KR101815185B1 - Manufacturing method of self-assembled nanopattern using ligth source - Google Patents
Manufacturing method of self-assembled nanopattern using ligth source Download PDFInfo
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- KR101815185B1 KR101815185B1 KR1020150115131A KR20150115131A KR101815185B1 KR 101815185 B1 KR101815185 B1 KR 101815185B1 KR 1020150115131 A KR1020150115131 A KR 1020150115131A KR 20150115131 A KR20150115131 A KR 20150115131A KR 101815185 B1 KR101815185 B1 KR 101815185B1
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- Prior art keywords
- block
- light
- self
- polymer
- block copolymer
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
- H01L21/0275—Photolithographic processes using lasers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/3141—Deposition using atomic layer deposition techniques [ALD]
- H01L21/3142—Deposition using atomic layer deposition techniques [ALD] of nano-laminates, e.g. alternating layers of Al203-Hf02
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/06—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions
- H01L29/0657—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions characterised by the shape of the body
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Abstract
The present invention relates to a method of manufacturing a nanopattern in which a pattern is formed by raising the temperature of a self-assembled polymer through irradiation of light, wherein the χN of the self-assembled polymer is lowered to 10.5 or less at a portion irradiated with light, And then inducing directional self-assembly.
Description
More particularly, the present invention relates to a method of manufacturing a nanopattern using self-assembly, and more particularly, to a method of manufacturing a nanopattern using self-assembly, wherein a light absorption layer is used to induce self- do.
A nanomaterial is a generic term for a material with a size of a few nanometers to a few hundred nanometers, or a structure of any of them. Every material reaches its nanometer level, thereby maximizing the surface area of the material as a whole. And exhibit unique physical / chemical properties and new optical, electrical and magnetic properties. These properties of nanomaterials enable fabrication of highly functional nanoelectronic / magnetic devices that could not be achieved with conventional organic-inorganic materials, but also can be applied to various fields such as energy, environment, medical treatment, It is one of the key factors to improve the quality of life of mankind. However, in order to actualize the expression of such nanomaterials, it is necessary to have a technology capable of effectively synthesizing / manufacturing nanomaterials having a uniform size and shape, and a spatial control technology capable of arranging them in a desired shape.
The nanostructures of self-assembled block copolymers can be used as one of the effective molds for realizing this. Generally, a block copolymer thin film forms various nanostructures having a region of several tens of nanometers in size through a fine phase separation process. The reason why the self-assembled structure using such a block copolymer receives the light is that a regular nanostructure having a size of 30 nm or less can be formed in a large area and a complex process such as photolithography is necessary because such a nanostructure is spontaneously formed It is not.
Among the materials used for self-assembly, the block copolymer generally undergoes phase separation when sufficient energy is applied through annealing to form a nanostructure in which spheres, cylinders, lamella, etc. are periodically arranged do. Since the nanostructure formed by the block copolymer has a thermodynamically stable structure, the nanostructure is spontaneously formed, and the shape and size of the nanostructure can be easily controlled by controlling the relative composition ratio and molecular weight of each block. In addition, since the formation of the block copolymer nano structure progresses in parallel, it is known that the mass production process can be applied.
However, in the conventional annealing method, since energy is applied to the entire specimen, self-assembly of molecules is induced in the entire area, and it is impossible to selectively self-assemble only the desired portion.
In order to solve this problem, several studies have been reported on the application of the zone annealing method to solid self-assembly and molecular self-assembly for single crystal fabrication. The zone annealing method is also referred to as zone melting or band zone melting method and can be performed by heating and melting rod-like solids (metals, semiconductors, etc.) using a narrow annular heating heater The partial melting is caused to occur with a narrow width and the heater is moved to slowly move the molten portion from one end of the rod-shaped sample to the other end.
For example, Alamgir Karim Group, NIST, USA, applied molecular self-assembly to a block copolymer specimen by applying a zone annealing method. In general, when a block copolymer is subjected to sufficient energy through annealing, molecules are self-assembled by the weak force between the secondary molecules. In this study, a thermal gradient was made using a heating block having a centimeter (㎝) size, and then a thermal gradient was applied to the block copolymer specimen using a linear motor to obtain a block copolymer cylinder aligned in one direction (The value obtained by first differentiating the fired ovulation temperature in a specific direction, which means the rate at which the temperature changes from one point to another, and the temperature difference between two points is divided by the distance.)
However, the heating block has only a very low thermal gradient of 17 deg. C / mm. Therefore, there is a problem that the degree of alignment is very low to apply the molecular self-assembly. In particular, it is more difficult to apply molecular self-assembly to the selective region, and it is further difficult to apply to the three-dimensional substrate.
Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a nano-pattern fabrication method using self-assembly, which induces self-assembly of molecules in a local region by applying a high- .
The present invention relates to a method of manufacturing nanopatterns using self-assembly.
In one embodiment of the present invention, a pattern is formed by raising the temperature of a self-assembled polymer through irradiation of light, wherein a χN of the self-assembled polymer is lowered to 10.5 or less at a portion irradiated with light, Lt; RTI ID = 0.0 > directional self-assembly. ≪ / RTI >
In the present invention, the self-assembled polymer comprises 1 to 100% by weight of a block copolymer and 0 to 99% by weight of a mutual coefficient (x) reduction agent.
In the present invention, the self-assembled polymer is characterized by satisfying the following
[Formula 1]
0.8T ODT ? T? 1 ? 3.0T ODT
(Where T 1 is the temperature of the self-assembled polymer and T ODT is the rule-random phase transition temperature of the block copolymer).
Also, the energy density of the light is 0.001 to 200,000 W / mm 2, the moving speed of the light is 0.001 nm / s to 100 cm / sec, and the focal length of the light may be 100 nm or more.
In the present invention, the self-assembled polymer is applied to the surface of the light absorbing layer, and the light absorbing layer has a light transmittance of 99.9% or less. The light absorbing layer has a transmittance of 99.9% or less and is composed of at least one selected from the group consisting of graphene oxide, carbon nanotubes, A thin film, a metal oxide thin film, and a transition metal chalcogenide thin film.
In the present invention, the block copolymer may be a polyurethane, an epoxy polymer, a polyarylene, a polyamide, a polyester, a polycarbonate, a polyimide, a polysulfone, a polysiloxane, a polysilazane, a polyether, a polyurea, a polyolefin, And may include two or more different repeating units selected from the group consisting of polystyrene-block-polymethyl methacrylate, polybutadiene-polybutyl methacrylate, polybutadiene-block-polydimethylsiloxane, Block-polyvinylpyridine, polybutadiene-block-polymethylmethacrylate, polybutadiene-block-polyvinylpyridine, polybutyl acrylate-block-polymethylmethacrylate, polybutylacrylate- Vinylpyridine, polyisoprene-block-polymethyl methacrylate, polyhexyl acrylate-block-poly Block-polybutyl methacrylate, polyisobutylene-block-polybutyl methacrylate, polyisobutylene-block-polybutyl methacrylate, polyisobutylene- Block-polybutyl methacrylate, polystyrene-block-polybutyl methacrylate, polystyrene-block-polybutyl methacrylate, polystyrene-block-polybutyl methacrylate, Block-polyvinylpyridine, isoprene, polystyrene-block-polydimethylsiloxane, polystyrene-block-polyvinylpyridine, polyethylethylene-block-polyvinylpyridine, polyethylene-block-polyvinylpyridine, polyvinylpyridine-block-polymethylmethacrylate, Block-polyisoprene, polyethylene oxide-block-polybutadiene, polyethylene oxide-block-polystyrene, polyethylene oxide-block-poly Block-polystyrene-block-polystyrene-block-polydimethylsiloxane, polystyrene-block-polyethylene oxide, polystyrene-block-polymethylmethacrylate-block-polystyrene, polybutadiene-block-polybutylmethacrylate- Block polybutadiene block polybutadiene block polybutadiene block polybutadiene block polybutadiene block polybutadiene block polybutadiene block polybutadiene block polyimide methacrylate block polybutadiene polybutadiene block polyvinylpyridine block polybutadiene polybutadiene block polybutadiene block polybutadiene poly Block-poly (n-butylacrylate) as an acrylic polymer, nitrile-block-poly (epsilon -caprolactone) as an acrylic polymer, polydimethylsiloxane- Block-polysulfone, polymethyl methacrylate-block-poly (2-hydroxyethyl methacrylate), polybutyl acrylate-block- Polyisoprene block-polyisoprene block-polyisoprene block-polyisoprene block-polyisoprene block-polyisoprene block-polyisoprene, polyhexylacrylate block-polyvinylpyridine Block-polyisobutylene, block-polyisobutylene, block-polyisobutylene, block-polyisobutylene, block-polyisoprene, Block-polyisobutylene, block-polyisobutylene, block-polyisobutylene, block-polyisobutylene, block-polybutylmethacrylate, Polybutylene terephthalate, polybutylene terephthalate, polybutylene terephthalate, polybutylene terephthalate, polybutylene terephthalate, polybutylene terephthalate, polybutylene terephthalate, polybutylene terephthalate, Block-polystyrene, block-polystyrene-block-polystyrene, block-polystyrene, block-polydimethylsiloxane-block-polystyrene, polystyrene-block-polyvinylpyridine-block-polystyrene, polyethylethylene-block-polyvinylpyridine Block-polyethylenes, block-polyethylenes, polyethylene-block-polyvinylpyridine-block-polyethylenes, polyvinylpyridine-block-polymethylmethacrylate-block-polyvinylpyridine, polyethylene oxide- Block-polybutadiene-block-polyethylene oxide, polyethylene oxide-block-polystyrene-block-polyethylene oxide, polyethylene oxide-block-polymethylmethacrylate-block-polyethylene oxide, polyethylene oxide- Block-Polyethylene Oxide and Polystyrene-Block-Polyethylene Oxide - block - can include any one or more selected from polystyrene.
The number average molecular weight of the block copolymer may be 3,000 to 30,000,000 g / mol.
In the present invention, the mutual coefficient (χ) reducing agent may be a random copolymer having a number average molecular weight of 1,000 to 3,000,000 g / mol. Specific examples thereof include a polyurethane, an epoxy polymer, a polyarylene, a polyamide, And may include two or more different unit repeating units selected from the group consisting of a carbonate, a polyimide, a polysulfone, a polysiloxane, a polysilazane, a polyether, a polyurea, a polyolefin, a vinyl-based addition polymer and an acrylic polymer.
In the present invention, the mutual coefficient (χ) reduction agent may more specifically include a repeating unit derived from 0 to 100% by weight of a styrene-based monomer and 100 to 0% by weight of a methacrylate-based monomer.
Another aspect of the present invention may be a semiconductor device including a nanopattern manufactured according to the above method.
According to the nanopattern manufacturing method of the present invention, a very high thermal gradient can be obtained by partially irradiating light, and the orientation of the magnetic molecule assembly can be arbitrarily adjusted by applying the annealing. In addition, self-assembly of molecules can be applied in a selective region by irradiating light even on a substrate which is not bent regardless of the shape of the substrate or on a non-flat substrate.
In addition, the nanopattern manufacturing method according to the present invention can form various aligned patterns only in a selective region, and the thus-produced block copolymer pattern can be used for pattern transfer. Thus, it can be applied to the pattern process of less than 10 nm which is sealed by the conventional semiconductor process, and it is possible to realize various circuit patterns through simple light irradiation without a prior photoresist pattern or chemical pattern.
FIG. 1 shows a schematic embodiment of a method of manufacturing a nanopattern using self-assembly according to the present invention.
2 is a flow chart illustrating a schematic embodiment of a method of manufacturing a nanopattern using self-assembly according to the present invention.
FIGS. 3 to 6 show SEM and schematic views of an embodiment of a method of manufacturing a nanopattern using self-assembly according to the type and shape of a substrate.
FIGS. 7 to 8 show the temperature gradients of the light absorbing layer at the time of light irradiation according to Example 1 by using an infrared camera (Flir, T400, USA).
FIG. 9 is a SEM and a graph showing a pattern formation pattern according to time and energy density in Example 2. FIG.
FIGS. 10 to 12 are SEMs and graphs illustrating pattern formation patterns according to the light scanning speed in Example 3. FIG.
13 shows an oriental order parameter according to the scanning speed of light.
FIG. 14 shows a correlation length according to the reciprocal of the light scanning speed.
FIG. 15 is a graph and an SEM of pattern formation according to scan time and temperature in Examples 1 to 3.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings. It should be understood, however, that the invention is not limited thereto and that various changes and modifications may be made without departing from the spirit and scope of the invention.
Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In addition, the following drawings are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. Therefore, the present invention is not limited to the following drawings, but may be embodied in other forms, and the drawings presented below may be exaggerated in order to clarify the spirit of the present invention. Also, throughout the specification, like reference numerals designate like elements.
Also, the singular forms as used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.
In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected."
In the present invention, the term " orientation order parameter (Psi) " indicates how far two or more patterns having a line shape are aligned in one direction. When the patterns are perfectly aligned in one direction, .
The term " correlation length " in the present invention indicates how certain patterns are related to each other in a certain pattern, and indirectly measures the domain size of the pattern, the pattern of the lamella pattern becomes close to infinity.
In order to apply self-assembly locally to a specific portion of a polymer substrate as described above, it is desired that the wavelength of the light, the size of the region of light to be irradiated, the energy density, The condition of the light is irradiated, and the χN value of the polymer thin film to be irradiated is kept within a specific range, so that the light irradiation region is instantaneously made disordered, and thus it is found that the pattern is formed very quickly and naturally Respectively.
In general, the formation of a microstructure of a specific shape through self-assembly of a block copolymer is affected by the physical / chemical properties of the unit blocks. When the block copolymer exists in a thin film state on the substrate, the polymer chain becomes fluid when the temperature exceeds the glass transition temperature. Therefore, in order to minimize the free energy due to the interface between the block copolymer and the substrate and the surface attraction, , Which is arranged on the substrate with a specific pattern. In this case, if one block has a selective interaction with the substrate, the alignment of the nanostructure parallel to the substrate occurs. Further, by adjusting the surface attraction of the substrate and the block copolymer, it is possible to adjust the orientation to be parallel or perpendicular to the substrate, thereby making it possible to produce a uniform pattern.
However, in the case of the conventional self-assembly pattern formation method, as described above, by forming the pattern by raising the temperature, it is only necessary to apply the temperature isotropically to the entire substrate, and instantaneously high temperature It is very difficult to induce self-assembly only in the corresponding portion.
The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a method and apparatus for selectively self-assembling only a portion irradiated through light irradiation, Unnecessary self-assembly that may occur in the portion can be suppressed. No special environment is required and the process can be carried out at room temperature and general air atmosphere. By adjusting the conditions such as the wavelength of light, the size of the region of the light to be irradiated, the energy density, and the scanning speed of the light, a very stable and identical pattern can be formed according to the monomers constituting the block copolymer.
In addition, only the portion irradiated with light is selectively self-assembled so that it is not affected by the shape of the substrate at all. For example, even if the irradiation position is curved, edge, irregular, etc., It is possible to form a pattern stably without being influenced by the material of the substrate such as glass, polyimide, and flexible, thereby completing the present invention.
The method of manufacturing a nanopattern using self-assembly according to the present invention is to form a nanopattern by raising the temperature of the self-assembled polymer through irradiation of light. Specifically, in the portion irradiated with light, χN of the self- To induce directional self-assembly after applying a completely disordered state.
More particularly, the present invention relates to a method for preparing a nanopattern,
a) forming a light absorbing layer on a substrate;
b) forming a polymer layer by coating a self-assembled polymer including a block copolymer on the surface of the light absorbing layer; And
c) irradiating the polymer layer with light and performing self-assembly to form a nanopattern;
. ≪ / RTI >
First, the light absorbing layer used in the above manufacturing method is for guiding the self-assembly of the polymer layer by transferring the light energy transmitted by the light irradiation to the thermal energy, and is formed of a material having a high light absorption coefficient and a good heat transfer characteristic desirable.
For example, the light absorption coefficient of the light absorption layer may be greater than the light absorption coefficient of the polymer layer, and the reflection coefficient of the light absorption layer may be higher than that of the polymer Layer may be less than the reflection coefficient of the layer. The light absorptivity of the light absorbing layer is not limited, but may be 0.001 to 99.99%, preferably 0.01 to 99.99%.
In the present invention, the light absorbing layer is not limited to the material of the light emitting layer. However, the light absorbing layer may be formed of a material selected from the group consisting of oxide graphene, carbon nanotubes, chemically modified graphene, amorphous carbon, silicon, ceramic thin film, metal thin film, metal oxide thin film and transition metal chalcogenide thin film And may include any one or two or more selected carbon materials or metals, non-metal thin films. Particularly, it is preferable to use a material having excellent mechanical durability because the light absorption layer is preferably made of graphene which has a honeycomb crystal lattice and is in the form of one-atom-thick planar sheets of a carbon atom, It is recommended to use chemically modified graphene (CMG). The chemically modified graphene is very thin and absorbs light well and has a very high light-to-heat conversion efficiency because it has low thermal conductivity unlike graphene using chemical vapor deposition (CVD). However, the present invention is not limited thereto, and if it is a substance having a high light absorption coefficient in addition to the above-mentioned substance, it can be used without any delay.
Fig. 2 shows an example using the chemically modified graphene in the present invention. As shown in FIG. 2, chemically modified graphene can be easily applied to a flexible substrate having an uneven substrate or a flexible substrate. A polymer layer is formed by coating a block copolymer, So that self-assembly can be applied.
In the present invention, the light absorbing layer may contain a dye (for example, a visible light dye, an ultraviolet dye, an infrared dye, a fluorescent dye, and a polarizing dye), a pigment, a metal, a metal compound, a metal film, And metal sulfides, and the like.
In the present invention, the dyes and pigments are not limited as long as they can convert light energy absorbed in light irradiation into heat energy. Examples of the dyes and pigments include di-ammonium dyes, metal-complex dyes, naphthalocyanine dyes, phthalocyanine dyes, polymethine dyes, anthraquinone dyes, porphyrin dyes and metal- Cyanine dyes, carbon black pigments, metal oxide pigments, metal sulfide pigments, graphite pigments, and mixtures thereof.
On the other hand, the absorption of light decreases as the thickness of the light absorbing layer decreases and the heat transfer decreases as the thickness of the light absorbing layer increases. Therefore, the thickness of the light absorbing layer is preferably limited to a suitable range in which light absorption and heat transfer are good. Nm to 1 cm. Furthermore, since the polymer layer is laminated on the upper surface of the light absorbing layer, the shape of the light absorbing layer can be freely changed according to the shape of the substrate, and the present invention is not limited thereto.
In the present invention, the substrate supports the light absorbing layer and the polymer layer. The substrate may be disposed on a surface of the light absorbing layer facing the surface on which the polymer layer is disposed, and may be used for polymer coating and thin film formation It is not limited to types and forms. For example, glass, silicon, ceramic, metal, polyimide (PI), polycarbonate (PC), polyethersulfone (PES), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyarylate (PAR), and cycloolefin (COC), and may have any shape such as curved, edge, irregular, or the like . Also, it is not affected by thickness.
For example, FIGS. 3 to 6 show the shape of the substrate (FIG. 4: glass pipette; FIG. 5: silicon edge; FIG. 6: imide film; FIG. 7: polyimide film Plane) was irradiated by SEM. As shown in the figure, a uniform and uniform pattern was formed regardless of the shape of the substrate.
Next, a polymer layer including a block copolymer may be formed on the surface of the light absorbing layer as in step b).
In the present invention, the polymer layer may include a block copolymer capable of forming a pattern through self-assembly. The block copolymer refers to a functional polymer in which two or more unit blocks having different structures or properties are bonded to each other through a covalent bond, and each unit block constituting the block copolymer has a chemical structure And have different physical properties and selective solubilities. This causes the block copolymer to form a self-assembled structure by phase separation or selective dissolution in solution or solid phase.
The fact that the block copolymer forms a microstructure of a specific shape through self-assembly is affected by the physical / chemical properties of the unit block. When the block copolymer exists in a thin film state on the substrate, the polymer chain becomes fluid when the temperature exceeds the glass transition temperature. Therefore, in order to minimize the free energy due to the interface between the block copolymer and the substrate and the surface attraction, , Which is arranged on the substrate with a specific pattern. In this case, if one block has a selective interaction with the substrate, the alignment of the nanostructure parallel to the substrate occurs. Further, by adjusting the surface attraction of the substrate and the block copolymer, it is possible to adjust the orientation to be parallel or perpendicular to the substrate, thereby making it possible to produce a uniform pattern.
For example, when a diblock copolymer consisting of two different structures is self-assembled on a bulk substrate, the volume fraction between each unit block constituting the block copolymer is determined by the volume fraction of each monomer unit It is primarily affected by the molecular weight of the block. The self-assembled structure of the block copolymer has cubic, double gyroid, and hexagonal packed column structures and two-dimensional structure, which are three-dimensional structures according to the volume ratio between the two unit blocks. a lamellar structure, and the like are determined. At this time, the size of each unit block in each structure is proportional to the molecular weight of the corresponding unit block.
The block copolymer according to the present invention may comprise one or more hydrophilic unit blocks and one or more hydrophobic unit blocks polymerized with each other. In this case, the molecular weight ratio of each unit block is preferably in the range of hydrophilic unit block 20 to 80: hydrophobic unit block 80 to 20, when the total block copolymer molecular weight is 100.
For example, a plate-shaped (lamellar) nanostructure having a patterned structure may be formed when the molecular weight ratio of each unit block is 50: 50, and a cylindrical nanostructure having a patterned structure may be formed when the molecular weight ratio is 70: 30 . In addition, a sialoid or spherical nanostructure may be formed according to the composition ratio, but the present invention is not limited thereto.
Examples of the block copolymer according to the present invention include polyurethane, epoxy polymer, polyarylene, polyamide, polyester, polycarbonate, polyimide, polysulfone, polysiloxane, polysilazane, polyether, polyurea, polyolefin , A vinyl-based addition polymer and an acrylic polymer, and more particularly to a composition comprising two or more different repeating units selected from the group consisting of polystyrene-block-polymethylmethacrylate, polybutadiene-polybutylmethacrylate polybutadiene-block-polybutylmethacrylate, polybutadiene-block-polydimethylsiloxane, polybutadiene-block-polymethylmethacrylate, polybutadiene-block-polyvinylpyridine polybutadiene-block-polyvinylpyridine, polybutyl acrylate-block-polymethylmethacrylate Polybutylene terephthalate, polybutylacrylate-block-polymethylmethacrylate, polybutylacrylate-block-polyvinylpyridine, polyisoprene-block-polyvinylpyridine, polyisoprene- Polyisoprene-block-polybutylmethacrylate, polyhexylacrylate-block-polyvinylpyridine, polyisobutylene-block-polybutylmethacrylate, , Polyisobutylene-block-polymethylmethacrylate, polyisobutylene-block-polybutylmethacrylate, polyisobutylene-block-polydimethylsiloxane, Polyisobutylene-block-polydimethylsiloxane, polybutylmethacrylate-block-polybutylacrylate polyacrylonitrile, polystyrene-block-polyacrylate, polyethylethylene-block-polymethylmethacrylate, polystyrene-block-polybutylmethacrylate, polystyrene- polybutadiene, polystyrene-block-polyisoprene, polystyrene-block-polydimethylsiloxane, polystyrene-block-polyvinylpyridine, Block-polyvinylpyridine, polyethylene-block-polyvinylpyridine, polyvinylpyridine-block-polymethylmethacrylate, polyethylene oxide-block-polyvinylpyridine, Block-polyisoprene, polyethylene oxide-block-polybutadiene (polyethyleneoxide-block-polyisoprene) e-block-polybutadiene, polyethyleneoxide-block-polystyrene, polyethyleneoxide-block-polymethylmethacrylate, polyethyleneoxide- block-polydimethylsiloxane, polystyrene-block-polyethyleneoxide, polystyrene-block-polymethylmethacrylate-block-polystyrene, polybutadiene- Polybutadiene-block-polybutadiene-block-polybutadiene, polybutadiene-block-polydimethylsiloxane-block-polybutadiene-block-polybutadiene, Polybutadiene-block-polymethylmethacrylate-block-polybut < / RTI > polybutadiene-block-polyvinylpyridine-block-polybutadiene, polybutyl acrylate-block-polybutylacrylate-block-polybutadiene- block-polyvinylpyridine-block-polybutylacrylate, polybutyl acrylate-block, polybutylacrylate-block-polyvinylpyridine-block- Polyisoprene-block-polyvinylpyridine-block-polyisoprene, polyisoprene-block-polymethylmethacrylate-block-polyisoprene, polyhexyl acrylate-block-polyvinylpyridine Polyhexylacrylate-block-polyvinylpyridine-block-polyhexylacrylate, polyisobutylene-block-polybutylmethacrylate Block-polyisobutylene-block-polyisobutylene, polyisobutylene-block-polyisobutylene, polyisobutylene-block-polyisobutylene, Polyisobutylene-block-polybutylmethacrylate-blockpolyisobutylene, polyisobutylene-block-polydimethylsiloxane-block-polyisobutylene-block polybutylmethacrylate-block-polybutylmethacrylate (polybutylmethacrylate-block-polybutylmethacrylate), polyethylethylene-block-polymethylmethacrylate Poly-ethylene-block-polymethylmethacrylate-block-polyethylethylene, polystyrene-block-polybutylmethacrylate-block-polystyrene polybutylene terephthalate, polystyrene-block-polybutylmethacrylate-block-polystyrene, polystyrene-block-polybutadiene-block-polystyrene, polystyrene-block-polyisoprene -block-polystyrene, polystyrene-block-polydimethylsiloxane-block-polystyrene, polystyrene-block-polyvinylpyridine-block-polystyrene ), Polyethylethylene-block-polyvinylpyridine-block-polyethylene-block-polyvinylpyridine-block-polyethylene (PTFE), polyethylene-block-polyvinylpyridine-block-polyethylene ), Polyvinylpyridine-block-polymethylmethacrylate-block-polyvinylpyridine-block-polymethylmethacrylate-block-polyvinylpyridine, Block-polyisoprene-block-polyethyleneoxide, polyethylene oxide-block-polybutadiene-block-polyethyleneoxide, polyethylene oxide-block- Block-polystyrene-block-polyethyleneoxide, polyethyleneoxide-block-polymethylmethacrylate-block-polyethyleneoxide, polyethyleneoxide-block-polystyrene-block-polyethyleneoxide, Block-polydimethylsiloxane-block-polyethyleneoxide, and polystyrene-block-polyethyleneoxide-block-polystyrene Use one or more However, not necessarily that the present invention is limited to this, and in addition, if the building block copolymer capable of forming a self-assembly according to but may also use of any of them.
In the present invention, if the block copolymer can form a pattern through self-assembly, it is not limited to the molecular weight, but may preferably be 3,000 to 30,000,000 g / mol, more preferably 30,000 to 3,000,000 g / mol in number average molecular weight. When the block copolymer has a number average molecular weight outside the above range, pattern formation does not occur properly or the viscosity increases greatly, making it difficult to form a polymer thin film having a uniform thickness.
The Reducing agent of Flory-huggins interaction parameter serves to reduce the value of χN in the polymer layer. Specifically, when the polymer layer is irradiated with light, the temperature of the pattern part in the polymer layer is And the χN value of the region irradiated with light is lowered to 10.5 or less to render the region disordered and rearrange the pattern of the block copolymer.
More specifically, when χ is a value that decreases with temperature (χα1 / T) and the temperature of the thin film continuously increases due to light irradiation to reach the T ODT (order-disordered phase transition temperature), the χ N value 10.5. However, depending on the block copolymer, the χN value does not fall below 10.5 even when the temperature is increased to any degree. By adding the mutual coefficient (χ) reducing agent, the χN value of the relevant part is lowered to 10.5 or less and the polymer pattern is rearranged .
In the present invention, the mutual coefficient (χ) reducing agent may be any one or two or more selected from a random copolymer, a block oligomer, a surface-treated inorganic particle and a solvent. However, And the present invention is not limited thereto.
In the present invention, the χN is a factor determining the self-assembly of the block copolymer, and the degree of polymerization (N) of the block copolymer to the flory-Huggins mutual coefficient χ of the block copolymer and the mutual modulus (χ) ). However, χ is a value that varies flexibly depending on the kind of polymer, molecular weight, kind of solvent, temperature and crosslinked structure.
In the present invention, the above-mentioned χ can be obtained by the following equation (2).
[Formula 2]
In the formula 2, V represents the volume of the composition, R represents the gas phase, T represents the temperature of the composition, and δ represents the solubility constant (δ 1 ) and the solubility constant (δ 2 ). The solubility constants of each component are obtained by dividing the sum of the Molar attraction constant ( F ) of each component by the molar volume according to the Group Contribution method.
In the case of a diblock copolymer in which two blocks are mutually symmetrical in a generally prepared block copolymer thin film including a solvent and the like, thermodynamic theory shows that micro-separation occurs when the χN is 10.5 or more (C. Park, J. Yoon , and EL Thomas, Polymer, 44/22, 6725 (2003)). This microphase separation is oriented in various forms such as a lamella, a double gyroid, a cylinder, and a body center cubic depending on the volume fraction of each block, and the diversity of such a structure can be connected to a variety of self-assembled microstructures.
However, as described above, in the self-assembled microstructure, many defects can be formed with disordered alignment direction when orienting the nano-domains, and therefore, when defects are formed, patterns including defects are fixed, .
In order to solve this problem, in the present invention, by further adding mutual coefficient (χ) reducing agent, the disordered state is induced by reducing the χN value temporarily to 10.5 or less at the portion irradiated with light. In this case, the mutual coefficient (χ) reducing agent temporarily induces the state of the block copolymer in the portion irradiated with light to become disordered, thereby naturally forming a pattern of the block copolymer.
As described above, the χN value is a value that can be changed depending on the kind of polymer, molecular weight, kind of solvent, temperature, crosslinking structure, etc. Therefore, a mutual coefficient (χ) reducing agent should be added so that χN value is less than 10.5 do. For example, assuming that the block copolymer is a polymethyl methacrylate-polystyrene copolymer and has a molecular weight of 25 k and 26 kg / mol, respectively, the molar fraction of the mutual coefficient (χ) reduction agent is referred to as Φ random and the mole fraction of the block copolymer If 1-Φ random, which, χN BP = 18 to Φ random = 0.4 when referred χN drawback is order-disorder transition (order-disorder transition) and the same value having a value equal to or less than 10.5, χN a drop below this value , The χN value of the entire thin film is lowered, and alignment of the fine nano patterns is not generated any more, resulting in an entirely disordered state.
When the χN value of the portion irradiated with the light is lowered to 10.5 or less, the energy barrier necessary for forming the pattern is greatly reduced. At the same time, the pattern is very fast and uniformly rearranged. And can be effectively manufactured.
In the present invention, the random copolymer means that two or more monomers are polymerized in an unordered manner, and is a concept as compared with the block copolymer. That is, the Tg of the block copolymer is different from that of the random copolymer by measuring the glass transition temperature (Tg) by the number of monomers, while the random copolymer has a single Tg and the manufacturing process is simpler. In the present invention, the random copolymer has a lower molecular weight than the block copolymer.
In the present invention, the random copolymer does not limit the repeating unit, the polymerization method and the like to the extent that the above objects can be achieved. Examples of the repeating unit include polyurethane, epoxy polymer, polyarylene, polyamide, polyester, polycarbonate, polyimide, polysulfone, polysiloxane, polysilazane, polyether, polyurea, polyolefin, Based polymer may further include at least one repeating unit selected from an acrylic polymer. Herein, the number of repeating units is more than one, for example, in the case of polyurethanes, diisocyanates and diamines are polymerized to have urethane bonds, and when the random copolymer is formed, Quot; means a form in which two or more polyurethanes having different structures are randomly bonded.
In the present invention, the repeating units contained in the random copolymer preferably include repeating units derived from the monomers constituting the block copolymer in common. For example, when a polymethyl methacrylate-block-polystyrene block copolymer is used, a preferable random copolymer includes a repeating unit derived from a styrene-based monomer and a repeating unit derived from a methacrylate-based monomer, In the case of pyridine-block-polymethylmethacrylate, preferred random copolymers include repeating units derived from vinylpyridine-based monomers and repeating units derived from methacrylate-based monomers.
In the present invention, the polymerization ratio is not limited, but it is preferable that the block copolymer contains 10 to 90% by weight of the styrene-based monomer and 90 to 10% by weight of the methacrylate-based monomer,
In the present invention, the random copolymer preferably has an average molecular weight smaller than that of the block copolymer, and preferably has a number average molecular weight of 1,000 to 3,000,000 g / mol. If the number average molecular weight is less than 1,000 g / mol, it can not be used as a mutual coefficient (χ) reducing agent because it does not have sufficient chemical preference. If the number average molecular weight is more than 3,000,000 g / mol, it can not be sufficiently mixed with the block copolymer thin film.
In the present invention, the block oligomer means that one or two or more monomers are polymerized in a small block form, and the degree of polymerization is not limited, but preferably 2 to 20 monomers or oligomers are polymerized. The kind of the monomer or oligomer is not limited, and the same or different monomers or oligomers may be polymerized with the block copolymer or the random copolymer.
Examples of oligomers usable in the production of block oligomers in the present invention include urethane oligomers, epoxy oligomers, arylene oligomers, amide oligomers, ester oligomers, carbonate oligomers, imide oligomers, sulfone oligomers, siloxane oligomers , Silane-based oligomers, ether-based oligomers, urea-based oligomers, vinyl-based addition polymers, and acrylate-based oligomers.
In the present invention, the surface-treated inorganic particles are prepared by coating a particle surface having an average particle diameter of several nanometers with a random copolymer, a block oligomer, a block copolymer or the like. As with the random copolymer or the block oligomer, It is possible to have the effect of reducing the χN value near the defect.
In the present invention, the material to be coated on the surface of the inorganic particles is not limited to the kind, and the random copolymer and the block oligomer described above may be coated. The coating thickness, treatment method and the like are not limited.
In the present invention, the inorganic particles are not particularly limited as long as they are coatable core particles, and both conductive and non-conductive particles are possible. The particle size is not limited, but the particle size of the inorganic particles is preferably small as the pattern is finer and the permeability is not affected without affecting the pattern shape. Therefore, it is preferably less than 20 nm, more preferably 0.1 to 10 nm.
In the present invention, the solvent is used to reduce the χ N value of the block copolymer, and is not limited to organic or inorganic. However, when the block copolymer is easily evaporated during the heat treatment for self-assembly, defect melting may not occur properly. Therefore, it is preferable to use a solvent having a boiling point of 170 ° C or more, preferably 170 to 220 ° C.
Examples of the solvent include, but are not limited to, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate acetate, diethylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, Dipropylene glycol propyl ether acetate, dipropylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monohexyl ether, Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, triethylene glycol monopropyl ether, ether solvents such as ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monobutyl ether; Gamma-valerolactone, delta-valerolactone, gamma-butylrolactone, gamma-hexalactone, gamma-octalactone, gamma-valerolactone, gamma- At least one lactone-based solvent selected from Gamma-decanolactone, Delta-octanolactone and Delta-dodecanolactone; And is selected from cyclohexylbenzene, dodecylbenzene, 1,2,3,4-tetramethylbenzene, o-dihydroxybenzene, and the like. Any one or more aromatic solvents; At least one sulfone solvent selected from the group consisting of dimethyl sulfoxide, sulfolane, dimethylsulfolane and dibutylsulfone; And the like. In addition to these, there may be mentioned dimethyl formamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, diisononyl Diisononyl-1,2-cyclohexane-
In the present invention, the mutual coefficient reducing agent can be freely adjusted depending on the molecular weight of the block copolymer or the kind of the mutual coefficient (χ) reducing agent, but it may include 10 to 50% by weight of 100% by weight of the whole mixture. If less than 10% by weight of the block copolymer composition is added, the defect melting effect is not sufficiently exhibited. If the block copolymer composition is added in an amount of more than 50% by weight, the overall χN value of the block copolymer composition is decreased to less than 10.5, .
For example, when the block constituting the block copolymer is polystyrene-polymethylmethacrylate, and each of 25 kg / mol and 26 kg / mol, the mutual coefficient (χ ) The reducing agent content is preferably 28 to 32% by weight of 100% by weight of the total mixture. However, as described above, the optimal composition ratio is in the range of 10 to 50% by weight depending on the molecular weight of the block copolymer, the molecular weight of the mutual modifier (x) reducing agent, and the like, And the present invention is not limited thereto.
After the polymer layer is formed on the surface of the light absorbing layer, the polymer layer can be self-assembled by irradiating light onto the polymer layer as in the step c).
In one embodiment of the present invention, the light induces self-assembly of the polymer layer by supplying energy to the light absorption layer or the polymer layer applied to the substrate. The light may be generated within a range that does not cause degradation of organic polymeric molecules The type of light, the wavelength size, the energy density, and the speed of light travel.
In the present invention, examples of the light include a solid laser for high output, a gas laser, and a gas laser with high stability. However, the present invention is not limited thereto, and the present invention is not limited to a specific light.
In the present invention, the light may be irradiated to the self-assembled material through the three-dimensional movement direction of the light source. Therefore, the present invention can be applied to a substrate having a three-dimensional structure in addition to a substrate having a two-dimensional structure. For example, the substrate can be applied to a bent substrate, a spherical substrate, or a hexahedral substrate or a semiconductor substrate having a complicated three-dimensional structure. That is, by using a stage including light having a three-dimensional movement direction, it is possible to selectively apply molecular self-assembly to a very small portion as if drawing a picture. Thus, it is very meaningful to selectively apply molecular self-assembly to a desired region, and it is highly compatible with various other methods and can be said to be a highly applicable technology in various forms.
In one embodiment of the present invention, the light may be locally illuminated and moved to form a pattern. A method of forming a pattern using light, which can locally irradiate light onto a substrate, allows selective alignment adjustment, and also has improved alignment control.
In one embodiment of the present invention, the light is not limited to a wavelength form, but can be used without problems if it has a wavelength in a region where there is no selective reaction with the block copolymer contained in the polymer layer. However, it is preferable that the block copolymer or the mutual coefficient (χ) reducing agent contained in the polymer layer has a visible light or near-infrared light and a far-infrared wavelength so as not to be thermally decomposed. For example, in the case of a block copolymer, cross linking reaction occurs in the case of irradiation with ultraviolet light having a wavelength greater than that of the ultraviolet region, so that self-assembly can not be applied. Therefore, the wavelength of the visible light region band or the near-infrared region band, which is not the wavelength of the ultraviolet region band, can be used without any problem.
More specifically, in the step c), it is preferable that the light absorbing layer satisfies the following
[Formula 1]
0.8T ODT ? T? 1 ? 3.0T ODT
(Where T 1 is the temperature of the light absorbing layer and T ODT is the rule-irregular phase transition temperature of the block copolymer).
Since the nanostructure formed by the block copolymer is thermodynamically stable, the nanostructure is spontaneously formed. However, in order for the block copolymer to form a nanostructure, it is necessary to re-arrange the chain of the block copolymer by applying energy to the polymer.
When light energy is applied to the polymer layer, the light absorbing layer converts the light energy into heat energy, and the polymer layer receives the heat energy. Such light-induced heating may disperse the chain of the block copolymer, and micro-phase separation may occur. When the temperature of the polymer layer further increases, various patterns such as a lamellar phase and a cylinder phase grow depending on the polymerization degree of the block copolymer. The problem is that these patterns are not arranged in a certain direction but are arbitrarily oriented, making it difficult to apply them as desired nano devices.
Therefore, it is necessary to adjust the temperature applied to the block copolymer to a specific range to obtain the desired aligned nanopattern. Particularly, as the temperature applied to the polymer increases, such a randomly oriented pattern is transformed into a disordered state, whereby the block copolymer is rearranged. In order to convert the pattern of the block copolymer into a disordered phase, it is preferable to raise the temperature of the light absorption layer to a temperature similar to the order-disorder phase transition temperature (T ODT ). That is, when the energy density, the scan speed, the irradiation time, and the like are adjusted so that the temperature of the light absorbing layer is in the range of the above-mentioned
In the present invention, T 1 in the
In order to satisfy Equation (1), the wavelength of light according to the present invention is preferably 400 nm or more, more specifically 500 to 15,000 nm. In the case of a shorter wavelength of less than 400 nm, it is difficult to form a uniform pattern due to cross-linking reaction between the block copolymers as described above, and even degradation may occur.
In the present invention, the energy density of light is a factor that induces self-assembly by controlling the temperature of the irradiated region of the polymer layer. Polymerization of the block copolymer contained in the polymer layer may vary depending on the polymerization density of the monomer or monomer. However, the temperature is generally in the range of about 100 to 300 ° C. If the temperature is exceeded, the polymer may be deteriorated, Is less than the above range, the self-assembly itself may not proceed, so it is important to control the energy density of light.
In the present invention, the energy density of light may be 0.001 to 200,000 W / mm 2, more preferably 0.01 to 500 W / mm 2, and most preferably 1 to 50 W / mm 2. When the energy density is less than 0.001 W / mm < 2 >, the self-assembly of the polymer layer does not progress. When the energy density is more than 2000 W / mm < 2 >, the crosslinking of the block copolymer may proceed or degrade. However, the energy density can be freely changed according to the polymeric monomer of the block copolymer for applying self-assembly, the molecular weight, the presence or absence of the mutual coefficient (χ) reducing agent, and the present invention is not limited thereto.
In the present invention, the moving speed of light is a factor determining the degree of self-assembly of the polymer layer to be irradiated irrespective of the traveling direction. When the moving speed of light increases, the thermal gradient and the temperature of the focused area decrease . Further, the higher the energy density, the higher the moving speed may be. Therefore, the molecular self-assembly can be efficiently applied to the substrate by appropriately calculating it and adjusting the moving speed of the light according to the above conditions. However, the present invention is not limited to the moving speed range, but may be adjusted to a moving speed range or more according to conditions such as the type of substrate, wavelength of light, focused area size or energy density.
In the present invention, the light traveling rate may be 0.001 nm / s to 100 cm / sec, preferably 1 nm / s to 10 cm / sec, and most preferably 10 nm / s to 1 cm / sec. If it is less than 0.1 nm / sec, the polymer may be burned out due to excessive energy supply, and self-assembly of the polymer may not be performed properly when it exceeds 100 cm / sec. However, the movement speed of the light can be freely changed according to the energy density, the polymeric monomer of the block copolymer for applying self-assembly, the molecular weight, the presence or absence of the mutual coefficient (χ) reducing agent, and the present invention is not limited thereto .
In the present invention, the focal width of the light can be freely adjusted to a desired region according to the size, shape and manufacturing intention of the substrate or the polymer layer, and the present invention is not limited thereto.
Hereinafter, the present invention will be described in more detail based on examples and comparative examples. However, the following examples and comparative examples are merely examples for explaining the present invention in more detail, and the present invention is not limited by the examples and the comparative examples.
(Example 1)
Graphene (CMG, transmittance: 89.2%, thickness: 2nm) was prepared and deposited on the substrate in order to investigate the temperature of the light absorption layer according to light irradiation. Next, Nd: YAG (neodymium-doped yttrium aluminum garnet) having a wavelength of 1064 nm, a pulse operation of 300 kHz, and a duration of 200 ns was irradiated. The temperature of the graphene was measured with a thermal imaging camera (Flir, T400, USA) while the laser irradiation was performed, and the results are shown in FIGS.
As shown in Fig. 7, temperatures other than the irradiated portion are at room temperature, and it can be seen that temperatures of 250 deg. C or more are concentrated in the range of the diameter of the irradiation center portion of 250 mu m. It was also found that the temperature of the center portion did not exceed 300 캜.
Fig. 8 shows the heat flow in the elliptical irradiation according to the finite element method (FEM) through a computer simulation. In FIG. 8, the temperature change of the elliptically irradiated portion (d x : 600 μm, d y : 100 μm) shows that the temperature rises effectively up to 280 ° C. within 400 ms. A very high temperature gradient (ca. 1.28 K / ㎛), which is difficult to achieve in a typical heating process, is recorded through a simple photothermal process.
(Example 2)
In order to investigate the pattern formation of the polymer layer according to the light irradiation time and the light energy density, the following experiment was conducted. First, CMG and a substrate laminate used in Example 1 were prepared. A polystyrene-block-polymethylmethacrylate copolymer (number average molecular weight PS: 25 kg / mo1, PMMA: 26 kg / mol) and a polystyrene-random-polymethylmethacrylate (number average molecular weight: 17 kg / mol) were mixed at a weight ratio of 7: 3 to form a polymer layer. The finished polymer layer was irradiated with the same laser as in Example 1, and self-assembly of the polymer layer was performed at different irradiation times and energy densities. The pattern form after irradiation was measured by SEM and is shown in Fig.
As shown in FIG. 9, at a low energy density of 10 W / mm 2 or less, a disordered or earthworm-like worm-like region appears irrespective of the irradiation time (regions i and ii in FIG. 9) It is interpreted as the lack of light energy to form.
When the energy density exceeds 10 W / mm < 2 >, the polymer layer starts to be aligned in a lamellar shape but is randomly arranged (Fig. 9 (iii) (Fig. 9 (iv)). (D x : 300 탆, d y : 100 탆) when the shape of the laser to be irradiated is irradiated in an elliptical shape (d x : 600 탆, d y : 100 탆) 40 mu m).
When the energy density exceeded 21.2 W / mm < 2 >, the pattern was formed as disordered and discontinuous phase, and a sort-unoriented transition pattern was generally observed (Fig. Further, when the energy density exceeded 23 W / mm < 2 >, it was confirmed that the polymer layer deteriorated and burned (Fig.
(Example 3)
In order to investigate the arrangement according to the scanning speed of light, the following experiment was performed. First, the CMG and the substrate laminate used in Example 1 were prepared. On the CMG surface, a polystyrene-block-polymethylmethacrylate copolymer (number average molecular weight: PS: 25 kg / : 26 kg / mol) and a polystyrene-random-polymethylmethacrylate (number average molecular weight: 17 kg / mo1) were mixed at a weight ratio of 7: 3 to form a polymer layer. The finished polymer layer was irradiated with the same laser as in Example 1, but the energy density was fixed at 18.3 W / mm < 2 > and the scan speed was set to 1000 nm / s, 500 nm / Respectively.
As shown in FIG. 10, when the scanning speed was 1000 nm / s, a weak alignment state was observed, and when the scanning speed was further reduced, a more oriented pattern was formed near 500 nm / s ( 11). When the scan speed was 250 nm / s or less, it was confirmed that the pattern was almost perfectly aligned in the scan direction.
FIGS. 13 and 14 describe this in more detail. First, FIG. 13 is a graph showing the degree of orientation of the block copolymer in one direction according to the scan speed, that is, . It can be seen that as the scanning speed of the laser increases, the degree of alignment decreases, and as the scanning speed decreases to 2,000 nm / s or less, the degree of alignment increases sharply.
FIG. 14 shows the correlation length according to the reciprocal of the scan speed (1 / v). Although there is a difference in degree of increase in the correlation length depending on the mole fraction (?) Of the block copolymer, .
The spontaneous pattern formation process is summarized in FIG. 15 by summarizing Examples 1 to 3. As shown in the upper part of FIG. 15, as the temperature rises and the irradiation time increases, thermal energy is constantly applied to the polymer layer, and such thermal energy improves dispersion and fine phase separation behavior of the block copolymer chain. Also, randomly oriented lamellar domains grow and vertical lamellar phases are aligned. In particular, in order to induce disordered state and rearrangement of the block copolymer constituting the polymer layer, it can be seen that the temperature of the light absorbing layer for supplying heat to the polymer layer must be maintained at T ODT or more.
In detail, in the case of mixing 30% of the mutual modulus (χ) reduction agent in the embodiment, it is preferable to use the copolymer of the part irradiated with the laser at a temperature of 280 ° C. We observed that the order-disorder transition occurred by lowering χN to less than 10.5. Also, when the laser passes through the irradiated portion, the temperature of the irradiated portion gradually falls to T ODT or lower, and it is confirmed that the aligned pattern is naturally aligned and fixed. On the other hand, it was confirmed that a weak alignment effect was observed if the temperature above T ODT was not sufficiently applied.
15, the randomization and rearrangement of the block copolymer were observed by SEM at a laser scanning rate of 100 nm / s, and the laser advancing direction was from the right to the left. As the laser scan progresses, the laser does not touch the laser, and the randomly arranged lamella phase changes to disordered state as the temperature rises due to the laser irradiation. When the temperature is further lowered, the defect of the block copolymer Is gradually disappeared, and a well-arranged self-assembly pattern is formed.
The lower end portion of FIG. 15 is an SEM observation of the arrangement of the cylinder (PS-b-PMMA, number average molecular weight PS 21.5 kg / mol,
While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.
Claims (16)
b) forming a polymer layer by coating a self-assembled polymer containing a block copolymer on the surface of the photo-thermal conversion layer; And
c) irradiating the polymer layer with light so that the Flory-Huggins mutual coefficient χ of the self-assembled polymer and the polymer N of the block copolymer N, χN, is less than 10.5, applying a completely disordered state only to the irradiated portion Directing self-assembly;
≪ / RTI >
Wherein the self-assembled polymer further comprises 10 to 99% by weight of a mutual coefficient (?) Reduction.
Wherein the self-assembled polymer satisfies the following formula 1 while light is irradiated.
[Formula 1]
0.8T ODT ? T? 1 ? 3.0T ODT
(Where T 1 is the temperature of the self-assembled polymer and T ODT is the rule-random phase transition temperature of the block copolymer).
Wherein the energy density of the light is 0.001 to 200,000 W / mm < 2 >.
Wherein the moving speed of the light is 0.001 nm / sec to 100 cm / sec.
Wherein the focal width of the light is 100 nm or more.
The light-to-heat conversion layer includes a light-to-heat conversion material for converting light energy into thermal energy,
Wherein the light-to-heat conversion layer has a light transmittance of 99.9% or less.
Wherein the block copolymer is selected from the group consisting of polyurethane, epoxy polymer, polyarylene, polyamide, polyester, polycarbonate, polyimide, polysulfone, polysiloxane, polysilazane, polyether, polyurea, polyolefin, Wherein the polymer comprises two or more different repeating units selected from the polymers.
Wherein the block copolymer has a number average molecular weight of 3,000 to 30,000,000 g / mol.
Wherein the mutual coefficient (?) Reducing agent is at least one selected from the group consisting of monomers, oligomers, homopolymers, copolymers and organic solvents.
Wherein the mutual coefficient (?) Reduction agent is a random copolymer having a number average molecular weight of 1,000 to 3,000,000 g / mol.
The random copolymer may be a polyurethane, an epoxy polymer, a polyarylene, a polyamide, a polyester, a polycarbonate, a polyimide, a polysulfone, a polysiloxane, a polysilazane, a polyether, a polyurea, a polyolefin, Wherein the polymer comprises two or more different repeating units selected from the polymers.
Wherein the random copolymer comprises repeating units derived from 10 to 90% by weight of the styrene-based monomer and 90 to 10% by weight of the methacrylate-based monomer.
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