 formed on various substrates, (b) a graph showing the water contact angle with respect to the substrate used in (a) above, (c) a glass pipette SEM pictures of the surface of the block copolymer film formed on the curved surface of (d) PNM _47nm coated AFM tips and SEM pictures of the cantilever.
9 is (a) a schematic diagram illustrating a method of manufacturing a layered block copolymer film using a layered PNM coating layer, (b) an oxygen plasma treatment or UV-treated area, and a region protected by a shadow mask. SEM pictures of the patterned PNM coating layer surface, and (c) SEM pictures of the layered block copolymer film surface formed using the patterned PNM coating layer.

Hereinafter, the present invention will be described in detail.

According to one embodiment of the present invention, 1) a solution containing the first block copolymer is added to water and the first block copolymer is interfacially self-assembled by interfacial self-assembly (ISA) at the air/water interface. forming a block copolymer layer; 2) transferring a part or all of the first block copolymer layer on a substrate to form a polymer nanomosaic (PNM) coating layer; And 3) coating a solution containing a second block copolymer on the polymer nano-mosaic coating layer and heat-treating to form a self-assembled second block copolymer layer, a method for producing a block copolymer film is provided .

According to the manufacturing method, the desired PNM coating layer can be obtained by interfacial self-assembly of the block copolymer at the air/water interface, and by using this, the surface energy can be controlled without limitation on the size, shape, and type of the substrate, A block copolymer film can be quickly and easily produced on a substrate with controlled surface energy.

Among the existing methods used to obtain a chemically neutral substrate, the method of grafting a brush/mat of a random copolymer onto a substrate is based on chemical adsorption through covalent bonding. Therefore, the process was complicated and there was a limitation in the target substrate. In contrast, the interfacial self-assembly (PNM coating layer formation) of the block copolymer characteristically manufactured and used in the manufacturing method of the present invention is based on irreversible physical adsorption using van der Waals attraction and hydrogen bonding. It can be universally applied to substrates of various shapes and materials.

Each component used in the manufacturing method will be described in detail below.

water

The type of water may be used without limitation, for example, distilled water, deionized water, ultrapure water (18.2 Mohm or more, tertiary water) or ultra-hyper pure water (25 Mohm). above, 4th order) can be used. More specifically, as the water, deionized water obtained by purifying distilled water using a water purification system (eg, Millipore Milli-Q Gradient system) may be used.

first block copolymer

The first block copolymer may be an amphiphilic block copolymer. Amphiphilicity is a property of having both hydrophilicity and lipophilicity, and when a block copolymer having these properties is added to the surface of water, it may cause interfacial self-assembly of the block copolymer at the air/water interface.

The first block copolymer includes a hydrophilic unit block and a hydrophobic unit block. The first block copolymer may be interfacially self-assembled at the air/water interface to form dot-, strand-, and plate-shaped patterns (hereinafter, referred to as dot patterns, strand patterns, and plate-shaped patterns). Such a shape may vary depending on the number average molecular weight ratio of the hydrophilic unit block and the hydrophobic unit block.

For example, if the number average molecular weight of the first block copolymer is 100%, when the number average molecular weight of the hydrophilic unit block is about 30% or more, the interfacial self-assembled first block copolymer layer may include a dot pattern. In addition, when the number average molecular weight of the hydrophilic unit block is greater than about 10% to less than 30%, the interfacial self-assembled first block copolymer layer may include a strand pattern. On the other hand, when the number average molecular weight of the hydrophilic unit block is about 10% or less, the interfacial self-assembled first block copolymer layer may include a plate-shaped pattern.

According to one embodiment of the present invention, the hydrophilic unit block of the first block copolymer may have a number average molecular weight fraction of 25% or more with respect to the total number average molecular weight of the first block copolymer.

Specifically, when the number average molecular weight of the first block copolymer is 100%, the number average molecular weight ratio of the hydrophilic unit block and the hydrophobic unit block may be 30:70 to 80:20. Specifically, the hydrophilic unit block and the hydrophobic unit block may have a number average molecular weight ratio of 30:70 to 75:25. More specifically, the hydrophilic unit block and the hydrophobic unit block may have a number average molecular weight ratio of 30:70 to 70:30.

The number average molecular weight of the hydrophilic unit block may be 3,000 g/mol to 200,000 g/mol, specifically 7,000 g/mol to 90,000 g/mol, and more specifically 9,000 g/mol to 80,000 g/mol.

The number average molecular weight of the hydrophobic unit block may be 3,000 g/mol to 300,000 g/mol, specifically 9,000 g/mol to 250,000 g/mol, and more specifically 12,000 g/mol to 200,000 g/mol.

The polydispersity index (PDI) of the first block copolymer is 1 to 3, specifically 1 to 2, more specifically 1 to 1.5, 1 to 1.2, 1 to 1.1, 1 to 1.0.8, 1 to 1.07 or 1 to 1.05. The PDI is calculated by dividing the weight average molecular weight by the number average molecular weight.

The first block copolymer can be used without limitation as long as it has the self-assembly characteristics, for example, polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA), polystyrene-block-poly(ethylene oxide) ) (PS-b-PEO), polystyrene-block-polydimethylsiloxane (PS-b-PDMS), polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) and polystyrene-block-poly( It may include one or more selected from the group consisting of 4-vinylpyridine) (PS-b-P4VP). Specifically, the first block copolymer is polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP), polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) and/or polystyrene -block-poly(methylmethacrylate) (PS-b-PMMA).

If PS-b-P2VP is used as the first block copolymer, the number average molecular weight of PS-b-P2VP is, for example, 18,000-b-9,000 g/mol, 44,000-b-18,500 g/mol, 45,000-b-49,000 g/mol, 50,900-b-29,100 g/mol, 79,000-b-36,500 g/mol or 180,000-b-77,000 g/mol.

The first block copolymer may be included in the solvent at a concentration of 0.1 mg/ml to 3 mg/ml, specifically 0.5 mg/ml to 2.0 mg/ml, more specifically 0.7 mg/ml to 1.5 mg/ml.

second block copolymer

The second block copolymer is not limited in molecular weight as long as it can form a pattern through self-assembly.

According to one embodiment of the present invention, the second block copolymer may include two different unit blocks, and in the unit block, the number average molecular weight fraction of one unit block with respect to the other unit block may be 60% or less.

More specifically, when the self-assembled structure of the second block copolymer is a lamellar structure, the number average molecular weight fraction of one unit block with respect to the other unit block may be 40% to 60%.

In addition, when the self-assembled structure of the second block copolymer is a cylindrical structure, the number average molecular weight fraction of one unit block with respect to the other unit block may be 20 to 40%.

In addition, when the self-assembled structure of the second block copolymer has a spherical structure, the number average molecular weight fraction of one unit block with respect to the other unit block may be less than 20%.

The total number average molecular weight of the second block copolymer may be 5,000 g/mol to 200,000 g/mol, specifically 15,000 g/mol to 150,000 g/mol, more specifically 20,000 g/mol to 110,000 g/mol.

If the number average molecular weight of the second block copolymer has a number average molecular weight that is out of the above range, it may be difficult to obtain a second block copolymer layer having a uniform thickness because the pattern formation does not occur properly or the viscosity is greatly increased. have.

The polydispersity index (PDI) of the second block copolymer may be 1 to 2.5, specifically 1 to 2, more specifically 1 to 1.5, 1 to 1.2, 1 to 1.1, or 1 to 1.05.

The second block copolymer can be used without limitation as long as it has the above self-assembly properties, but polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA), polystyrene-block-poly(ethylene oxide) (PS) -b-PEO), polystyrene-block-polydimethylsiloxane (PS-b-PDMS), polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) and polystyrene-block-poly(4-vinyl) pyridine) (PS-b-P4VP) may include at least one selected from the group consisting of. Specifically, the second block copolymer includes polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) and/or polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP). can do.

If PS-b-PMMA is used as the second block copolymer, the number average molecular weight of PS-b-PMMA is, for example, 25,000-b-26,000 g/mol, 35,000-b-37,000 g/mol, 52,000-b-52,000 g/mol, or 64,000-b-35,000 g/mol, and when PS-b-P2VP is used, the number average molecular weight of PS-b-P2VP is 45,000-b-49,000 g/mol can be

The second block copolymer is 0.2 wt% to 3 wt%, specifically 0.4 wt% to 2 wt%, more specifically 0.5 wt% to 1.5 wt%, based on the total weight of the solution containing the second block copolymer % may be included.

menstruum

The solutions used in each of steps 1) and 2) are chloroform, methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide and dimethyl One or more solvents selected from the group consisting of acetamide may be included. Specifically, the solvent may be toluene, tetrahydrofuran, chloroform, or a mixture thereof.

Board

As the substrate, various substrates may be used without limitation. The substrate may be applied to a three-dimensional substrate in addition to the two-dimensional substrate, for example, a curved substrate, a spherical substrate, or a hexahedral substrate, a semiconductor substrate having a complex three-dimensional structure, and the like, without limitation. Specifically, the substrate may be a two-dimensional or three-dimensional substrate including at least one selected from the group consisting of metal, metal oxide, ceramic, and polymer, and more specifically, silicon (Si), aluminum oxide (Al ₂ O). ₃ ), hafnium oxide (HfO ₂ ), indium tin oxide (ITO), molybdenum (Mo), nickel (Ni), silicon nitride (Si ₃ N ₄ ), titanium oxide (TiO ₂ ), tungsten (W), zinc oxide ( ZnO ₂ ), silver (Au), polyimide (PI), platinum (Pt), tantalum (Ta), and a two-dimensional substrate or a three-dimensional substrate containing at least one selected from the group consisting of tantalum nitride (TaN) Can be used.

Method for producing block copolymer film (A)

1 is a schematic diagram illustrating a method of manufacturing a block copolymer film according to an embodiment of the present invention. Hereinafter, each process will be described in detail step by step with reference to FIG. 1 .

1) First block copolymer layer forming step

In the method for producing a block copolymer film according to an embodiment of the present invention, step 1) is performed by adding a solution containing the first block copolymer to water, as in (a) of FIG. Interfacial self-assembly (ISA) of the first block copolymer at the interface to form the interfacial self-assembled first block copolymer layer.

The water may be added to a commonly used container or water tank, but is not limited thereto. Specifically, water may be added into the water tank using the Langmuir-Blodgett (LB) equipment. The Langmuir-Blodgett device according to an embodiment of the present invention is schematically shown in FIG. 2(a).

By adding water to the water tank and adding several to tens of drops of a solution containing the first block copolymer, the first block copolymer is interfacially self-assembled at the air/water interface to form a first block copolymer layer .

The interfacial self-assembly may be accomplished by evaporating the solvent in the solution for 5 seconds to 60 minutes, specifically 10 seconds to 40 minutes, and more specifically 30 seconds to 20 minutes.

According to an embodiment of the present invention, as shown in (a) of FIG. 2, the first block copolymer including the hydrophobic unit block and the hydrophilic unit block is interfacially self-assembled at the air/water interface, whereby the first block a hydrophobic aggregate having a dot pattern in which the copolymer layer is derived from the hydrophobic unit block; and a plurality of hydrophilic chain molecules derived from the hydrophilic unit block and linked to the hydrophobic aggregate.

The dot pattern may be changed into a strand pattern or a plate-shaped pattern, etc. according to the number average molecular weight ratio of the hydrophilic unit block and the hydrophobic unit block of the first block copolymer, as in (b) of FIG. 2 .

The hydrophobic aggregates of the dot pattern may have an average diameter of 20 nm to 300 nm, specifically 30 nm to 100 nm, and more specifically 40 nm to 80 nm. In this case, the average diameter means a number mean diameter, and the hydrophobic aggregate diameter of each dot pattern observed using a scanning electron microscope (SEM) and image analysis software based on a unit area of 1 mm 2 It can be calculated by measuring.

2) Polymer nano-mosaic (PNM) coating layer formation step

In the method for producing a block copolymer film according to an embodiment of the present invention, step 2) is performed by transferring a part or all of the first block copolymer layer on a substrate as shown in FIG. This is a step of forming a mosaic (PNM) coating layer.

Since the first block copolymer layer is formed in the form of a film on the surface of water, part or all of the first block copolymer layer may be transferred onto the substrate by hand or using a tool. In addition, after the desired substrate is immersed in water to laminate the first block copolymer layer on the substrate, the substrate may be moved out of water to form a PNM coating layer on the substrate.

3) Forming the second block copolymer layer

In the method for producing a block copolymer film according to an embodiment of the present invention, in step 3), a second block copolymer layer self-assembled by coating a solution containing a second block copolymer on the PNM coating layer and heat-treating it is the step of forming

The coating may be performed by spin coating, bar coating, dip coating, or roll coating, and specifically may be performed by spin coating.

The thickness of the second block copolymer layer may be about 10 nm to 100 nm, specifically about 15 nm to 80 nm, and more specifically about 20 nm to 60 nm. The thickness of the second block copolymer layer may be measured using a spectroscopic ellipsometer (M-2000V, J.A. Woollam Co.).

In addition, the second block copolymer may be spin-coated on the PNM coating layer to a thickness equal to the domain spacing. Accordingly, in the present specification, unless there is a specific reference on the thickness of the second block copolymer layer, it may be interpreted as coated on the PNM coating layer with the same thickness as the domain spacing of the second block copolymer.

In addition, the heat treatment may be performed at 120° C. to 250° C. for 10 minutes to 30 hours, specifically, at 150° C. to 200° C. for 10 minutes to 25 hours.

Method for producing block copolymer film (B)

In the method for producing a block copolymer film according to another embodiment of the present invention, 1') a solution containing the first block copolymer is added to water, and the first block copolymer is interfacially self-assembled at the air/water interface ( ISA) to form a first interfacial self-assembled block copolymer layer; 2') transferring a part or all of the first block copolymer layer onto a substrate to form a polymer nanomosaic (PNM) coating layer; 3') patterning the polymer nano-mosaic coating layer; and 4') coating a solution containing a second block copolymer on the patterned polymer nano-mosaic coating layer and heat-treating to form a self-assembled second block copolymer layer. By the above method, a layered PNM coating layer and a layered block copolymer layer can be formed.

According to the manufacturing method, 1') and 2') were carried out in the same manner as described in steps 1) and 2) of the method (A) of the block copolymer film according to an embodiment of the present invention. A coating layer may be formed.

The step 3') is a step of patterning the PNM coating layer, and as shown in the schematic diagram of FIG. sccm, CUTE-1MPR, Femto Science Inc.) or UV treatment (it can be performed under various conditions, specifically, λ = 254 nm, UV lamp of ^{40 mW/cm 2 ).} A shadow mask may be used during the patterning, and the shadow mask may be, for example, a Cu TEM grid (G400-C3, Gilder Grids).

Step 4') is a step of coating a solution containing a second block copolymer on the patterned PNM coating layer and heat-treating it to form a self-assembled second block copolymer layer, wherein step 4') is the method of the present invention. By performing the same method as described in step 3) of the method for producing a block copolymer film (A) according to an embodiment, a second block copolymer layer is formed on the patterned PNM coating layer to form a layered block copolymer film can be manufactured.

The second block copolymer layer includes block copolymer nanoregions oriented parallel to the substrate on the etched PNM coating layer, and block copolymer nanoregions oriented perpendicular to the substrate on the unetched PNM coating layer. can do.

According to the manufacturing method (B) of the block copolymer film, since various patterns aligned on the PNM coating layer can be formed in a selective region, it can be applied and used in various semiconductor processes.

Morphology of the first block copolymer layer and the polymer nanomosaic (PNM) coating layer

According to one embodiment of the present invention, the morphologies of the first block copolymer layer and the PNM coating layer have the same morphology.

The morphology of the first block copolymer layer and the PNM coating layer can be confirmed by measuring the surface of the first block copolymer layer or the PNM coating layer with a scanning electron microscope (SEM).

According to one embodiment of the present invention, the morphology of the PNM coating layer may vary depending on the surface pressure of the 1-block copolymer layer.

The surface pressure of the first block copolymer layer may be 1 mN/m to 30 mN/m, specifically 1 mN/m to 15 mN/m, and more specifically 1 mN/m to 12 mN/m. The surface pressure of the first block copolymer layer can be adjusted by controlling the surface area of water in step 1). However, as long as the surface pressure in the above range is satisfied, the method for controlling the surface area of water is not particularly limited, but the present invention provides a computer-controlled KSV NIMA KN 2002 Langmuir Blojet equipment equipped with a platinum Wilhelmy plate according to an embodiment. By using it, it is possible to control the surface area of water at a constant compression rate.

When the surface pressure of the first block copolymer layer exceeds 30 mN/m, the hydrophobic aggregates of the dot pattern derived from the hydrophobic unit block in the first block copolymer layer may be non-uniformly arranged, and on the PNM coating layer It is difficult to form a second vertical block copolymer layer. On the other hand, even when the surface pressure of the first block copolymer layer is less than 1 mN/m, the same effect as when the surface pressure is 1 mN/m is exhibited, but there may be problems such as partial coating failure.

In addition, the dot pattern formed on the PNM coating layer may form a denser dot pattern as the surface pressure of the first block copolymer layer increases.

According to one embodiment of the present invention, when the first block copolymer having a number average molecular weight of 18,000-b-9,000 g/mol is used, when the surface pressure is 1 mN/m to 12 mN/m, the surface pressure is As it increases, the PNM coating layer may have a denser pattern. Also, the dot pattern may have a uniform pattern arranged in a hexagonal nanostructure. If the surface pressure exceeds 12 mN/m, the dot pattern may be converted into a quasi-square arrangement instead of a hexagonal nanostructure.

According to another embodiment of the present invention, when the first block copolymer having a number average molecular weight of 44,000-b-18,500 g/mol or a number average molecular weight of 79,000-b-36,500 g/mol is used, the surface pressure is 1 mN When the /m to 15 mN/m, the PNM coating layer may have a denser pattern as the surface pressure increases. Also, the dot pattern may have a uniform pattern arranged in a hexagonal nanostructure. If the surface pressure exceeds 15 mN/m, the dot pattern may be converted into a quasi-square arrangement rather than a hexagonal nanostructure arrangement.

Morphology of the second block copolymer layer

The morphology of the second block copolymer layer can be confirmed by measuring the surface of the second block copolymer layer with a scanning electron microscope (SEM). The second block copolymer layer includes block copolymer nano-regions oriented perpendicular to the substrate. The block copolymer nanoregion oriented perpendicular to the substrate may be a lamella-type structure.

According to one embodiment of the present invention, the morphology of the second block copolymer layer may vary depending on the morphology of the first block copolymer layer and the PNM coating layer.

Specifically, when the surface pressure of the first block copolymer layer is 1 mN/m and 30 mN/m, the second block copolymer layer may include block copolymer nanoregions oriented perpendicular to the substrate.

In addition, the morphology of the second block copolymer layer may vary according to the number average molecular weight of the hydrophilic unit block and the hydrophobic unit block of the first block copolymer and the second block copolymer.

According to one embodiment of the present invention, a first block copolymer having a number average molecular weight of 18,000-b-9,000 g/mol is used, and a second block copolymer having a number average molecular weight of 25,000-b-26,000 g/mol is used. When used, when the surface pressure is 10 mN/m to 12 mN/m, the second block copolymer layer may include block copolymer nanoregions oriented perpendicular to the substrate.

According to another embodiment of the present invention, a first block copolymer having a number average molecular weight of 18,000-b-9,000 g/mol is used, and a number average molecular weight of 35,000-b-37,000 g/mol or a number average molecular weight of 52,000 -b-52,000 g/mol of the second block copolymer is used, when the surface pressure is 1 mN/m to 12 mN/m, the second block copolymer layer is a block copolymer oriented perpendicular to the substrate It may include nano-regions.

Characteristics of block copolymer films

The present invention provides a block copolymer film prepared by the above manufacturing method.

According to one embodiment of the present invention, the morphology of the second block copolymer layer may vary depending on the morphology of the first block copolymer layer and the PNM coating layer. Specifically, since the domain orientation of the nano-region of the second block copolymer oriented perpendicular to the substrate may vary depending on the pattern density of the PNM coating layer, the surface pressure of the first block copolymer layer is adjusted to form the pattern of the PNM coating layer. By controlling the density to control the surface energy of the coated substrate, it is possible to form a second block copolymer nanoregion having a desired orientation.

According to another embodiment of the present invention, in the second block copolymer layer, when the PNM coating layer has a neutral surface energy, the nano-regions of the second block copolymer may be vertically oriented. Here, the term 'neutral surface energy' means that the PNM coating layer has the same interfacial energy with respect to the substrate rising on the coating layer. If the PNM coating layer has a neutral surface energy, the difference in chemical interface energy for two different blocks of the block copolymer coated thereon becomes the same.

Specifically, when the PNM coating layer has a water contact angle of about 60° to 90° and a surface energy of 20 dyne/cm to 40 dyne/cm, the second block copolymer layer is oriented perpendicular to the substrate. It may include a block copolymer nano region. If the water contact angle of the PNM coating layer is less than 60 ° or exceeds 90 °, the neutral surface energy condition of the nano-region of the second block copolymer for the PNM coating layer does not match, so the second block copolymer is vertical Orientation may be difficult.

According to another embodiment of the present invention, the domain spacing of the nano-region of the second block copolymer oriented perpendicular to the substrate may have a close relationship with the domain spacing of the PNM coating layer.

Specifically, if the D _L is the 25 nm to 55 nm, may be in the D _PNM is 40 nm to 120 nm, wherein the D _PNM this can be smaller than 1.2, the square of D _L (D _L ^1.2). More specifically, when the D _L is about 28 nm, the D _PNM has a vertical lamellar structure oriented in a range of greater than about 40 nm to about 55 nm or less, and when the D _L is about 45 nm, the D _PNM is The vertical lamellar structure was oriented in greater than about 40 nm to about 90 nm or less, and when the D _L was about 54 nm, the D _PNM confirmed that the vertical lamellar structure was oriented in more than about 40 nm to about 120 nm or less did.

_{In addition, the gap (D L} ) between the lamellar structures, which is the second block copolymer nano region, may be smaller than the distance between the domains (D _{PNM ) of the PNM coating layer.}

According to another embodiment of the present invention, the block copolymer film is a two-dimensional substrate or a three-dimensional substrate including at least one selected from the group consisting of metals, metal oxides, ceramics and polymers, etc. The size, shape and type of the substrate It can be manufactured by variously applying without limitation.

[Example]

The present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to these examples.

The meanings of the abbreviations used in the following examples and figures are as follows.

- PS-b-P2VP: polystyrene-block-poly(2-vinylpyridine)

- PS-b-PMMA: polystyrene-block-poly(methyl methacrylate)

- ISA: interfacial self-assembly

- PNM: Polymer nanomosaic

- PNM _47nm : PNM coating layer with a uniform dot pattern having an average diameter of 47 nm

- PNM _58nm : PNM coating layer with a uniform dot pattern having an average diameter of 58 nm

- PNM _70nm : PNM coating layer with a uniform dot pattern having an average diameter of 70 nm

- PS-b-PMMA (25-26k) or SM (25-26k): PS-b-PMMA having a number average molecular weight of 25,000-b-26,000 g/mol

- PS-b-PMMA (35-37k) or SM (35-37k): PS-b-PMMA having a number average molecular weight of 35,000-b-37,000 g/mol

- PS-b-PMMA (52-52k) or SM (52-52k): PS-b-PMMA having a number average molecular weight of 52,000-b-52,000 g/mol

- PS-b-PMMA (64-35k) or SM (64-35k): PS-b-PMMA having a number average molecular weight of 64,000-b-35,000 g/mol

- PS-b-P2VP (18-9k): PS-b-P2VP with a number average molecular weight of 18,000-b-9,000 g/mol

- PS-b-P2VP (44-18.5k): PS-b-P2VP with a number average molecular weight of 44,000-b-18,500 g/mol

- PS-b-P2VP (45-49k): PS-b-P2VP with a number average molecular weight of 45,000-b-49,000 g/mol

- PS-b-P2VP (79-36.5k): PS-b-P2VP with a number average molecular weight of 79,000-b-36,500 g/mol

- PDI: polydispersity index

- D _L : domain spacing of lamellar structure, which is a block copolymer nano region

- D _PNM : PNM coating layer domain spacing

The measuring instruments used in the following examples are as follows:

- Scanning electron microscope (SEM): Hitachi S-4800 field emission scanning electron microscope (high vacuum, 1 keV).

- Grazing angle incident small angle X-ray scattering (GISAXS): PLS-II 9A U-SAXS beamline at Pohang Accelerator Laboratory (PAL), Korea

- Film thickness measurement: spectroscopic ellipsometer (M-2000V, J.A. Woollam Co.)

The components and equipment used in the examples below were as follows:

- PS-b-P2VP: Polymer Source, Inc.

Molecular weight of PS-b-P2VP:

18,000-b-9,000 g/mol (18-9k, PDI = 1.08);

44,000-b-18,500 g/mol (44-18.5k, PDI = 1.07);

45,000-b-49,000 g/mol (45-49k, PDI = 1.07);

79,000-b-36,500 g/mol (79-36.5k, PDI = 1.05)

- PS-b-PMMA: Polymer Source, Inc.

Molecular weight of PS-b-PMMA:

25,000-b-26,000 g/mol (25-26k, PDI = 1.06);

35,000-b-37,000 g/mol (35-37k, PDI = 1.09);

52,000-b-52,000 g/mol (52-52k, PDI = 1.09);

64,000-b-35,000 g/mol (64-35k, PDI = 1.09)

- Chloroform: Sigma-Aldrich, HPLC grade, 99.9%

- Toluene: Sigma-Aldrich, anhydrous, 99.8%

- Deionized water: deionized water (18.2 MΩ/cm) purified with distilled water using the Millipore Milli-Q Gradient system

- Atomic force microscope (AFM) tip used for PNM coated substrate: Bruker tip (RTESP) with cantilever length 125 μm and tip radius 8 nm

- Substrate: Si wafer, Waferbiz

- Langmuir-Blodgett (LB) equipment: Computer-controlled KSV NIMA KN 2002 Langmuir Blodgett equipment equipped with a Langmuir trough with a ^{maximum size of 273 cm 2 and a platinum Wilhelmy plate.} Keep the water temperature in the water tank at room temperature. All symmetric barrier compressions proceeded at a barrier velocity of 5 mm/min (3.75 cm ² /min).

<Production of block copolymer film>

Example 1-1

Step 1) Formation of the first block copolymer layer

As the first block copolymer, PS-b-P2VP having a number average molecular weight of 18,000-b-9,000 g/mol was dissolved in chloroform at a concentration of 1 mg/ml to prepare 30 μL of a solution containing PS-b-P2VP.

Deionized water was put into the tank of the Langmuir-Blodgett (LB) equipment, and 6 drops of the solution containing the PS-b-P2VP was spread on the surface of the deionized water. By evaporating the solvent in the solution for about 20 minutes, PS-b-P2VP was interfacially self-assembled (ISA) to obtain a first block copolymer layer. At this time, the surface pressure was reduced to 1 mN/m, 5 mN/m, 8 mN/m, 10 mN/m, 12 mN/m, and 15 mN/m, respectively, while compressing the symmetrical barrier in the water tank at a rate of 5 mm/min. , 20 mN/m, and 30 mN/m.

Step 2) Formation of polymer nanomosaic (PNM) coating layer

A clean Si wafer was prepared as a substrate.

A portion of the Si wafer was immersed in a water bath in which the first block copolymer layer was formed, and the first block copolymer layer was laminated on the Si wafer through a Langmuir-Blodgett (LB) equipment to form a PNM coating layer on the substrate. .

Step 3) Formation of the second block copolymer layer

The solution containing the second block copolymer was spin-coated on the PNM coating layer obtained in step 2) at 2000 rpm to form a film having a thickness of about 24 nm.

As the solution containing the second block copolymer, a solution obtained by dissolving PS-b-PMMA having a number average molecular weight of 25,000-b-26,000 g/mol in toluene at a concentration of 1% by weight as the second block copolymer was used.

By heat-treating the spin-coated film at about 190° C. under vacuum for 24 hours to self-assemble PS-b-PMMA on the PNM coating layer in a vertical direction to form a second block copolymer layer, the second block copolymer layer is A block copolymer film comprising PS-b-PMMA nanoregions oriented perpendicular to the substrate was obtained.

Examples 1-2 to 1-4

As shown in Table 1 below, the number average molecular weight of PS-b-PMMA as the second block copolymer in step 3) of Example 1-1 was 35,000-b-37,000 g/mol and 52,000-b-52,000 g/mol, respectively. mol, and 64,000-b-35,000 g/mol, except that the thickness of the second block copolymer layer was changed, a block copolymer film was obtained in the same manner as in Example 1-1.

Examples 1-5

As shown in Table 1 below, in step 3) of Example 1-1, PS-b-P2VP having a number average molecular weight of 45,000-b-49,000 g/mol was used as the second block copolymer. A block copolymer film was obtained in the same manner as in Example 1-1.

Examples 2-1 to 2-3

As shown in Table 1 below, in step 1) of Example 1-1, PS-b-P2VP having a number average molecular weight of 44,000-b-18,500 g/mol was used as the first block copolymer, and in step 3) As the second block copolymer, the number average molecular weight of PS-b-PMMA was changed to 25,000-b-26,000 g/mol, 35,000-b-37,000 g/mol, and 52,000-b-52,000 g/mol, respectively, and the second A block copolymer film was obtained in the same manner as in Example 1-1, except that the thickness of the block copolymer layer was changed.

Examples 3-1 to 3-3

As shown in Table 1 below, in step 1) of Example 1-1, PS-b-P2VP having a number average molecular weight of 79,000-b-36,500 g/mol was used as the first block copolymer, and in step 3) The number average molecular weight of PS-b-PMMA as the second block copolymer was changed to 25,000-b-26,000 g/mol, 35,000-b-37,000 g/mol, and 52,000-b-52,000 g/mol, respectively, and the second A block copolymer film was obtained in the same manner as in Example 1-1, except that the thickness of the block copolymer layer was changed.

Example 4

The PNM coating layer obtained in step 2) of Example 1-1 was patterned. The patterning was performed by selectively mounting the shadow mask using a Cu TEM grid (G400-C3, Gilder Grids) as a shadow mask, followed by oxygen plasma treatment (60 W, 10 sccm, CUTE-1MPR, Femto Science Inc.) The PNM coating layer was patterned by a reactive ion etching method.

A solution obtained by dissolving PS-b-PMMA having a number average molecular weight of 25,000-b-26,000 g/mol in toluene at a concentration of 1 wt% on the patterned PNM coating layer was spin-coated at 2000 rpm to form a film with a thickness of about 24 nm did.

The spin-coated film was heat treated at about 190° C. under vacuum for 24 hours to self-assemble PS-b-PMMA on the PNM coating layer in a vertical direction to form a second block copolymer layer. In this case, the second block copolymer layer includes PS-b-PMMA nano-regions oriented parallel to the substrate on the PNM coating layer exposed to the reactive ion etching, and on the PNM coating layer not exposed to the reactive ion etching on the substrate. PS-b-PMMA nanoregions oriented perpendicular to each other were included.

[Table 1]

Experimental example

Experimental Example 1: Scanning electron microscope (SEM) measurement

The surfaces of the PNM coating layer and the block copolymer film obtained in the above Examples were respectively observed with a scanning electron microscope (SEM).

<PNM coating layer of Examples 1-1 to 1-3, and morphology of the block copolymer film>

_{3 is (a) SEM photograph of the surface of the PNM 47nm} coating layer according to the surface pressure of the first block copolymer layer, (b) SEM of the block copolymer film surface of Example 1-1 according to the surface pressure of the first block copolymer layer Photograph, (c) SEM photograph of the block copolymer film surface of Example 1-2 according to the surface pressure of the first block copolymer layer, and (d) Example 1-3 according to the surface pressure of the first block copolymer layer It is an SEM photograph of the block copolymer film surface.

As shown in (a) of FIG. 3 , as the surface pressure of the first block copolymer layer increased from 1 mN/m to 12 mN/m, the pattern of the _{PNM 47 nm coating layer aligned in the initial hexagonal nanostructure became more dense.}

In addition, Examples 1-1 to 1- using PS-b-PMMA having number average molecular weights of 25,000-b-26,000 g/mol, 35,000-b-37,000 g/mol, and 52,000-b-52,000 g/mol, respectively 3, the surface of the block copolymer film was observed by SEM in order to examine the pattern of the nano region of the block copolymer film.

As can be seen from (b) to (d) of Figure 3, the block copolymer film of Example 1-1 is a substrate only when the surface pressure of the first block copolymer layer is 10 mN/m and 12 mN/m PS-b-PMMA nanoregions (lamellar structures) oriented perpendicular to The block copolymer film included PS-b-PMMA nano-regions oriented perpendicular to the substrate in a wide range where the surface pressure of the first block copolymer layer was 1 mN/m to 12 mN/m (Fig. 3 ( first 5 columns of c) and (d)). When the surface pressure of the first block copolymer layer was 15 mN/m or more, both block copolymer nanoregions oriented parallel to the substrate or block copolymer nanoregions oriented perpendicular to the substrate appeared.

On the other hand, Fig. 4 (a) PNM SEM picture of size distribution and PNM _47nm coating layer surface of the dot pattern formed on a _47nm coating layer, (b) SEM photograph of a size distribution and PNM _58nm coating layer surface of the dot pattern formed on a PNM _58nm coating layer, and (c) a SEM image of the size distribution and the surface of the coating layer PNM _{70nm 70nm} PNM dot pattern formed on the coating layer. The SEM images used for the analysis were 1764X1764 nm, 2904X2904 nm, and 2940X2940 nm, respectively.

As can be seen from (a) of Figure 4, the surface pressure of the first block copolymer layer increases to 1 mN / m, 5 mN / m, 8 mN / m, 10 mN / m, and 12 mN / m Accordingly, it can be seen that the uniform dot pattern having an average diameter of 47 nm is arranged in a hexagonal nanostructure and more densely distributed. 4(b) and 4(c) also, as the surface pressure increases from 1 mN/m to 15 mN/m, 58 nm (FIG. 4(b)) and 70 nm (FIG. 4), respectively It can be seen that the uniform dot pattern having the average diameter of (c)) is arranged in a hexagonal nanostructure and more densely distributed.

<PNM coating layer of Examples 2-1 to 2-3, and morphology of block copolymer film>

_{6a (a) and (d) are PS- with a} number average molecular weight of 44,000-b-18,500 g/mol (PNM 58nm, Examples 2-1 to 2-3) and 79,000-b-36,500 g/mol, respectively When b-P2VP (PNM _70nm , Examples 3-1 to 3-3) was used, the surface pressure of the first block copolymer layer was 1 mN/m, 5 mN/m, 10 mN/m, 15 mN/m, and It is a SEM photograph of the surface of the PNM coating layer and the block copolymer film according to 20 mN/m.

Specifically, as can be seen in the first row of each of (a) and (d) of Figure 6a, PNM _{58nm of Examples 2-1 to 2-3 and PNM 70nm} coating layer of Examples 3-1 to 3-3 _{Similar to the pattern of the PNM 47nm} coating layer of Examples 1-1 to 1-3, as the surface pressure of the first block copolymer layer increased from 1 mN/m to 15 mN/m, the uniform dot pattern had a hexagonal shape. It can be seen that the nanostructures are arranged and more densely distributed. On the other hand, _{the patterns of the PNM 58} nm and PNM _{70 nm} coating layers were converted to a quasi-square arrangement rather than a hexagonal nanostructure arrangement at a surface pressure higher than 15 mN/m.

On the other hand, the self-assembly of the second block copolymer was different depending on the average diameter of the dot pattern formed on the PNM coating layer below it.

Specifically, the surface pressure window from PNM _47nm form a PNM _58nm and PNM as to _70nm mean diameter of the point pattern increases formed in PNM coating layer, in a vertically oriented block copolymer nm region to the substrate perpendicular to the lamellar type structure gradually decreased. _{For example, in the case of the block copolymer film of Example 1-1 having a PNM of 47 nm} in FIGS. 3 (b) to (d), the surface pressure of the first block copolymer layer is 10 mN/m and 12 mN/m The second block copolymer layer formed a vertical lamellar structure, which is a PS-b-PMMA nanoregion oriented perpendicular to the substrate, as shown in the second row of FIG. 6A (a) and (d), PNM _{It was confirmed that} both the 58nm and PNM _70nm coating layers did not form a vertical lamellar structure even at a surface pressure of 10 mN/m and 15 mN/m.

Therefore, it was confirmed that the change in the average diameter of the dot pattern formed on the PNM coating layer affects the surface pressure window forming the vertical lamellar structure.

Meanwhile, FIG. 6b is a SEM photograph of the block copolymer film of Example 1-5, vertically oriented with PS-b-P2VP having a number average molecular weight of 45,000-b-49,000 g/mol.

On the other hand, (b), (c), (e), and (f) of Figure 6a are _GISAXS of the PNM 58nm coating layer of _{Examples 2-1 to 2-3 and the PNM 70nm} coating layer of Examples 3-1 to 3-3 1D data, which will be described in detail in Experimental Example 2 below.

Experimental Example 2: Grazing angle incident small angle X-ray scattering (GISAXS) measurement

In order to investigate the internal nanostructure of the second block copolymer layer including the block copolymer nanoregion formed vertically on the PNM coating layer of the embodiment, the vertical lamellar structure, which is the block copolymer nanoregion oriented perpendicular to the substrate, Grazing angle incidence small angle X-ray scattering (GISAXS) analysis was performed by varying the angle of incidence.

GISAXS measurements were performed on the PLS-II 9A U-SAXS beamline at the Pohang Accelerator Laboratory (PAL), Korea. In the GISAXS measurement, the energy of X-rays was 11.025 keV (wavelength, λ = 1.12454 Å), the angle of incidence was varied from 0.06 to 0.17°, and the distance between the sample and the detector was 6367.87 mm for the pattern formed on the PNM coating layer, PS-b- 4444.63 mm for the PMMA membrane (second block copolymer layer). Scatter patterns were collected using a 2D CCD detector (SX-165, Rayonix).

For reference, the GISAXS provides information on the surface at angles of incidence lower than the critical angle of the material (about ≒0.12° for PS-b-PMMA at 11 keV), and at angles of incidence higher than the critical angle for the penetrating portion of the membrane. provide information. Accordingly, relative structural information from the surface of the second block copolymer layer to the substrate was obtained by gradually changing the incidence angle of GISAXS of 0.06 to 0.17°.

<GISAXS measurement of block copolymer films of Examples 1-1 to 1-3>

5 is (a) _{an expected cross-sectional photograph of a PS-b-PMMA nanoregion} (lamellar structure) formed vertically on a PNM 47nm coating layer, (b) Example 1-1 at various angles of incidence of 0.06 to 0.17°; Grazing Angle Incident Small Angle X-Ray Scattering (GISAXS) of Block Copolymer Films 2D data, (c) GISAXS 2D data of the block copolymer film of Examples 1-2 at various angles of incidence from 0.06 to 0.17°, (d) Block aerials of Examples 1-3 at various angles of incidence from 0.06 to 0.17° GISAXS 2D data of the copolymer film, (e) GISAXS 1D profile of the block copolymer film of Example 1-1 at various angles of incidence from 0.06 to 0.17°, (f) Example 1- at various angles of incidence from 0.06 to 0.17° GISAXS 1D profile of the block copolymer film of 2, and (g) GISAXS 1D profile of the block copolymer film of Examples 1-3 at various angles of incidence from 0.06 to 0.17°.

1:2:3:… for all films and angles of incidence. Symmetrical periodic vertical stripes with proportions appeared, indicating that the vertical lamellar structures were fully developed from the film surface to the substrate. Some of the GISAXS 2D data showed additional scattering peaks at low q indicated by the red arrows in FIGS. 5(b) and 5(c). These additional peaks only appear at higher angles of incidence, indicating the presence of specific structures in the vicinity of the substrate.

(루트 3)의 비율로 정확하게 일치한다는 것이 발견되었다. 이 결과로부터, 수직 라멜라형 구조체는 표면으로부터 기판까지 완전히 전파되었고, 또한 코팅 및 열처리 후에도 여전히 PNM 코팅층의 패턴이 그 구조를 유지한다는 것이 확인되었다.As can be seen from (e) to (g) of Figure 5, additional peaks except for the peak from the vertical lamellar structure become stronger as the angle of incidence increases, and the peak from the pattern _{of the PNM 47nm coating layer below it and 1} :

(Route 3) was found to be an exact match. From this result, it was confirmed that the vertical lamellar structure completely propagated from the surface to the substrate, and the pattern of the PNM coating layer still maintained the structure even after coating and heat treatment.

<GISAXS measurement of block copolymer films of Examples 2-1 to 2-3>

On the other hand, (b) of Figure 6a is _{GISAXS 1D data of the PNM 58nm} coating layer, (c) GISAXS 1D of the block copolymer film of Example 2-2 at various incident angles of 0.06 to 0.17° at a surface pressure of 10 m/Nm data, (e) _{GISAXS 1D data of the PNM 70 nm} coating layer, and (f) GISAXS 1D data of the block copolymer film of Example 3-3 at various incident angles of 0.06 to 0.17° at a surface pressure of 10 m/Nm.

)을 명확히 나타내었으며, 그의 1차 피크 위치는 감소된 격자 크기를 나타내며 점차적으로 더 높은 q 범위로 증가하였다. 15 mN/m보다 높은 π에 대한 GISAXS 1D 데이터에서, PNM_58nm 및 PNM_70nm의 넓은 산란 피크는 정사각형 정렬의 전형적인 피크 비율(1:

)를 나타냈다.As shown in the GISAXS analysis of Figure 6a (b) and (e), from the GISAXS 1D data at 1 mN/m of surface pressure for _{PNM 58} nm and PNM _{70 nm to the GISAXS 1D data at 15 mN/m, PNM 58 nm} and _{the scattering peak of PNM 70nm} has a typical peak ratio of hexagonal alignment (1:

), and its primary peak position showed a decreased lattice size and gradually increased to a higher q range. In the GISAXS 1D data for π higher than 15 mN/m, _{the broad scattering peaks of PNM 58} nm and PNM _{70 nm show} a typical peak ratio of square alignment (1:

) was shown.

On the other hand, as can be seen from (c) and (f) of Figure 6a, the change in the average diameter of the dot pattern formed in the PNM coating layer did not affect the internal structure of the vertical lamellar structure.

Specifically, the vertical lamellar structures formed on the block copolymer films of Examples 2-2 and 3-3 were completely propagated from the surface to the substrate, and the pattern of the PNM coating layer still maintained its structure even after coating and heat treatment. that was confirmed

Experimental Example 3: Water contact angle measurement

First, the water contact angle of the PNM coating layer obtained in Examples 1 to 3 was measured, and the change in the water contact angle on the PNM coating layer according to the surface pressure of the first block copolymer layer was observed. The water contact angle was measured with a KRUSS DSA100 instrument.

7 is (a) a graph showing the change in the water contact angle on the PNM coating layer according to the surface pressure of the first block copolymer layer, (b) the point formed on the PNM coating layer The diameter of the dot pattern (a) / The distance between the centers of the pattern ( d _cc ) is a graph showing the change in contact angle, and (c) a graph showing the relationship between the domain orientation of the PS-b-PMMA nano region (lamellar structure) and the domain spacing ratio of the PNM coating layer.

Specifically, as can be seen from (a) of Figure 7 _{, the contact angles of the PNM 47nm} , PNM _58nm and PNM _70nm coating layers were gradually controlled by changing the surface pressure of the first block copolymer layer, and the PNM coating layer was not formed. The contact angle of the unexposed Si substrate was about 40°.

Pattern of the PNM coating layer arranged in a hexagonal form a contact angle (when the PNM _47nm 1 to 12 mN / m, PNM _58nm and PNM for _70nm 1 to 15 mN / m) is uniform with the surface increases pressure of the copolymer layer first block increases, the contact angle of the coating layer of a square array pattern PNM (PNM for _47nm 15 to 30 mN / m, when the PNM _58nm and _70nm PNM 20 to 30 mN / m) of was irregularly dispersed while.

In addition, as can be seen from (b) of FIG. 7, the PNM _pattern of the hexagonally aligned region (1 to 12 mN/m for PNM ₄₇ nm, 1 to 15 mN/m for PNM 58 nm and PNM _{70 nm) is} Their contact angles were compared using the Cassie equation as a function of the selected, standardized variable, a/d _{cc (d cc} is the center-to-center distance between points of the PNM, and a is its mean diameter). It was confirmed that the contact angle of the PNM coating layer was in good agreement with the theoretical value expected by the Cassie equation of Equation 1 below.

<Equation 1>

In Equation 1 above,

f _PS and f _P2VP are the area ratio of PS hydrophobic aggregates and the area ratio of P2VP hydrophilic chain molecules of the dot pattern included in the PNM coating layer, respectively,

θ _PS and θ _P2VP are Young contact angles on a chemically homogeneous substrate composed of PS or P2VP, respectively,

θ _PNM is the effective contact angle of the PNM coating layer.

As can be seen from (c) of FIG. 7 , it was confirmed that the domain spacing of the second block copolymer nanoregion oriented perpendicular to the substrate had a close relationship with the domain spacing of the PNM coating layer. _{Specifically, when the domain spacing (D L} ) of the lamellar structure, which is the second block copolymer nano region, was smaller than the domain spacing (D _PNM ) of the PNM coating layer, the lamellar structure was vertically oriented with respect to the substrate.

Specifically, when the D _L is about 28 nm, the D _PNM has a vertical lamellar structure oriented at about 55 nm or less, and when the D _L is about 45 nm, the D _PNM is vertical at about 90 nm or less The lamellar structure was oriented, and when the D _L was about 54 nm, the D _PNM confirmed that the vertical lamellar structure was oriented at about 120 nm or less.

Experimental Example 4: Confirmation of applicability of various substrates

As in Example 1-2, PS-b-P2VP having a number average molecular weight of 18,000-b-9,000 g/mol as a first block copolymer, and a number average molecular weight of 52,000-b-52,000 g/mol as a second block copolymer To confirm the applicability of various substrates using mol PS-b-PMMA, in addition to Si substrates, Al ₂ O ₃ , HfO ₂ , ITO, Mo, Ni, Si ₃ N ₄ , TiO ₂ , W, ZnO ₂ , A block copolymer film was prepared using a substrate such as Au, polyimide (PI), Pt, Ta, and TaN. The surface of each block copolymer film thus obtained was confirmed by SEM photographs to observe whether PS-b-PMMA nanoregions (vertical lamellar structures) oriented perpendicular to the various substrates were generated.

Figure 8 (a) is a SEM photograph of the surface of the block copolymer film of Example 1-3 formed using PS-b-PMMA having a number average molecular weight of 52,000-b-52,000 g/mol on various substrates. As can be seen from (a) of FIG. 8 , it can be confirmed that PS-b-PMMA nanoregions oriented vertically on the PNM coating layer were successfully created by applying the 14 various substrates in addition to the Si substrate.

FIG. 8(b) is a graph showing water contact angles with respect to various substrates as shown in FIG. 8(a). As can be seen in FIG. 8(b), it was confirmed that the water contact angle of the PNM coating layer can be adjusted to about 80° by controlling the surface energy of various substrates.

On the other hand, (c) of FIG. 8 shows PNM _{47 nm, a} coating layer (surface pressure: 10 mN/m), and SEM images showing the possibility of subsequent BCP nanopattern formation. As can be seen from (c) of FIG. 8, by successfully forming a PNM coating layer on the curved surface of a glass pipette, and a second block copolymer layer (nano-pattern) on the PNM coating layer, even on a three-dimensional (3D) substrate It was confirmed that the manufacturing method of the present invention can be easily applied.

Furthermore, (d) of FIG. 8 is _{an SEM photograph of an AFM tip and a cantilever coated with PNM 47} nm at a surface pressure of 10 mN/m, wherein the PNM coating layer is at the edge of an atomic force microscope (AFM) cantilever. It was confirmed that it can be effectively applied to more sophisticated 3D structures, including the sub-micron-sized 3D features of the surface forming the AFM tip.

Experimental Example 4: SEM measurement of the layered block copolymer film surface

The SEM of the surface of the layered block copolymer film formed in Example 4 was measured. A schematic diagram illustrating a method for manufacturing a hierarchical block copolymer film in which the PNM coating layer is patterned and the second block copolymer layer is formed on the patterned PNM coating layer is shown in FIG. 9 (a), and oxygen plasma treatment or UV treatment SEM images of the surface of the PNM coating layer selectively patterned according to the region and the region protected by the shadow mask, and the surface of the layered block copolymer film formed using the patterned PNM coating layer are shown in FIGS. 9 (b) and (c), respectively. ) is shown.

As shown in (b) of FIG. 9 , it was confirmed that a patterned PNM coating layer was generated by selective oxygen plasma treatment using a shadow mask.

In addition, as shown in Fig. 9(c), the PS-b-PMMA nano-regions were vertically oriented on the PNM coating layer protected by the shadow mask, whereas parallel nano-regions were formed in the oxygen plasma-treated region, It was confirmed that a layered nanopattern (layered block copolymer film) could be formed.

Claims (23)

1) adding a solution containing the first block copolymer to water and interfacial self-assembly (ISA) of the first block copolymer at an air/water interface to form an interfacial self-assembled first block copolymer layer;
2) transferring a part or all of the first block copolymer layer on a substrate to form a polymer nanomosaic (PNM) coating layer; and
3) coating a solution containing a second block copolymer on the polymer nanomosaic coating layer and heat-treating to form a self-assembled second block copolymer layer,
The first block copolymer comprises a hydrophilic unit block and a hydrophobic unit block,
The method for producing a block copolymer film, wherein the hydrophilic unit block of the first block copolymer has a number average molecular weight fraction of 25% or more with respect to the total number average molecular weight of the first block copolymer.
The method of claim 1,
The first block copolymer layer having a surface pressure of 1 mN / m to 30 mN / m, a method for producing a block copolymer film.
3. The method of claim 2,
The first block copolymer layer having a surface pressure of 1 mN / m to 15 mN / m, a method for producing a block copolymer film.
delete The method of claim 1,
The method for producing a block copolymer film, wherein the hydrophilic unit block has a number average molecular weight of 3,000 g / mol to 200,000 g / mol.
The method of claim 1,
a hydrophobic aggregate of the first block copolymer layer having a dot pattern derived from the hydrophobic unit block; and a plurality of hydrophilic chain molecules derived from the hydrophilic unit block and linked to the hydrophobic aggregate.
7. The method of claim 6,
The method for producing a block copolymer film, wherein the hydrophobic aggregate of the dot pattern has an average diameter of 20 nm to 300 nm.
6. The method of claim 5,
The first block copolymer having a polydispersity index (PDI) of 1 to 3, a method for producing a block copolymer film.
The method of claim 1,
The second block copolymer comprises two different unit blocks,
The method for producing a block copolymer film, wherein the number average molecular weight fraction of one unit block to another unit block in the unit block is 60% or less.
10. The method of claim 9,
The second block copolymer having a number average molecular weight of 5,000 g / mol to 200,000 g / mol, a method for producing a block copolymer film.
11. The method of claim 10,
The second block copolymer has a polydispersity index (PDI) of 1 to 2.5, a method of producing a block copolymer film.
The method of claim 1,
The first block copolymer and the second block copolymer are polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA), polystyrene-block-poly(ethylene oxide) (PS-b-PEO), respectively; Polystyrene-block-polydimethylsiloxane (PS-b-PDMS), polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) and polystyrene-block-poly(4-vinylpyridine) (PS-b) -P4VP) comprising at least one selected from the group consisting of, a method for producing a block copolymer film.
The method of claim 1,
The solutions used in each of steps 1) and 2) are chloroform, methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide and dimethyl A method for producing a block copolymer film, comprising at least one solvent selected from the group consisting of acetamide.
The method of claim 1,
The method for producing a block copolymer film, wherein the interfacial self-assembly is made by evaporating the solvent in the solution for 5 seconds to 60 minutes.
The method of claim 1,
The polymer nano-mosaic coating layer has a water contact angle of 60 ° to 90 °, and has a surface energy of 20 dyne / cm to 40 dyne / cm, a method for producing a block copolymer film.
The method of claim 1,
The method for producing a block copolymer film, wherein the substrate is a two-dimensional or three-dimensional substrate comprising at least one selected from the group consisting of metal, metal oxide, ceramic and polymer.
The method of claim 1,
The method for producing a block copolymer film, wherein the coating is performed by spin coating, bar coating, dip coating or roll coating.
The method of claim 1,
The method for producing a block copolymer film, wherein the heat treatment is performed at 120 ° C to 250 ° C for 10 minutes to 30 hours.
The method of claim 1,
The second block copolymer layer comprising a block copolymer nano-regions oriented perpendicular to the substrate, a method for producing a block copolymer film.
1') adding a solution containing the first block copolymer to water and interfacial self-assembly (ISA) of the first block copolymer at an air/water interface to form an interfacial self-assembled first block copolymer layer;
2') transferring a part or all of the first block copolymer layer onto a substrate to form a polymer nanomosaic (PNM) coating layer;
3') patterning the polymer nano-mosaic coating layer; and
4') coating a solution containing a second block copolymer on the patterned polymer nanomosaic coating layer and heat-treating to form a self-assembled second block copolymer layer,
The first block copolymer comprises a hydrophilic unit block and a hydrophobic unit block,
The method for producing a block copolymer film, wherein the hydrophilic unit block of the first block copolymer has a number average molecular weight fraction of 25% or more with respect to the total number average molecular weight of the first block copolymer.
21. The method of claim 20,
The method for producing a block copolymer film, wherein the patterning is performed in an etching manner by oxygen plasma treatment or UV treatment.
22. The method of claim 21,
The second block copolymer layer includes a block copolymer nanoregion oriented parallel to the substrate on the etched polymer nanomosaic coating layer, and a block copolymer oriented perpendicular to the substrate on the unetched polymer nanomosaic coating layer A method for producing a block copolymer film comprising a nano region.
A block copolymer film prepared according to claim 1 or 20 .

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