JP2006334693A - Nanostructure, porous nanostructure, functional nanostructure, and method of manufacturing same - Google Patents

Nanostructure, porous nanostructure, functional nanostructure, and method of manufacturing same Download PDF

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JP2006334693A
JP2006334693A JP2005160022A JP2005160022A JP2006334693A JP 2006334693 A JP2006334693 A JP 2006334693A JP 2005160022 A JP2005160022 A JP 2005160022A JP 2005160022 A JP2005160022 A JP 2005160022A JP 2006334693 A JP2006334693 A JP 2006334693A
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JP4897947B2 (en
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Yokun Kin
容薫 金
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Furukawa Electric Co Ltd:The
古河電気工業株式会社
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Abstract

Provided are a nanostructure, a porous nanostructure and a functional nanostructure capable of forming a regular nanopattern having a large area at a low cost, and a method for producing them.
A nanostructure (1) formed on a substrate (3) using a soft lithography method, comprising a block copolymer comprising two kinds of polymer components and having a regular phase separation structure. Nanostructure (1) comprising at least one substructure part (2).
[Selection] Figure 1

Description

  The present invention relates to nanostructures, porous nanostructures and functional nanostructures, and methods for producing the same, and in particular, the present invention relates to nanostructures capable of forming large-area regular nanopatterns at low cost. The present invention relates to porous nanostructures and functional nanostructures, and methods for producing them.

  With the advancement of electronic component performance, the need for fine patterns and structures is increasing. For example, with the miniaturization and high integration of semiconductor electronic devices and the high recording density of recording media, nanoscale processing techniques for the device fabrication are required. In the conventional photolithography technique used for manufacturing a semiconductor electronic device, the processing limit is 100 nm. In lithography using an electron beam or ion beam, finer processing is possible and ultrafine processing of several nanometers to several tens of nanometers is possible, but the processing cost is high and the processing time is long.

In recent years, soft lithography has attracted attention as one of lithography techniques. This method is a method in which a soft material solution such as a polymer is poured into a fine mold and cured by ultraviolet irradiation or heating as it is to transfer a fine three-dimensional structure onto a substrate and perform microfabrication. It is used to develop microfluidic chips such as Total Analysis System and DNA chips.
However, in this method, PDMS (polydimethylsiloxane) resin is usually used as a mold. However, since the mold is softer than that made of metal, dimensional accuracy is difficult to obtain, and a pattern (groove) of several tens of nm is formed. It was not a suitable method.

On the other hand, it is known that the AB block copolymer in which the polymer component A and the polymer component B are bonded spontaneously forms a regular nanopattern by self-assembly. Here, “self-organization” refers to the phenomenon of spontaneously creating an ordered structure according to only the intrinsic properties of nanomaterials under external conditions. This phenomenon is caused by the balance between the repulsive interaction between the A block and the B block and the elastic energy of both blocks. The regular structure of the block copolymer consists of a sea-island structure in which one block region is phase-separated in a dot shape according to the composition ratio of the A block and B block, and a cylinder in which one block region is phase-separated in a rod shape Various structures, such as a co-continuous structure in which one block area is phase-separated as a stack of tetrapods, and a lamellar structure in which two phases of one block and the other block are alternately stacked in a plane A simple structure can be formed.
If this property is utilized, it is possible to form a single-layer regularly arranged pattern by simply dissolving the block copolymer in an appropriate solvent and coating it on the workpiece (for example, patent document). 1). Along with recent miniaturization and high integration of semiconductor electronic devices and high recording density of recording media, large-area nanopatterns are required.

As described above, it is difficult to form a nanopattern of 100 nm or less by the top-down method using lithography, but it is expected as an effective means for forming a large-area pattern. On the other hand, in the bottom-up method using a block copolymer, a regular nanopattern of about several tens of nanometers can be easily formed by self-assembly. Therefore, a method has been proposed in which both are combined and the block copolymer is used for lithography (for example, see Non-Patent Document 1 or 2). Thereby, a large-area pattern having a desired shape composed of regular nano-patterns can be easily produced by photolithography.
Non-Patent Document 1 describes that a pattern is formed by dissolving a block copolymer in a volatile solvent such as toluene and applying it onto a substrate on which irregularities (grooves) are formed by photolithography. However, the method described in Non-Patent Document 1 assumes that irregularities are formed on the substrate, but in order to actually manufacture a device, it is necessary to remove such irregularities on the substrate. There was a problem that there were many restrictions on use.
In Non-Patent Document 2, the pattern surface of a PDMS mold poured with a block copolymer dissolved in a volatile solvent such as toluene is brought into close contact with the substrate surface, and the mold is removed after the block copolymer is heated and cured. By doing so, it is described that a pattern is formed on a substrate. In this method, it is not necessary to form irregularities as in the method described in Non-Patent Document 1, and there are few substrate restrictions, and a pattern can be formed on both organic and inorganic substrates.

  In the block copolymer, phase separation occurs due to repulsive interaction as described above, and a regular domain arrangement (also referred to as a microdomain structure or a microphase separation structure) is formed. Here, the “domain” means an island-like region in the case of the sea-island structure, and a cylinder-like region in the case of the cylinder structure. When viewed two-dimensionally, the domains are regularly arranged in a staggered pattern (honeycomb shape), and in particular, in a cylindrical domain, they are oriented in a certain direction and regularly aligned. Such domain arrangement formation can be observed on the order of several nanometers to several tens of nanometers, but when viewed on the order of several hundred nanometers to several micrometers, one grain (crystal grain) in which a plurality of domains are regularly arranged is formed. is doing. Here, “grain” refers to a region in which a regular domain sequence is formed with one domain serving as a nucleus. Usually, a plurality of domains are formed as a nucleus to form grains, and a plurality of grains are formed as a whole.

Thus, the block copolymer forms a hierarchical structure. This will be described in more detail with reference to FIG. 6 reproduced from FIG. 1 described in Non-Patent Document 3. FIG. 6 shows the structure of the block copolymer at various scales. FIG. 6 (a) shows a polymer component, FIG. 6 (b) shows one molecule of the block copolymer, and FIG. FIG. 6D shows a microdomain structure formed by a plurality of block copolymer molecules, and FIG. 6D shows a structure composed of a plurality of grains.
The polymer component of the block copolymer described in FIG. 6 is polybutadiene and polystyrene, and the size of the repeating monomer unit of polystyrene is about 0.5 nm (FIG. 6A). The block copolymer shown in FIG. 6 is a chain of these polymer components, one molecule of which is a bridge made of a cylindrical polystyrene block at both ends of a loop made of a thread-like polybutadiene block. The (bridge) portion is coupled to each other, and the cross-section of the bridge portion has a diameter of about 20 nm (FIG. 6B). When a plurality of block copolymer molecules are viewed together, regular microdomains in a staggered lattice (honeycomb shape) in which cylindrical bridge portions (domains) are aligned in the same direction at equal intervals of about 40 nm. A structure is formed (FIG. 6C). As described above, a plurality of domains are regularly arranged to form one grain. However, when viewed macroscopically, the block copolymer shown in FIG. 6 generally has a diameter of about 5 μm. A polycrystalline structure composed of a plurality of grains is formed (FIG. 6D). In FIG. 6D, the black part in each grain represents a cylindrical domain, and the part represented by a black dot represents a cross-sectional part (or end face part) of the cylindrical domain. That is, a regular array is formed in each grain, but each grain is oriented in a different direction, and the block copolymer shown in FIG. 6 forms a three-dimensional bulk body.

  As shown in FIG. 6D, the domains are regularly arranged in one grain. However, since each grain is formed independently, a deviation occurs at the boundary between grains. In the case of a cylindrical domain, each grain has a different orientation (for example, see Non-Patent Document 3). Therefore, it has a microphase-separated structure that is regularly arranged only in grains, but since it becomes an irregular arrangement in which a plurality of grains are aggregated as a whole, conventionally, a block copolymer has been used. Forming an aread nanopattern was not practical.

  As a method for controlling the orientation of the domain arrangement of the block copolymer, a method using a crystalline solvent such as benzoic acid is known (for example, see Non-Patent Document 4). In this method, the orientation of the domain arrangement of the block copolymer can be controlled by crystallizing a solvent such as benzoic acid in which the block copolymer is dissolved. However, since this method also forms a plurality of grains, there is a problem in that a deviation occurs at the boundary between the grains and the regularity of the pattern is inferior.

  In addition, a block copolymer film having a vertically aligned lamellar structure regularly arranged in one direction is manufactured by using a zone cooling method in which the block copolymer film is heated to a predetermined temperature range in order for each predetermined region and then cooled. The method of doing is also known (for example, refer patent document 2). However, the method described in Patent Document 2 has a problem that it is very time consuming and not practical.

JP 2001-151834 A JP 2005-060583 A J.Y.Cheng et al., "Applied Physics Letters", 2002, Vol.81, No.19, p.3657-3659 T.Deng et al., "Langmuir", 2002, Vol.18, No.18, p.6719-6722 C.Christian et al., "Chem.Mater.", 1996, Vol.8, No.8, p.1702-1714 C. Park et al., "Applied Physics Letters", 2001, Vol.79, No.6, p.848-850

  An object of the present invention is to provide a nanostructure, a porous nanostructure and a functional nanostructure capable of forming a large-area regular nanopattern at low cost, and a method for producing them.

As a result of intensive studies in order to solve the above problems, the present inventors have combined a top-down lithography technique with a bottom-up pattern formation technique based on self-organization of block copolymers. When producing a nanostructure capable of forming a nanopattern with an area, a plurality of substructure parts made of a rectangular block copolymer having a width (short side) equal to or smaller than the grain size are arranged in the width direction. As a result, the number of grains in the block copolymer constituting the sub-structure portion is close to a single number, and the number of boundaries between grains is reduced. We found that nanostructures capable of forming a typical nanopattern can be provided at low cost. Furthermore, the present inventors made it possible to make the number of grains of the block copolymer constituting the substructure one.
In addition, the present inventors use a template that transfers a nanostructure composed of at least one substructure portion onto a substrate and forms the substructure portion so that the width of the substructure portion is equal to or smaller than the grain size. Using a crystalline organic solvent having a melting point higher than the glass transition point of the copolymer, a solution in which the block copolymer is dissolved in the solvent is poured into the mold, and either the substrate or the mold is melted by the melting point of the crystalline solvent. Crystallization of the crystalline solvent by applying a temperature gradient between the substrate and the mold while keeping the other temperature lower than the melting point of the crystalline solvent and higher than the glass transition temperature of the block copolymer. It was found that nanostructures capable of forming large-area regular nanopatterns with few defects can be manufactured by controlling the orientation of the domain arrangement. Furthermore, the inventors of the present invention have developed a nanostructure that can form a regular nanopattern with a large number of defects by crystallizing a crystalline solvent by sequentially cooling each predetermined region using a zone cooling method. It was found that the body can be manufactured at a higher speed than before.
The present invention has been made based on these findings.

That is, the present invention
(1) A nanostructure formed on a substrate using a soft lithography method, at least one substructure composed of a block copolymer having two regular polymer components and having a regular phase separation structure A nanostructure having a portion,
(2) At least one substructure which is a nanostructure formed on a substrate by using a soft lithography method and is composed of a block copolymer having two regular polymer components and having a regular phase separation structure A nanostructure according to item (1), wherein the width of the substructure part is equal to or less than the grain size of the block copolymer,
(3) The phase separation structure of the block copolymer is a sea-island structure in which one of the two polymer components constituting the block copolymer is phase-separated into an island region and the other into a sea region. The nanostructure according to (1) or (2),
(4) The composition ratio of the two polymer components constituting the block copolymer is in the range of 1:99 to 15:85 or 85:15 to 99: 1 in volume ratio. Nanostructures,
(5) The nanostructure according to (3) or (4), wherein the island-shaped regions in the phase-separated structure of the block copolymer have a diameter of 100 nm or less and an arrangement interval between the island-shaped regions is 10 to 100 nm. body,

(6) The phase separation structure of the block copolymer is a cylinder structure in which one of the two polymer components constituting the block copolymer is phase-separated into a cylindrical region (1) or (2 The nanostructure according to item),
(7) The phase separation structure of the block copolymer is a cylinder structure in which one of the two polymer components constituting the block copolymer is phase-separated into a cylindrical region, The nanostructure according to item (6), wherein the length direction is arranged perpendicular to the substrate surface,
(8) The phase separation structure of the block copolymer is a cylinder structure in which one of the two polymer components constituting the block copolymer is phase-separated into a cylindrical region, The nanostructure according to item (6), wherein the length direction is arranged parallel to the substrate surface,
(9) The composition ratio of the two polymer components constituting the block copolymer is in the range of 20:80 to 35:65 or 65:35 to 80:20 by volume ratio (6) to (8 ) The nanostructure according to any one of
(10) The diameter of the cylindrical region in the phase separation structure of the block copolymer is 100 nm or less, the length of the cylindrical region is 50 nm to 50 mm, and the arrangement interval between the cylindrical regions is 10 to 100 nm. The nanostructure according to any one of (6) to (9),

(11) The island-shaped region or the cylindrical region in the phase separation structure of the block copolymer is formed as a single layer (two-dimensionally) on the substrate (1) to (6) or (8) The nanostructure according to any one of to (10),
(12) Of the two types of polymer components constituting the block copolymer, one is a polymer component having a carbon double bond in the main chain, and the other is a polymer component having no carbon double bond in the main chain The nanostructure according to any one of (1) to (11),
(13) The polymer component having a carbon double bond in the main chain is any one selected from the group consisting of polyisoprene, polybutylene and polychloroprene, and has no carbon double bond in the main chain The nano of any one of (1) to (12), wherein the component is any one selected from the group consisting of polystyrene, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate, polyacrylamide and polyacrylonitrile. Structure,

(14) The nanostructure according to any one of (1) to (13), wherein an aspect ratio of the width / height of the substructure portion is in a range of 0.1 to 10.
(15) Any of (1) to (14), wherein the width of the substructure part constituting the nanostructure is 100 nm to 10 μm, the height of the substructure part is 1 μm or less, and the distance between the substructure parts is 25 to 500 nm. The nanostructure according to claim 1,
(16) The nanostructure according to any one of (1) to (15), wherein the material of the substrate is silicon, silicon nitride, glass, metal, metal oxide, or heat resistant resin,

(17) The method for producing a nanostructure according to any one of (1) to (16),
(A) A block copolymer formed of two kinds of polymer components and forming a regular phase-separated structure having a pattern with a width less than the grain size formed on the upper surface is used to crystallize the block copolymer. The solution dissolved in the crystalline organic solvent is injected into the pattern formed on the upper surface of the mold held at a temperature equal to or higher than the melting point of the crystalline organic solvent,
(B) The upper surface of the mold filled with the block copolymer solution is adhered to the substrate surface,
(C) While maintaining the temperature of the surface of the mold on the substrate side at a temperature equal to or higher than the melting point of the crystalline organic solvent, the temperature of the surface opposite to the substrate of the mold is lower than the melting point of the crystalline organic solvent. And cooling to above the glass transition temperature of the block copolymer,
(E) the method comprising removing the template;
(18) The step (c)
(C-1) While maintaining the temperature of the surface of the mold on the substrate side at a temperature equal to or higher than the melting point of the crystalline organic solvent, the temperature of one end of the surface opposite to the substrate of the mold is set to the crystalline organic Cooling below the melting point of the solvent and above the glass transition temperature of the block copolymer,
(C-2) The method for producing a nanostructure according to (17), wherein the cooling in step (c-1) is sequentially performed at a predetermined speed from one end to the other end of the mold,

(19) The method for producing a nanostructure according to any one of (1) to (16),
(A) A block copolymer formed of two kinds of polymer components and forming a regular phase-separated structure having a pattern with a width less than the grain size formed on the upper surface is used to crystallize the block copolymer. The solution dissolved in the crystalline organic solvent is injected into the pattern formed on the upper surface of the mold held at a temperature equal to or higher than the melting point of the crystalline organic solvent,
(B) The upper surface of the mold filled with the block copolymer solution is adhered to the substrate surface,
(D) The temperature of the substrate is lower than the melting point of the crystalline organic solvent while maintaining the temperature of the surface opposite to the substrate of the mold at a temperature equal to or higher than the melting point of the crystalline organic solvent, and the block weight Cool above the glass transition temperature of the coalesced,
(E) the method comprising removing the template;
(20) The step (d)
(D-1) The temperature at one end of the substrate is lower than the melting point of the crystalline organic solvent while maintaining the temperature of the surface opposite to the substrate of the mold at a temperature equal to or higher than the melting point of the crystalline organic solvent. And cooling to above the glass transition temperature of the block copolymer,
(D-2) The method for producing a nanostructure according to (19), wherein the cooling in step (d-1) is sequentially performed at a predetermined speed from one end of the substrate to the other end.

(21) The nanostructure according to any one of (17) to (20), wherein a groove having a width of 100 nm to 10 μm and a depth of 1 μm or less is formed, and a mold having a distance between the grooves of 25 to 500 nm is used. Production method,
(22) The method for producing a nanostructure according to any one of (17) to (21), wherein polydimethylsiloxane or polyurethane is used as the template material.
(23) The method for producing a nanostructure according to any one of (17) to (22), wherein a template whose surface is coated with a material in which fluororesin particles are dispersed in an adhesive is used,
(24) The method for producing a nanostructure according to any one of (17) to (22), wherein a template whose surface is coated with a fluororesin having a functional group at a terminal is used,

(25) After removing the template in step (e) in the method according to any one of (17) to (24), a region where the polymer component having a carbon double bond in the main chain is phase-separated is formed. A method for producing a porous nanostructure in which pores are formed by etching,
(26) The method for producing a porous nanostructure according to (25), wherein ozone etching, fluorine ion etching, ultraviolet etching, or plasma etching is used as the etching method.
(27) A porous nanostructure produced by the method according to (25) or (26), comprising at least one substructure part in which pores are regularly arranged,

(28) A method for producing a functional nanostructure in which the pores provided in the porous nanostructure according to (25) or (26) are filled with a functional element,
(29) The method for producing a functional nanostructure according to item (28), wherein the functional element is any one of an optical functional element, a semiconductor element, and a magnetic element, and (30) (28) or (29) Provided is a functional nanostructure produced by the method described above and including at least one substructure portion in which functional elements are regularly arranged.

The nanostructure in the present invention is usually composed of a “substrate” and a “substructure portion” formed on the substrate. The “substructure part” in the present invention refers to a structure part that can form a regular pattern arrangement (nanopattern) of nanometer order on its surface or inside, and the nanostructure of the present invention is formed on a substrate. It has at least one substructure part.
The nanostructure of the present invention is a nanostructure having a substructure in which a regular pattern arrangement (nanopattern) of nanometer order is formed on the surface or inside thereof, and has at least one substructure portion, Each of the sub-structure parts is composed of almost one grain, and the grain is formed of a hierarchical structure composed of regularly arranged domains.

The nanostructure of the present invention can form a regular nanopattern having a large area and no defects. The nanostructure of the present invention can be used as an optical filter, a diffraction grating, or the like. Moreover, the porous nanostructure of the present invention can be applied to various uses such as optical uses. In addition, the functional porous nanostructure of the present invention using a magnetic element can be used as a magnetic recording medium. Further, semiconductor fine particles, conductive fine particles, ferroelectric fine particles, phase change fine particles, photochromic fine particles, thermochromic particles, By using non-magnetic fine particles such as chromic fine particles and electrochromic fine particles, it can be applied to a wide range of uses such as wiring, sensors and memories.
According to the method of the present invention, a nanostructure capable of forming a regular nanopattern having a large area and no defects can be provided at high speed and at low cost.

Hereinafter, the present invention will be described in detail.
One preferred embodiment of the present invention is shown in FIG. Hereinafter, in the description of each drawing, the same elements are denoted by the same reference numerals. FIG. 1 is a perspective view of one embodiment of the nanostructure of the present invention. The nanostructure 1 of the present invention has at least one substructure portion 2 composed of a block copolymer having two regular polymer components and having a regular phase separation structure, and is formed on a substrate 3. Has been. Here, the width of the substructure portion 2 is formed to be equal to or smaller than the grain size of the block copolymer.

  The nanostructure of the present invention is formed on a substrate using a soft lithography method. This is because the soft lithography method can form a large area pattern at low cost. As described above, the soft lithography method is a method in which a soft material solution such as a polymer is poured into a fine mold, and the fine three-dimensional structure is transferred onto the substrate by being cured by ultraviolet irradiation or heating to perform fine processing. is there. A specific method will be described later.

The nanostructure of the present invention is formed on a substrate by utilizing the self-organizing property of the block copolymer. Thereby, a nano pattern can be easily formed at low cost.
The block copolymer used in the present invention is a linear copolymer composed of two types of polymer components, and is a copolymer in which different types of polymer component blocks are bonded to the ends of one type of polymer component block. Here, the block refers to a portion made of a kind of polymer component. In the present specification, when the two types of polymer components are A and B, respectively, the portion composed of the polymer component A and the portion composed of the polymer component B are referred to as A block and B block, respectively.

The block copolymer used in the present invention may have any structure as long as it has a regular phase separation structure. For example, an AB type block copolymer in which one A block having a structure of -A-B- and one B block are bonded may be used. In addition, an ABA type block copolymer in which an A block is bonded to both ends of a B block having a structure of -A-B-A-, or both ends of an A block having a structure of -B-A-B- Alternatively, a B-A-B type block copolymer in which a B block is bonded may be used. Further, a block copolymer composed of a plurality of A blocks and B blocks having a structure of- (AB) n -may be used.

  The two polymer components used in the present invention may be any as long as they form a regular phase separation structure, but preferably one is a polymer component having a carbon double bond in the main chain and the other is Is a combination of polymer components having no carbon double bond in the main chain. The region where the polymer component having a carbon double bond in the nanostructure of the present invention is phase-separated can be decomposed by ozone etching or the like to provide pores and form a porous nanostructure. Moreover, a functional nanostructure can also be formed by filling the void | hole provided in this way with a functional element.

Examples of the polymer component having a carbon double bond in the main chain used in the present invention include polybutadiene, polyisoprene, polychloroprene and other polyene polymers, but the present invention is not limited thereto. .
Examples of the polymer component having no carbon double bond in the main chain used in the present invention include polystyrene, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate, polyacrylamide, and polyacrylonitrile. The invention is not limited to these examples. In the present invention, polystyrene is particularly preferred.
The number average molecular weight of the block copolymer used in the present invention is preferably 1,000 to 1,000,000, more preferably 10,000 to 500,000.
The block copolymer used in the present invention is preferably a copolymer of polyisoprene and polystyrene, or a copolymer of polybutadiene and polystyrene, but the present invention is not limited to these.

  The block copolymer used in the present invention can be synthesized by any method, but the living polymerization method is particularly preferred. In the living polymerization method, the molecular weight and copolymer ratio can be precisely controlled, and a block copolymer having a narrow molecular weight distribution can be obtained. A living anion polymerization method or a living cation polymerization method is known, and a block copolymer is obtained by starting polymerization with one type of monomer by using a polymerization initiator that generates an anion or cation, and sequentially adding other monomers. (For example, see the Polymer Society of Japan, “Polymer Alloys-Fundamentals and Applications”, 1st edition, Tokyo Kagaku Dojin, 1981, p. 11-20, etc.).

  As the regular phase separation structure of the block copolymer in which two types of blocks, A block and B block, are chemically bonded, one block region is an island-like region, and the other block region is a sea-like region. Sea-island structure phase-separated into regions, cylinder structure in which one block region is phase-separated into rods (cylindrical region), a co-continuous structure in which one block region is phase-separated as if tetrapods were stacked, one block There is a lamellar structure in which two phases of the block and the other block are alternately laminated in a planar shape, and various structures can be formed according to the composition ratio of the A block and the B block. The composition ratio of the two polymer components constituting the block copolymer is preferably in the range of 1:99 to 99: 1 by volume ratio.

  In the present invention, the phase separation structure of the block copolymer is preferably a sea-island structure or a cylinder structure. The island-shaped region or the cylindrical region may be formed two-dimensionally (single layer) or three-dimensionally on the substrate, but the island-shaped region or cylindrical region may be a single layer. It is preferably formed in a two-dimensional manner.

When the phase separation structure of the block copolymer is a sea-island structure, the composition ratio of the two polymer components constituting the block copolymer varies depending on the type of the block copolymer, but is 1: 99-15: It is preferably in the range of 85 or 85:15 to 99: 1, and more preferably in the range of 5:95 to 15:85 or 85:15 to 95: 5.
The shape of the island-like region is spherical or almost spherical, and the diameter is preferably 100 nm or less, more preferably 10 to 100 nm, and still more preferably 15 to 80 nm. In addition, the arrangement interval between the island regions is preferably 10 to 100 nm, and more preferably 15 to 80 nm.

When the phase separation structure of the block copolymer is a cylinder structure, the length direction of the cylinder structure may be arranged parallel to the substrate surface or may be arranged vertically. When they are arranged in parallel, they can be used for microchannels, and when they are arranged vertically, they can be used for magnetic elements.
When the phase separation structure of the block copolymer is a cylinder structure, the composition ratio of the two polymer components constituting the block copolymer varies depending on the type of the block copolymer but is 20:80 to 40: The range is preferably 60 or 60:40 to 80:20, and more preferably 20:80 to 35:65 or 65:35 to 80:20. For example, in the case of a block copolymer of polystyrene and polybutadiene, the ratio is particularly preferably 35:65 or 65:35.
The diameter of the cylindrical region is preferably 100 nm or less, more preferably 10 to 100 nm, and further preferably 15 to 80 nm. The length of the cylindrical region is applicable to 50 nm to 50 mm. An increase in the area of the nanostructure such that the length of the cylindrical region is 50 mm can be achieved by controlling the width of the substructure and the temperature condition within a predetermined range in the phase separation process. When the length direction of the cylinder structure is arranged parallel to the substrate surface, the length is preferably 10 to 50 mm, and the length direction of the cylinder structure is perpendicular to the substrate surface. When they are arranged, it is practically preferable to be 50 nm to 1 μm, and more preferably 100 to 500 nm. Further, the arrangement interval between the cylindrical regions is preferably 10 to 100 nm, and more preferably 15 to 80 nm.

When the phase separation structure of the block copolymer is a lamella structure, the phases forming the lamella structure are preferably arranged perpendicular to the substrate surface.
When the phase separation structure of the block copolymer is a lamellar structure, the composition ratio of the two polymer components constituting the block copolymer varies depending on the type of the block copolymer, but is 40: 60-60: The range is preferably 40, and more preferably 45:55 to 55:45.
The thickness of the phase forming the lamella structure is preferably 1 μm or less, more preferably 50 nm to 1 μm, and even more preferably 100 to 500 nm.

The nanostructure of the present invention has at least one substructure part composed of a block copolymer composed of two kinds of polymer components and having a regular phase separation structure, and the width of the substructure part is It is less than the grain size of the block copolymer. If a plurality of grains are formed, defects occur in the regular arrangement at the boundaries between the grains. However, the present invention can prevent the occurrence of defects by the sub-structure part composed of a number of grains close to a single. it can. From the viewpoint of preventing the occurrence of defects, the structure of the block copolymer constituting the substructure portion in the present invention is preferably composed of as few grains as possible, more preferably composed of almost one grain. It is particularly preferred that the grains consist of
As will be described later, the shape of the sub-structure portion in the present invention is not particularly limited, but when the sub-structure portion is a rectangular parallelepiped shape, the short side is defined as the width and the long side is defined as the length. Further, when the sub-structure portion is coin-shaped (cylindrical), the diameter of the coin is defined as the width.

In the present invention, the width of the substructure portion is preferably equal to or less than the grain size of the block copolymer. The grain size of the block copolymer varies depending on the type of the block copolymer. For example, it is known that the block copolymer of polystyrene and polybutadiene has a diameter of about 300 nm. The width of the substructure portion in the present invention is preferably 100 nm to 10 μm, more preferably 10 nm to 1 μm, but is appropriately determined according to practical use.
From the viewpoint of reducing the number of grains in order to reduce defects, the length of the substructure part is preferably not more than the grain size of the block copolymer, and is preferably in the same range as described above. As will be described later, when the temperature is controlled using a crystalline solvent to produce the substructure portion, the formation of a plurality of grains can be suppressed while controlling the orientation of the domains, so that the size may be longer than the size of the grains. Specifically, the length of the substructure portion is applicable to 50 nm to 50 mm, and 10 to 50 mm is practically preferable.

The height of the substructure portion can be applied in the range of 50 nm to 1000 nm, and is appropriately determined according to practical use. In particular, when the block copolymer is phase-separated into a sea-island structure or when it is phase-separated into a cylinder structure and its length direction is arranged parallel to the substrate surface, when forming a two-dimensional array of single layers, The height of the substructure portion is preferably 50 to 100 nm. A sub-structure part in which domains are arranged in a two-dimensional manner in a single layer is preferable because the function can be easily controlled in practical use.
On the other hand, when the block copolymer is phase-separated into a cylinder structure and its length direction is arranged perpendicular to the substrate surface, or when the phase separation into a lamellar structure and each phase is arranged perpendicular to the substrate surface, The height of the structure part is preferably 50 to 1000 nm.
The aspect ratio of the width / height of the substructure portion is preferably in the range of 0.1-10.

  The nanostructure of the present invention has at least one substructure portion, but the number thereof is not particularly limited, and may be one or more (preferably plural), but is appropriately determined according to practical use. Further, the shape of the sub-structure portion is not particularly limited, and is appropriately determined according to practical use such as a rectangular parallelepiped shape or a coin shape, but is a rectangular parallelepiped shape as in the preferred embodiment of the present invention shown in FIG. Is preferred. The distance between the sub-structure parts is preferably 25 to 500 nm in consideration of the mechanical properties of the resinous mold, but the present invention is not limited to this.

The material of the substrate used in the present invention is not particularly limited and any material can be used. For example, in addition to silicon, silicon nitride (SiN, Si 2 N 3 , Si 4 N 3 ), etc., glass, metal oxide Alternatively, a heat-resistant resin or a metal such as copper may be used.

Next, the manufacturing method of the nanostructure of this invention is demonstrated.
The nanostructure of the present invention can be produced by a method including the following steps (a), (b), (c) and (e).
(A) A block copolymer formed of two kinds of polymer components and forming a regular phase-separated structure having a pattern with a width less than the grain size formed on the upper surface is used to crystallize the block copolymer. Injecting the solution dissolved in the crystalline organic solvent into the pattern formed on the upper surface of the mold held at a temperature equal to or higher than the melting point of the crystalline organic solvent.
(B) A step of bringing the upper surface of the mold filled with the block copolymer solution into close contact with the substrate surface.
(C) While maintaining the temperature of the surface of the mold on the substrate side at a temperature equal to or higher than the melting point of the crystalline organic solvent, the temperature of the surface opposite to the substrate of the mold is lower than the melting point of the crystalline organic solvent. And cooling to a temperature equal to or higher than the glass transition temperature of the block copolymer.
(E) removing the template.

  In step (a), first, a template is used in which a pattern having a width equal to or less than the grain size of a block copolymer that is formed of two polymer components and forms a regular phase separation structure is formed on the upper surface. This pattern is transferred onto a substrate in a step described later to form a nanostructure having a substructure portion. And the nanostructure which can form a regular nano pattern with few grains and few defects can be produced by making the width | variety of a pattern into below the magnitude | size of the grain of a block copolymer.

As a material for the mold, PDMS (polydimethylsiloxane) resin is usually used, but the present invention is not limited to this. For example, polyurethane or the like can be used in addition to polydimethylsiloxane. In the present invention, PDMS is particularly preferable.
The template used in the present invention can be produced by an arbitrary method, and can be produced by, for example, an optical lithography technique.
Each of the grooves (patterns) formed on the mold forms a substructure portion by casting. Accordingly, the width of the groove is preferably equal to or smaller than the grain size of the block copolymer. Specifically, the thickness is preferably 100 nm to 10 μm, more preferably 10 nm to 1 μm, but is appropriately determined according to practical use. Further, the depth of the groove is applicable to 50 nm to 1000 nm, and is appropriately determined according to practical use. Moreover, although it is preferable that the space | interval of grooves is 25-500 nm, this invention is not limited to this.

  If the mold releasability is poor, removal of the template in step (e), which will be described later, cannot be performed well, and the formed nanostructure or template may be broken. Further, depending on the solvent used, the template may be dissolved. Therefore, it is preferable to coat the mold surface with a fluororesin or the like. Any method can be used as a coating method, for example, as described in T.Deng et al., "Langmuir", 2002, Vol.18, No.18, p.6719-6722, The mold surface may be coated with a material in which fluororesin particles are dispersed in an adhesive, or the mold surface may be coated with a fluororesin having a functional group.

  In step (a), the above block copolymer is dissolved in a crystalline organic solvent. By using a crystalline organic solvent and crystallizing the solvent in step (c) or (d) described later, the orientation of the domain arrangement of the block copolymer can be controlled. The crystallization temperature (melting point) of the crystalline organic solvent needs to be a temperature exceeding the glass transition point of the block copolymer. The crystalline organic solvent is appropriately determined in consideration of the relationship between the melting point (crystallization temperature) of the solvent and the glass transition temperature of the block copolymer, the solubility of the block copolymer, and the like. Examples include benzoic acid and anthracene, but the present invention is not limited to these. In the present invention, benzoic acid is particularly preferred. Moreover, although the density | concentration of a crystalline organic solvent is determined suitably, Preferably it is 10-60 mass%, More preferably, it is 20-50 mass%.

  Next, the prepared solution is injected into a pattern formed on the upper surface of the mold. At this time, it is necessary to keep the temperature of the template above the melting point of the crystalline organic solvent so that the crystalline organic solvent does not crystallize simultaneously with the injection.

  In step (b), the upper surface (surface on which the pattern is formed) of the mold filled with the block copolymer solution is brought into close contact with the substrate surface. At that time, the excess block copolymer solution overflowing from the mold is withdrawn.

  In step (c), while maintaining the temperature of the surface of the mold on the substrate side at a temperature equal to or higher than the melting point of the crystalline organic solvent, the temperature of the surface of the mold opposite to the substrate is set to the temperature of the crystalline organic solvent. It is cooled below the melting point and above the glass transition temperature of the block copolymer. In this way, the temperature of the substrate is maintained at a temperature equal to or higher than the melting point of the crystalline organic solvent, and a temperature gradient is provided by cooling the surface of the mold opposite to the substrate so that the crystalline organic solvent It is possible to crystallize on the template and to determine the orientation of the domain sequence of the block copolymer in a certain direction.

  Further, in step (c), (c-1) one end of the surface of the mold opposite to the substrate while maintaining the temperature of the surface of the template on the substrate side at a temperature equal to or higher than the melting point of the crystalline organic solvent. The temperature of the part is lower than the melting point of the crystalline organic solvent and is equal to or higher than the glass transition temperature of the block copolymer, and (c-2) the cooling of the step (c-1) is started from one end of the mold. It is preferable to sequentially carry out at a predetermined speed up to the other end. That is, it is preferable to perform a zone cooling method in which the mold is sequentially cooled to a predetermined temperature for each predetermined region. Thereby, the grain boundaries of the block copolymer can be eliminated, and the orientation of the domain arrangement can be regularly arranged in one direction. Moreover, a regular domain arrangement can be formed at high speed by using a crystalline solvent and performing zone cooling.

This zone cooling method will be described with reference to FIGS. 2 and 3 show one embodiment of the method for producing a nanostructure of the present invention. FIG. 2 is a front sectional view of the nanostructure, and FIG. 3 is a plan sectional view. 2 is a cross-sectional view taken along line II-II in FIG. 3, and FIG. 3 is a cross-sectional view taken along line III-III in FIG. Referring to FIG. 2, the mold 5 is disposed in close contact with the substrate 3, and the substructure portion 2 made of the block copolymer phase-separated into the island-like region 21 and the sea-like region 22 by the template 5 is the substrate. 3 is modeled above. A crystallized solvent 4 crystallized in a gap with the mold 5 is disposed above the substructure portion 2, and a cooling plate 6 is disposed on the mold 5. In FIG. 3, benzoic acid is crystallized by cooling the portion where the plate 6 indicated by the dotted line is in contact with the mold 5. In FIG. 3, reference numeral 23 denotes a region that has not yet undergone phase separation. By gradually cooling the plate 6 while moving it gradually, benzoic acid is crystallized little by little.
The moving speed at the time of zone cooling is determined in consideration of the crystallization speed of the crystalline solvent. For example, when the crystalline solvent is benzoic acid, it is preferably 2 mm / s or less, more preferably 500 nm / s to 100 μm / s.

In step (e), after the block copolymer and the crystalline organic solvent are cured by cooling, the template is removed.
Through the above steps, the nanostructure of the present invention can be produced. By changing the composition ratio of the two polymer components in the block copolymer to be used, nanostructures having various phase separation structures such as a sea-island structure, a cylinder structure, and a lamellar structure can be produced.

Instead of the step (c), the following step (d) may be performed.
(D) The temperature of the substrate is lower than the melting point of the crystalline organic solvent while maintaining the temperature of the surface opposite to the substrate of the mold at a temperature equal to or higher than the melting point of the crystalline organic solvent, and the block weight Cooling to above the glass transition temperature of the coalescence.
In this method, unlike the step (c), the crystalline organic solvent is crystallized on the substrate by cooling the substrate, and accordingly, the orientation of the block copolymer is determined in a certain direction, and is regular and free of defects. Nano patterns can be formed. However, in this method, it is necessary to determine conditions under which the crystalline organic solvent is not removed during the etching described later.

  Further, in step (d), (d-1) while maintaining the temperature of the surface opposite to the substrate of the mold at a temperature equal to or higher than the melting point of the crystalline organic solvent, the temperature of one end of the substrate is Cooling below the melting point of the crystalline organic solvent and above the glass transition temperature of the block copolymer, (d-2) cooling in the step (d-1) is predetermined from one end to the other end of the substrate It is preferable to carry out sequentially at the speeds. That is, it is preferable to perform a zone cooling method in which the substrate is sequentially cooled to a predetermined temperature for each predetermined region. Thereby, the grain boundaries of the block copolymer can be eliminated, and the orientation of the domain arrangement can be regularly arranged in one direction. A preferable moving speed at the time of zone cooling is the same as that in the above steps (c-1) and (c-2).

After the removal of the template in step (e), it is preferable to provide holes by etching the region where the polymer component having a carbon double bond in the main chain is phase-separated. As a result, a porous nanostructure having regularly arranged pores can be produced. Any method can be used as the etching method, and examples thereof include ozone etching, fluorine ion etching, ultraviolet etching, and plasma etching. In the present invention, ozone etching or fluorine ion etching is particularly preferable.
The porous nanostructure in which the pores of the present invention are regularly arranged is an optical filter or diffraction grating that uses the difference in thickness between the pores formed on the surface and other portions, as the arrangement is used. Etc. can be used.

For example, the porous structure of the present invention can be provided with functionality by utilizing the pores provided in the porous nanostructure, and the pores are filled with various functional elements. Thus, a functional nanostructure in which functional elements are regularly arranged can be obtained.
In addition to the above, it is also conceivable to impart functionality to the nanostructure using a replica of the nanostructure.
Applications utilizing the pores of the porous structure include applications such as optical waveguides and fluid microchannels. In particular, in the case of a cylindrical separation layer, application to a microchannel is effective. Examples of functional elements in which the pores are filled with functional elements include optical functional elements, magnetic elements, semiconductor elements, conductor elements, ferroelectric elements, phase change elements, photochromic elements, thermochromic elements, electro Although a chromic element etc. are mentioned, this invention is not limited to these.
The functional nanostructure of the present invention can be applied to a wide range of applications. For example, when a magnetic element is used, it can be used as a high-density magnetic recording medium, and when a semiconductor fine particle is used, it can be used for a highly integrated circuit. In addition, various functions can be exhibited by using various functional elements such as organic transistors, biochips, solar cells, displays, nanowires, and chemical substance detection sensors.

As an application example of the present invention, an optical functional element, a semiconductor element or a magnetic element is particularly preferable. More specifically, the application to an optical functional element, a magnetic element, etc. will be described below.
For example, as an optical functional element, it can be used for a photonic crystal. For example, a photonic band gap can be formed, the above-described optical waveguide or diffraction grating can be formed, and further, it can be applied to a light emitting element. Conceivable. In addition, application to an optical storage medium using a photonic crystal is also conceivable. In particular, by filling the pores with a light emitting material, a light emitting element having a short emission spectrum width, a low threshold laser, or the like can be realized.

  As an application example to a magnetic element, application to a magnetic recording medium or the like can be expected. By filling the pores of the functional nanostructure with ferromagnetic particles such as Co, Fe, and Ni, a patterned medium in which the ferromagnetic metal particles in the nanopattern are one memory unit can be realized. Further, by using a pulse plating method or the like to produce a magnetoresistive multilayer film in which ferromagnetic layers are alternately formed between nonmagnetic layers, a magnetic storage medium having a higher density and higher sensitivity using the GMR effect is obtained. Can also be used. As the ferromagnetic metal used for the magnetoresistive film utilizing the GMR effect, for example, a material made of a ferromagnetic metal mainly composed of Co, Fe, Ni or at least one of them can be used. Can be made of Cu, Ag, Au, or a nonmagnetic metal containing at least one of them as a main component. A magnetic storage medium in which a magnetoresistive film is formed in the pores of a nanostructure is described in, for example, Japanese Patent Application Laid-Open No. 10-283618.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.

Example 1
(Production of mold)
First, a photo-curable photoresist (novolak resin, σ-quinonediazide, AZ-1300 series, trade name, manufactured by Shipley Co., Ltd.) is applied on a Si substrate, and an Hg-g line is applied to portions other than the pattern through a predetermined pattern original plate. After exposing (436 nm) for 30 seconds, the unirradiated portion of the photoresist was removed, and a pattern groove having a width of 300 nm and a depth of 100 nm was formed on the substrate. The cured photoresist was removed by post-baking to produce a convex substrate. On the prepared substrate, 10 ml of tridecafluoro-1,1,2,2-tetrahydrooctyltrichlorosilane (manufactured by United Chemical Technology) was applied.
Next, a PDMS (polydimethylsiloxane) precursor (Sylgard 184, trade name, manufactured by Dow Corning) was applied on the prepared pattern substrate, and the substrate was heated at 60 ° C. for 2 hours to cure PDMS. Then, a pattern was transferred and a mold having a concave shape was produced. On the produced mold, a fluoropolymer release agent was applied and polymerized to give a coating having a thickness of about 10 nm (Nanos B treatment, trade name, manufactured by T & K Co., Ltd.).

(Preparation of block copolymer solution)
A solution (concentration 30% by mass, 150 ° C.) in which a block copolymer of polystyrene (number average molecular weight: 61000) and polybutadiene (number average molecular weight: 11000) was dissolved in benzoic acid was prepared.

(Production of nanostructures)
A block copolymer solution (150 ° C.) is poured into the pattern groove of the mold heated to 150 ° C., and the excess solution overflowed is removed. Then, a silica substrate heated to 150 ° C. is placed on the mold and adhered. I let you. As shown in FIGS. 2 and 3, a part of the mold (surface opposite to the substrate) is brought into contact with the plate at 110 ° C., and benzoic acid is crystallized little by little while moving the substrate at 1 μm / s. (Zone cooling method). After the above cooling, the template was further brought into contact with a plate at 60 ° C. to similarly perform zone cooling to cool the block copolymer, and then the template was removed from the substrate to produce a nanostructure on the substrate.

When the cross section of the nanostructure was observed with a field emission scanning electron microscope (FE-SEM; S-4700, trade name, manufactured by Hitachi High-Tech Co., Ltd.), a film of benzoic acid crystallized on the top (about 45 nm) ) And a block copolymer film (about 40 nm) were confirmed at the bottom. Reactive ion etching on nanostructures (RIE, CF 4 / O 2 , trade name: RIE-10NR, manufactured by Samco Co., Ltd.) to form benzoic acid, and half the thickness of block copolymer film Etching was performed. When the etching surface was observed with an atomic force microscope (AFM; phase image, MFD-3D, trade name, manufactured by Asylum Research Co., Ltd.), a sub-structure portion transferred from the pattern groove of the mold was formed on the substrate. It has a sea-island structure that is phase-separated into polystyrene-like sea-like regions constituting the sub-structure part, and polybutadiene domains are regularly arranged at intervals of about 20 nm in diameter and 49 nm in the island-like regions. It was confirmed. No grain boundaries were observed and no defects were observed in the pattern arrangement.

Example 2
A nanostructure was produced in the same manner as in Example 1 except that the substrate was brought into close contact with the mold, and then a part of the substrate was brought into contact with a 110 ° C. plate and cooled.
When the cross-section of the nanostructure was observed with FE-SEM in the same manner as in Example 1, a block copolymer film was formed on the upper part (about 40 nm) and a crystallized benzoic acid film was formed on the lower part (about 45 nm). Was confirmed. After the etching treatment in the same manner as in Example 1, when observed by AFM, the block copolymer constituting the substructure portion has a sea-island structure in which polybutadiene is phase-separated into island-like regions and polystyrene is separated into sea-like regions. The island-like regions had a diameter of about 20 nm and were regularly arranged at intervals of 49 nm. Grain boundaries were not observed, and no defects were observed in the pattern arrangement.

Example 3
The depth of the pattern groove of the mold was set to 150 nm, and a solution (concentration 30% by mass) of a block copolymer of polystyrene (number average molecular weight: 45000) and polyisoprene (number average molecular weight: 12000) dissolved in benzoic acid. 150 ° C.), and after the substrate was brought into close contact with the mold, the entire surface of the mold (the surface opposite to the substrate) was brought into contact with the 110 ° C. plate and cooled. In the same manner, a nanostructure was produced.
When the prepared nanostructure was observed with FE-SEM in the same manner as in Example 1, crystallized benzoic acid (about 80 nm) was formed on the upper part of the block copolymer (about 60 nm) constituting the substructure part. It was a film. After the etching treatment in the same manner as in Example 1, when observed by AFM, the block copolymer constituting the substructure part has a cylinder structure in which polyisoprene is phase-separated into a cylindrical region, and the cylinder structure The length direction of was arranged perpendicular to the substrate surface. The cylindrical regions had a diameter of about 25 nm and were regularly arranged at intervals of 48 nm. Grain boundaries were not observed, and no defects were observed in the pattern arrangement.
The produced nanostructure is shown in FIG. 4A is a front sectional view of the nanostructure produced in Example 3, and FIG. 4B is a plan view. FIG. 4A is a cross-sectional view taken along the line IV-IV in FIG. Referring to FIG. 4, a plurality of substructure portions 2 constituting a nanostructure are formed on a substrate 3, and a block copolymer constituting the substructure portion 2 is a cylindrical region 24 and a cylinder surrounding it. Phase separation is performed in the surrounding region 25, and the length direction of the cylinder structure 24 is arranged perpendicular to the substrate 3.

Example 4
A nanostructure was produced in the same manner as in Example 3 except that the substrate was brought into close contact with the mold, and then the entire surface on the substrate side was brought into contact with a 110 ° C. plate and cooled.
The prepared nanostructure was observed with FE-SEM in the same manner as in Example 1. As a result, a block copolymer (about 60 nm) was formed on the crystallized benzoic acid (about 80 nm) constituting the substructure portion. It was a film. After the etching process, the block copolymer constituting the substructure part has a cylinder structure in which polyisoprene is phase-separated into a cylindrical region, and the length direction of the cylinder structure is the substrate surface. It was arranged perpendicular to. The cylindrical regions had a diameter of about 25 nm and were regularly arranged at intervals of 48 nm. Grain boundaries were not observed, and no defects were observed in the pattern arrangement.

Example 5
A nanostructure was produced in the same manner as in Example 1 except that the block copolymer of polystyrene and polyisoprene used in Example 3 was used.
When the produced nanostructure was observed with FE-SEM in the same manner as in Example 1, the substructure portion transferred from the pattern groove of the template was formed on the substrate, and the block weight constituting the substructure portion was determined. Crystallized benzoic acid was deposited (about 80 nm) on the top of the coalescence (about 60 nm). After the etching process, the block copolymer constituting the substructure part has a cylinder structure in which polyisoprene is phase-separated into a cylindrical region, and the length direction of the cylinder structure is the substrate surface. Were arranged horizontally against. The cylindrical regions had a diameter of about 24 nm and were regularly arranged at 47 nm intervals. Grain boundaries were not observed, and no defects were observed in the pattern arrangement.
The produced nanostructure is shown in FIG. FIG. 5A shows a front view of the nanostructure produced in Example 5, and FIG. 5B shows a plan sectional view. FIG. 5B is a cross-sectional view taken along the line VV in FIG. Referring to FIG. 5, a plurality of substructure portions 2 constituting a nanostructure are formed on a substrate 3, and a block copolymer constituting the substructure portion 2 is a cylindrical region 24 and a cylinder surrounding it. Phase separation is performed in the surrounding region 25, and the length direction of the cylinder structure 24 is arranged in parallel to the substrate 3.

Example 6
A nanostructure was produced in the same manner as in Example 2 except that the block copolymer of polystyrene and polyisoprene used in Example 3 was used.
When the produced nanostructure was observed with FE-SEM in the same manner as in Example 1, a crystallized benzoic acid film was formed (about 80 nm) on the substrate, and a block copolymer (about 60 nm) was formed thereon. The sub-structure part composed of After the etching process, the block copolymer constituting the substructure part has a cylinder structure in which polyisoprene is phase-separated into a cylindrical region, and the length direction of the cylinder structure is the substrate surface. Were arranged horizontally against. The cylindrical regions had a diameter of about 24 nm and were regularly arranged at 47 nm intervals. Grain boundaries were not observed, and no defects were observed in the pattern arrangement.

Example 7
The nanostructure produced in Example 1 was irradiated with ozone, and the polybutadiene portion was etched to produce a porous nanostructure. Furthermore, when RIE was performed on the nanostructure in the same manner as in Example 1 and observed by AFM, pores having a diameter of about 22 nm were regularly arranged at intervals of 47 nm, and no defects were observed in the pattern arrangement. .

Example 8
A functional nanostructure was prepared by filling a cobalt platinum alloy into the nanoholes of the porous nanostructure prepared in Example 7 by electrodeposition. When the nanostructures were observed by AFM in the same manner as in Example 1, the magnetic elements were regularly arranged at intervals of 20 nm, and no defects were observed in the pattern arrangement.

FIG. 1 is a perspective view of one embodiment of the nanostructure of the present invention. FIG. 2 shows one embodiment of the method for producing a nanostructure of the present invention, and is a front sectional view taken along the line II-II in FIG. FIG. 3 shows an embodiment of the method for producing a nanostructure of the present invention, and is a cross-sectional plan view taken along the line III-III in FIG. 4 shows the nanostructure produced in Example 3. FIG. 4 (a) is a front sectional view taken along the line IV-IV of FIG. 4 (b), and FIG. 4 (b) is Example 3. It is a top view of the nanostructure produced by 1. FIG. 5 shows the nanostructure produced in Example 5. FIG. 5A is a front view of the nanostructure produced in Example 5, and FIG. 5B is FIG. 5A. It is a VV arrow top view. FIG. 6 shows the structure of the block copolymer at various scales. FIG. 6 (a) shows a polymer component, FIG. 6 (b) shows one molecule of the block copolymer, and FIG. FIG. 6D shows a microdomain structure formed by a plurality of block copolymer molecules, and FIG. 6D shows a structure composed of a plurality of grains.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Nanostructure 2 Substructure part 21 Island-like area | region 22 Sea-like area | region 23 The area | region which is not phase-separated 24 Cylinder-like area | region 25 Cylinder surrounding area | region 3 Board | substrate 4 Crystallized crystalline solvent 5 Template 6 Cooling plate

Claims (30)

  1.   A nanostructure formed on a substrate using a soft lithography method, and having at least one substructure part composed of two types of polymer components and a block copolymer having a regular phase separation structure. A nanostructure.
  2.   A nanostructure formed on a substrate using a soft lithography method, and having at least one substructure part composed of two types of polymer components and a block copolymer having a regular phase separation structure. The nanostructure according to claim 1, wherein the width of the substructure portion is equal to or less than the grain size of the block copolymer.
  3.   The phase separation structure of the block copolymer is a sea-island structure in which one of two kinds of polymer components constituting the block copolymer is phase-separated into an island region and the other into a sea region. 3. The nanostructure according to 1 or 2.
  4.   The nanostructure according to claim 3, wherein the composition ratio of the two polymer components constituting the block copolymer is in the range of 1:99 to 15:85 or 85:15 to 99: 1 in volume ratio. .
  5.   The nanostructure according to claim 3 or 4, wherein the island-shaped regions in the phase-separated structure of the block copolymer have a diameter of 100 nm or less, and an arrangement interval between the island-shaped regions is 10 to 100 nm.
  6.   The nano structure according to claim 1 or 2, wherein the phase separation structure of the block copolymer is a cylinder structure in which one of two kinds of polymer components constituting the block copolymer is phase-separated into a cylindrical region. Structure.
  7.   The phase separation structure of the block copolymer is a cylinder structure in which one of the two polymer components constituting the block copolymer is phase-separated into a cylindrical region, and the length direction of the cylinder structure The nanostructure according to claim 6, wherein are arranged perpendicular to the substrate surface.
  8.   The phase separation structure of the block copolymer is a cylinder structure in which one of the two polymer components constituting the block copolymer is phase-separated into a cylindrical region, and the length direction of the cylinder structure 7. The nanostructure according to claim 6, wherein are arranged in parallel to the substrate surface.
  9.   The composition ratio of the two polymer components constituting the block copolymer is in the range of 20:80 to 35:65 or 65:35 to 80:20 by volume ratio. The nanostructure according to item.
  10.   The diameter of the cylindrical region in the phase separation structure of the block copolymer is 100 nm or less, the length of the cylindrical region is 50 nm to 50 mm, and the arrangement interval between the cylindrical regions is 10 to 100 nm. Item 10. The nanostructure according to any one of Items 6 to 9.
  11.   The island-shaped region or the cylindrical region in the phase separation structure of the block copolymer is formed as a single layer (two-dimensionally) on the substrate. The nanostructure according to 1.
  12.   Of the two types of polymer components constituting the block copolymer, one is a polymer component having a carbon double bond in the main chain, and the other is a polymer component having no carbon double bond in the main chain Item 12. The nanostructure according to any one of Items 1 to 11.
  13.   The polymer component having a carbon double bond in the main chain is any one selected from the group consisting of polyisoprene, polybutylene and polychloroprene, and the polymer component having no carbon double bond in the main chain is polystyrene. The nanostructure according to any one of claims 1 to 12, which comprises any one selected from the group consisting of polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate, polyacrylamide and polyacrylonitrile.
  14.   The nanostructure according to any one of claims 1 to 13, wherein an aspect ratio of the width / height of the substructure portion is in a range of 0.1 to 10.
  15.   The width of the substructure part which comprises a nanostructure is 100 nm-10 micrometers, the height of a substructure part is 1 micrometer or less, and the space | interval of substructure parts is 25-500 nm, The any one of Claims 1-14 Nanostructures.
  16.   The nanostructure according to any one of claims 1 to 15, wherein a material of the substrate is silicon, silicon nitride, glass, metal, metal oxide, or heat resistant resin.
  17. A method for producing a nanostructure according to any one of claims 1 to 16, wherein
    (A) A block copolymer formed of two kinds of polymer components and forming a regular phase-separated structure having a pattern with a width less than the grain size formed on the upper surface is used to crystallize the block copolymer. The solution dissolved in the crystalline organic solvent is injected into the pattern formed on the upper surface of the mold held at a temperature equal to or higher than the melting point of the crystalline organic solvent,
    (B) The upper surface of the mold filled with the block copolymer solution is adhered to the substrate surface,
    (C) While maintaining the temperature of the surface of the mold on the substrate side at a temperature equal to or higher than the melting point of the crystalline organic solvent, the temperature of the surface opposite to the substrate of the mold is lower than the melting point of the crystalline organic solvent. And cooling to above the glass transition temperature of the block copolymer,
    (E) removing the template;
  18. Step (c)
    (C-1) While maintaining the temperature of the surface of the mold on the substrate side at a temperature equal to or higher than the melting point of the crystalline organic solvent, the temperature of one end of the surface opposite to the substrate of the mold is set to the crystalline organic Cooling below the melting point of the solvent and above the glass transition temperature of the block copolymer,
    (C-2) The method for producing a nanostructure according to claim 17, wherein the cooling in step (c-1) is sequentially performed at a predetermined speed from one end to the other end of the mold.
  19. A method for producing a nanostructure according to any one of claims 1 to 16, wherein
    (A) A block copolymer formed of two kinds of polymer components and forming a regular phase-separated structure having a pattern with a width less than the grain size formed on the upper surface is used to crystallize the block copolymer. The solution dissolved in the crystalline organic solvent is injected into the pattern formed on the upper surface of the mold held at a temperature equal to or higher than the melting point of the crystalline organic solvent,
    (B) The upper surface of the mold filled with the block copolymer solution is adhered to the substrate surface,
    (D) The temperature of the substrate is lower than the melting point of the crystalline organic solvent while maintaining the temperature of the surface opposite to the substrate of the mold at a temperature equal to or higher than the melting point of the crystalline organic solvent, and the block weight Cool above the glass transition temperature of the coalesced,
    (E) removing the template;
  20. Step (d)
    (D-1) The temperature at one end of the substrate is lower than the melting point of the crystalline organic solvent while maintaining the temperature of the surface opposite to the substrate of the mold at a temperature equal to or higher than the melting point of the crystalline organic solvent. And cooling to above the glass transition temperature of the block copolymer,
    (D-2) The method for producing a nanostructure according to claim 19, wherein the cooling in step (d-1) is sequentially performed at a predetermined speed from one end to the other end of the substrate.
  21.   21. The method for producing a nanostructure according to any one of claims 17 to 20, wherein a template having a width of 100 nm to 10 [mu] m and a depth of 1 [mu] m or less is used, and a distance between the grooves is 25 to 500 nm.
  22.   The method for producing a nanostructure according to any one of claims 17 to 21, wherein polydimethylsiloxane or polyurethane is used as a material of the template.
  23.   The method for producing a nanostructure according to any one of claims 17 to 22, wherein a mold having a surface coated with a material in which fluororesin particles are dispersed in an adhesive is used.
  24.   The method for producing a nanostructure according to any one of claims 17 to 22, wherein a template whose surface is coated with a fluororesin having a functional group at a terminal is used,
  25.   25. After removing the template in step (e) in the method according to any one of claims 17 to 24, the region where the polymer component having a carbon double bond in the main chain is phase-separated is etched to provide pores. A method for producing a porous nanostructure.
  26.   26. The method for producing a porous nanostructure according to claim 25, wherein ozone etching, fluorine ion etching, ultraviolet etching, or plasma etching is used as the etching method.
  27.   27. A porous nanostructure produced by the method of claim 25 or 26, comprising at least one substructure part in which pores are regularly arranged.
  28.   The manufacturing method of the functional nanostructure which fills the functional element in the pore provided in the porous nanostructure of Claim 25 or 26.
  29.   The method for producing a functional nanostructure according to claim 28, wherein the functional element is any one of an optical functional element, a semiconductor element, and a magnetic element.
  30. A functional nanostructure produced by the method according to claim 28 or 29, wherein the functional element includes at least one substructure part in which functional elements are regularly arranged.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007125665A (en) * 2005-11-07 2007-05-24 Hitachi Ltd Fine structural body and method for manufacturing fine structural body
JP2008266469A (en) * 2007-04-20 2008-11-06 Univ Of Tokyo Method for producing nanophase separated structure by polymer blend
JP2010527137A (en) * 2006-03-23 2010-08-05 マイクロン テクノロジー, インク. Topography-oriented patterning
CN101269791B (en) 2007-03-23 2010-11-24 国际商业机器公司 Method of forming nanoscale structures and nanoscale structures
US7931819B2 (en) 2006-08-15 2011-04-26 Kabushiki Kaisha Toshiba Method for pattern formation
US8105952B2 (en) 2007-09-26 2012-01-31 Kabushiki Kaisha Toshiba Method of forming a pattern
JP2012051958A (en) * 2010-08-31 2012-03-15 Univ Of Tokyo Method for producing nanoperiodic structure by polymer mixed system
JP2013227479A (en) * 2011-09-15 2013-11-07 Wisconsin Alumni Research Foundation Directed assembly of block copolymer film between chemically patterned surface and second surface
US10438626B2 (en) 2007-12-07 2019-10-08 Wisconsin Alumni Research Foundation Density multiplication and improved lithography by directed block copolymer assembly

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* Cited by examiner, † Cited by third party
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KR101852172B1 (en) 2011-07-01 2018-04-25 동우 화인켐 주식회사 Method for manufacturing nano structure

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61146301A (en) * 1984-12-19 1986-07-04 Daicel Chem Ind Ltd Membrane and its preparation
JPH10330494A (en) * 1997-05-29 1998-12-15 Katsunori Funaki Microphase separation structure of polymer and its formation
JP2005060583A (en) * 2003-08-18 2005-03-10 Kansai Tlo Kk Method for producing block copolymer membrane having vertically oriented lamella structure

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61146301A (en) * 1984-12-19 1986-07-04 Daicel Chem Ind Ltd Membrane and its preparation
JPH10330494A (en) * 1997-05-29 1998-12-15 Katsunori Funaki Microphase separation structure of polymer and its formation
JP2005060583A (en) * 2003-08-18 2005-03-10 Kansai Tlo Kk Method for producing block copolymer membrane having vertically oriented lamella structure

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007125665A (en) * 2005-11-07 2007-05-24 Hitachi Ltd Fine structural body and method for manufacturing fine structural body
JP2010527137A (en) * 2006-03-23 2010-08-05 マイクロン テクノロジー, インク. Topography-oriented patterning
US7931819B2 (en) 2006-08-15 2011-04-26 Kabushiki Kaisha Toshiba Method for pattern formation
CN101269791B (en) 2007-03-23 2010-11-24 国际商业机器公司 Method of forming nanoscale structures and nanoscale structures
JP2008266469A (en) * 2007-04-20 2008-11-06 Univ Of Tokyo Method for producing nanophase separated structure by polymer blend
US8105952B2 (en) 2007-09-26 2012-01-31 Kabushiki Kaisha Toshiba Method of forming a pattern
US10438626B2 (en) 2007-12-07 2019-10-08 Wisconsin Alumni Research Foundation Density multiplication and improved lithography by directed block copolymer assembly
JP2012051958A (en) * 2010-08-31 2012-03-15 Univ Of Tokyo Method for producing nanoperiodic structure by polymer mixed system
JP2013227479A (en) * 2011-09-15 2013-11-07 Wisconsin Alumni Research Foundation Directed assembly of block copolymer film between chemically patterned surface and second surface
US9718250B2 (en) 2011-09-15 2017-08-01 Wisconsin Alumni Research Foundation Directed assembly of block copolymer films between a chemically patterned surface and a second surface

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