JP2010005971A - Minute structure and method of manufacturing thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin replica mold for nano imprint, forming a highly precise metallic replica mold, hardly breaking even if foreign matter and protrusions exist, causing little transferring defective region even to a transferring object with waves. <P>SOLUTION: In the minute shaped structure composed of a support member, a buffering layer and a pattern layer formed with fine irregular patterns on the surface, the buffering layer is disposed between the support member and pattern layer, the pattern layer is composed of resin formed by curing a resin composition consisting of two or more kinds of organic components with different functional groups and a cation polymerizable catalyst, and the support member and pattern layer transmit light of a wavelength of 365 nm or more. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a fine transfer mold for pressing a mold having a fine concavo-convex pattern formed on a surface thereof onto a transfer target body to form a fine concavo-convex pattern on the surface of the transfer target.

  2. Description of the Related Art In recent years, semiconductor integrated circuits have been miniaturized and integrated, and photolithography equipment has been improved in accuracy as a pattern transfer technique for realizing fine processing. However, the processing method has approached the wavelength of the light source for light exposure, and the lithography technology has also approached its limit. Therefore, in order to advance further miniaturization and higher accuracy, an electron beam drawing apparatus, which is a kind of charged particle beam apparatus, has been used in place of lithography technology.

  Unlike the batch exposure method in pattern formation using a light source such as an i-line or excimer laser, the pattern formation using an electron beam employs a method of drawing a mask pattern. The exposure (drawing) takes time and the pattern formation takes time. Therefore, as the memory capacity increases to 256 mega, 1 giga, and 4 giga, the integration density increases dramatically, the pattern density increases, and the pattern formation time increases correspondingly, and the throughput may be remarkably inferior. Concerned. Therefore, in order to increase the speed of the electron beam drawing apparatus, development of a collective figure irradiation method in which various shapes of masks are combined and irradiated with an electron beam collectively to form an electron beam with a complicated shape is underway. . As a result, while miniaturization of the pattern has been promoted, there has been a drawback that the electron beam drawing apparatus needs to be enlarged and complicated, and the apparatus cost is increased.

  On the other hand, as a technique for performing fine pattern formation at low cost, a mold (mold) having the same pattern as the pattern to be formed on the substrate is applied to the resin film layer formed on the surface of the substrate to be transferred. A nanoimprint technique for transferring a predetermined pattern by embossing is known. According to this nanoimprint technology, it is possible to form a fine structure of 25 nanometers or less by transfer using a silicon wafer as a mold.

  However, in an imprint technique that enables formation of a fine pattern, a method for producing a mold in which a fine pattern is formed is one of the problems. Usually, the imprint mold is produced on a quartz or Si wafer by using the above-mentioned photolithography technique or electron beam drawing technique. Therefore, in addition to being very expensive, if there are foreign objects or protrusions on the transfer substrate during transfer, the expensive mold is damaged, and the occurrence of transfer defects near the foreign objects or protrusions is a major issue. It was. On the other hand, Patent Document 1 discloses a technique of replicating a resin replica mold using a photolithography technique or an electron beam drawing technique as a master mold for a mold produced on a quartz or Si wafer.

JP 2007-245684 A

  Patent Document 1 discloses a technique that can form a resin replica having a high aspect ratio structure by using an elastic body having a glass transition temperature (Tg) of 30 ° C. or less as a replica mold material. When forming a metallic replica such as Ni from this resin replica, a conductive electrode is formed on the resin replica and a transfer replica mold is prepared by electroplating. As a result of studying replica mold fabrication, the nanoscale pattern shape is easily affected by the conductive electrode formation process, and this process is formed at a temperature higher than room temperature such as sputtering film formation or electroless plating. It has been found that the pattern accuracy is impaired when the glass transition temperature of the resin replica material is lower than the process temperature.

  Also, when a pattern is transferred to a resin film formed on a hard substrate such as a Si wafer using a mold such as Si or quartz, if there are protrusions or foreign matter on the substrate surface, It was found that the fine concavo-convex pattern on the mold surface was damaged, and a wide range of transfer failure areas were generated around the protrusions and foreign matter. Further, when waviness is present on the surface of the substrate to be transferred, the mold cannot follow the waviness, resulting in transfer failure.

  Therefore, the object of the present invention is for nanoimprinting, which can form a high-precision metal replica mold, is less likely to be damaged even if foreign matter and protrusions are present, and has few transfer failure regions even on a swelled transfer target. The object is to provide a resin replica mold.

  The above-mentioned problem is, firstly, in a fine-shaped structure composed of a support member and a pattern layer having a fine concavo-convex pattern formed on the surface, the pattern layer comprises two or more organic components having different functional groups and a cation. The problem is solved by using a fine structure which is made of a resin obtained by curing a resin composition comprising a polymerizable catalyst, and the support member and the pattern layer transmit light having a wavelength of 365 nm or more.

  Second, in a finely shaped structure including a support member, a buffer layer, and a pattern layer having a fine concavo-convex pattern formed on the surface, the buffer layer is disposed between the support member and the pattern layer. And the said pattern layer is comprised from resin which hardened the resin composition which consists of 2 or more types of organic components from which a functional group differs, and a cationic polymerizable catalyst, The said supporting member, the said buffer layer, and the said pattern layer are The problem is solved by using a microstructure that transmits light having a wavelength of 365 nm or more.

  The support member used in the present invention is not particularly limited in material, size, and manufacturing method as long as it has a function of holding the pattern layer. The material may be a silicon wafer, various metal materials, glass, quartz, ceramic, plastic or the like having strength and workability. Specifically, Si, SiC, SiN, polycrystalline Si, Ni, Cr, Cu, and those containing one or more of these are exemplified. In particular, quartz is preferable because it has high transparency and the pattern layer or the buffer layer is a photocurable material because the resin is efficiently irradiated with light.

  Moreover, it is preferable that the surface of these supporting members is subjected to a coupling treatment for enhancing the adhesive force with the pattern layer and the buffer layer.

  The pattern layer of the present invention is formed by pressing and curing a master mold on a resin composition comprising two or more organic components having different functional groups and a cationically polymerizable catalyst, which is a liquid master formed on the surface of a support member. Is done. Therefore, the uneven shape is a shape obtained by inverting the uneven pattern of the master mold. Curing is performed by light irradiation, heat curing, or a combination thereof.

  Since the pattern layer after curing can transmit light having a wavelength of 365 nm or more, the microstructure of the present invention can be used as a replica mold for optical nanoprinting. Further, Tg in the present invention is a temperature at which the elastic modulus and linear expansion coefficient of the material greatly change before and after that, and can be evaluated by a viscoelasticity evaluation apparatus, a linear expansion coefficient evaluation apparatus, a differential scanning calorimeter, or the like. The pattern layer Tg after curing in the present invention is preferably as high as possible, and when it is 50 ° C. or higher, a replica mold with high pattern accuracy is realized when an electrode layer is formed by electroless plating and then a replica mold is produced by electroplating. it can.

  Furthermore, when the microstructure of the present invention is used as a nanoimprint mold, a release layer is formed on the surface of the pattern layer of the present invention to reduce interaction with the transfer target. As the release layer material, a fluorine-based surfactant or a silicone-based surfactant can be used. As a fluorosurfactant, a perfluoroalkyl-containing oligomer and a perfluoroalkyl-containing oligomer solution dissolved in a solvent can be used. Further, a hydrocarbon chain bonded to a perfluoroalkyl chain may be used. In addition, a structure in which an ethoxy chain or a methoxy chain is bonded to a perfluoroalkyl chain may be used. Further, a structure in which siloxane is bonded to these perfluoroalkyl chains may be used. In addition, a commercially available fluorosurfactant can also be used. In the release layer, these surfactants may be covalently bonded to the surface of the pattern layer, or may simply be in volume.

  The resin composition constituting the pattern layer of the present invention comprises two or more organic components having different functional groups and a cationic polymerizable catalyst. The organic component has a functional group of any one of an epoxy group, an oxetanyl group, and a vinyl ether group. The organic component basically does not include a solvent component that does not have a reactive functional group, but even if it includes a solvent component that does not have a reactive functional group that is unintentionally mixed in the manufacturing process of the organic component, It does not inhibit the effect. Specific organic components having an epoxy group of the present invention include bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, aliphatic cyclic epoxy resins, and naphthalene type epoxy resins. , Biphenyl type epoxy resin, bifunctional alcohol ether type epoxy resin and the like. Examples of the organic component having an oxetanyl group include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 3-ethyl-3- (phenoxymethyl). ) Oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] Examples include methyl} oxetane, oxetanylsilsesquioxane, phenol novolac oxetane and the like. Further, organic components having vinyl ether groups include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, isophthalic acid. Examples include di (4-vinyloxy) butyl, di (4-vinyloxy) butyl glutarate, di (4-vinyloxy) butyltrimethylolpropane trivinyl ether, 2-hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, and the like. The As mentioned above, although the organic component which has any functional group of an epoxy group, oxetanyl group, and vinyl ether group was illustrated, it is not limited. Any epoxy group, oxetanyl group, or vinyl ether group formed in the molecular chain can be basically used in the present invention. Of these organic components, a polyfunctional organic component having a plurality of functional groups in one organic component is particularly preferable because it contributes to increasing the crosslinking point of the cured product and increasing Tg.

  The cationic polymerizable catalyst of the present invention is an electron-saving reagent, has a cation generation source, and is not particularly limited as long as it can cure organic components by heat or light, and a known cationic polymerization catalyst should be used. Can do. In particular, a cationically polymerizable catalyst that initiates curing by ultraviolet rays is preferable because it can form a concavo-convex pattern at room temperature and can form a replica from a master mold with higher accuracy. Examples of the cationically polymerizable catalyst include iron-allene complex compounds, aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, pyridinium salts, aluminum complexes / silyl ethers, protonic acids, Lewis acids, and the like. Specific examples of the cationic polymerization catalyst that initiates curing by ultraviolet rays include IRGACURE 261 (manufactured by Ciba Geigy), Optmer SP-150 (manufactured by Asahi Denka Kogyo Co., Ltd.), Optmer SP-151 (manufactured by Asahi Denka Kogyo Co., Ltd.), Optomer SP-152 Asahi Denka Kogyo Co., Ltd.), Optomer SP-170 (Asahi Denka Kogyo Co., Ltd.), Optmer SP-171 (Asahi Denka Kogyo Co., Ltd.), Optomer SP-172 (Asahi Denka Kogyo Co., Ltd.), UVE-1014 ( General Electronics Co., Ltd.), CD-1012 (Sartomer Co., Ltd.), Sun-Aid SI-60L (Sanshin Chemical Co., Ltd.), Sun-Aid SI-80L (Sanshin Chemical Co., Ltd.), Sun-Aid SI-100L (Sanshin Chemical Industry) , Sun Aid SI-110 (manufactured by Sanshin Chemical Industry Co., Ltd.), Sun Aid SI-180 (manufactured by Sanshin Chemical Industry Co., Ltd.) CI-2064 (manufactured by Nippon Soda Co., Ltd.), CI2639 (manufactured by Nippon Soda Co., Ltd.), CI-2624 (manufactured by Nippon Soda Co., Ltd.), CI-2481 (manufactured by Nippon Soda Co., Ltd.), Uvacure 1590 (Daicel UCB), Uvacure 1591 (Daicel UCB) ), RHODORSILPhotoInItiator 2074 (Rhone-Poulein), UVI-6990 (Union Carbide), BBI-103 (Midori Chemical), MPI-103 (Midori Chemical), TPS-103 (Midori Chemical) , MDS-103 (manufactured by Midori Chemical), DTS-103 (manufactured by Midori Chemical), DTS-103 (manufactured by Midori Chemical), NAT-103 (manufactured by Midori Chemical), NDS-103 (manufactured by Midori Chemical) , CYRAURE UVI 6990 (Union Carbide Japan) and the like. These polymerization initiators can be applied alone, but can also be used in combination of two or more. In addition, it can also be applied in combination with known polymerization accelerators and sensitizers.

  In addition, the resin composition of the present invention may contain a surfactant for enhancing the adhesion with the support member. Moreover, you may add additives, such as a polymerization inhibitor, as needed.

  The buffer layer of the present invention is not particularly limited as long as it is an elastic body that is elastically deformed at room temperature. The role of the buffer layer is placed between the hard support member and the pattern layer, so that when there is a foreign object or protrusion, it is elastically deformed together with the pattern layer, preventing damage to the fine uneven pattern on the surface of the pattern layer, and transferring. It plays a role of minimizing the defective area. In addition, even when undulation is present on the surface of the transfer substrate, it plays a role of following the undulations on the surface of the pattern layer. For this reason, the buffer layer of the present invention uses a material whose elastic modulus is lower than that of the pattern layer and whose thickness is thick. Further, when the microstructure is used for optical nanoimprinting, a material that transmits light having a wavelength of 365 nm or more is used.

  Specific buffer layer materials include fluorine rubber, fluorosilicone rubber, acrylic rubber, hydrogenated nitrile rubber, ethylene propylene rubber, chlorosulfonated polystyrene rubber, epichlorohydrin rubber, butyl rubber, urethane rubber, polycarbonate (PC) / acrylonitrile butadiene. Styrene (ABS) alloy, polysiloxane dimethylene terephthalate (PCT) / polyethylene terephthalate (PET), copolymerized polybutylene terephthalate (PBT) / polycarbonate (PC) alloy, polytetrafluoroethylene (PTFE), fluorinated ethylene propylene heavy Combined (FEP), polyarylate, polyamide (PA) / acrylonitrile butadiene styrene (ABS) alloy, modified epoxy resin, modified polyolefin, etc. It is shown. In addition, epoxy resin, unsaturated polyester resin, epoxy isocyanate resin, maleimide resin, maleimide epoxy resin, cyanate ester resin, cyanate ester epoxy resin, cyanate ester maleimide resin, phenol resin, diallyl phthalate resin, urethane resin, Various resins such as cyanamide resin and maleimide cyanamide resin and polymer materials obtained by combining two or more of these may be used, but are not limited thereto.

  By using the microstructure of the present invention, the Tg of the pattern layer becomes equal to or higher than the metal replica formation temperature, and a highly accurate metal replica mold can be formed. In addition, by adopting a structure having a buffer layer between the pattern layer, the support member, and the buffer layer, even if there are foreign matters or protrusions in the layer, it is difficult to break, and even a transfer defect region with a wavy transfer object It is possible to provide a resin replica mold for nanoimprinting with a small amount.

  The first embodiment of the microstructure of the present invention is a microstructure having a support member and a pattern layer having a fine concavo-convex pattern formed on the surface, wherein the pattern layer has different functional groups. It is made of a resin obtained by curing a resin composition comprising at least one kind of organic component and a cationically polymerizable catalyst, and the support member and the pattern layer transmit light having a wavelength of 365 nm or more.

  The second embodiment of the microstructure of the present invention is a microstructure having a support member, a buffer layer, and a pattern layer having a fine concavo-convex pattern formed on the surface, wherein the buffer layer is the support The pattern layer is disposed between a member and the pattern layer, and the pattern layer is made of a resin obtained by curing a resin composition comprising two or more organic components having different functional groups and a cationic polymerizable catalyst, and the support The member, the buffer layer, and the pattern layer transmit light having a wavelength of 365 nm or more.

  The support member used in the present invention is not particularly limited in material, size, and manufacturing method as long as it has a function of holding the pattern layer. The material may be a silicon wafer, various metal materials, glass, quartz, ceramic, plastic or the like having strength and workability. Specifically, Si, SiC, SiN, polycrystalline Si, Ni, Cr, Cu, and those containing one or more of these are exemplified. In particular, quartz is preferable because it has high transparency and the pattern layer or the buffer layer is a photocurable material because the resin is efficiently irradiated with light.

  Moreover, it is preferable that the surface of these supporting members is subjected to a coupling treatment for enhancing the adhesive force with the pattern layer and the buffer layer.

  The pattern layer of the present invention is formed by pressing and curing a master mold on a resin composition comprising two or more organic components having different functional groups and a cationically polymerizable catalyst, which is a liquid master formed on the surface of a support member. Is done. Therefore, the uneven shape is a shape obtained by inverting the uneven pattern of the master mold. As a curing method, curing is performed by light irradiation, heat curing, and a combination thereof.

  Since the pattern layer after curing can transmit light having a wavelength of 365 nm or more, the microstructure of the present invention can be used as a replica mold for optical nanoprinting. Further, Tg in the present invention is a temperature at which the elastic modulus and linear expansion coefficient of the material greatly change before and after that, and can be evaluated by a viscoelasticity evaluation apparatus, a linear expansion coefficient evaluation apparatus, a differential scanning calorimeter, or the like. The Tg of the pattern layer after curing in the present invention is preferably as high as possible, and when the replica mold is produced by electroplating after forming the electrode layer by electroless plating, a replica mold with high pattern accuracy is obtained. realizable.

  Furthermore, when the microstructure of the present invention is used as a nanoimprint mold, a release layer is formed on the surface of the pattern layer of the present invention to reduce interaction with the transfer target. As the release layer material, a fluorine-based surfactant or a silicone-based surfactant can be used. A perfluoroalkyl-containing oligomer solution in which a perfluoroalkyl-containing oligomer is dissolved in a solvent can be used as the fluorosurfactant. Further, a hydrocarbon chain bonded to a perfluoroalkyl chain may be used. In addition, a structure in which an ethoxy chain or a methoxy chain is bonded to a perfluoroalkyl chain may be used. Further, a structure in which siloxane is bonded to these perfluoroalkyl chains may be used. In addition, a commercially available fluorosurfactant can also be used. In the release layer, these surfactants may be covalently bonded to the surface of the pattern layer, or may simply be in volume.

  The resin composition constituting the pattern layer of the present invention comprises two or more organic components having different functional groups and a cationic polymerizable catalyst. The organic component has a functional group of any one of an epoxy group, an oxetanyl group, and a vinyl ether group. The organic component basically does not include a solvent component that does not have a reactive functional group, but even if it includes a solvent component that does not have a reactive functional group that is unintentionally mixed in the manufacturing process of the organic component, It does not inhibit the effect. Specific organic components having an epoxy group of the present invention include bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, aliphatic cyclic epoxy resins, and naphthalene type epoxy resins. , Biphenyl type epoxy resin, bifunctional alcohol ether type epoxy resin and the like. Examples of the organic component having an oxetanyl group include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 3-ethyl-3- (phenoxymethyl). ) Oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] Examples include methyl} oxetane, oxetanylsilsesquioxane, phenol novolac oxetane and the like. Further, organic components having vinyl ether groups include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, isophthalic acid. Examples include di (4-vinyloxy) butyl, di (4-vinyloxy) butyl glutarate, di (4-vinyloxy) butyltrimethylolpropane trivinyl ether, 2-hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, and the like. The As mentioned above, although the organic component which has any functional group of an epoxy group, oxetanyl group, and vinyl ether group was illustrated, it is not limited to this. Any epoxy group, oxetanyl group, or vinyl ether group formed in the molecular chain can be basically used in the present invention. Among these organic components, a polyfunctional organic component having a plurality of functional groups in one organic component is particularly preferable because it contributes to increasing the crosslinking point of the cured product and increasing Tg.

  The cationic polymerizable catalyst of the present invention is an electron-saving reagent, has a cation generation source, and is not particularly limited as long as it can cure organic components by heat or light, and a known cationic polymerization catalyst should be used. Can do. In particular, a cationically polymerizable catalyst that initiates curing by ultraviolet rays is preferable because it can form a concavo-convex pattern at room temperature and can form a replica from a master mold with higher accuracy. Examples of the cationically polymerizable catalyst include iron-allene complex compounds, aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, pyridinium salts, aluminum complexes / silyl ethers, protonic acids, Lewis acids, and the like. Specific examples of the cationic polymerization catalyst that initiates curing by ultraviolet rays include IRGACURE 261 (manufactured by Ciba Geigy), Optmer SP-150 (manufactured by Asahi Denka Kogyo Co., Ltd.), Optmer SP-151 (manufactured by Asahi Denka Kogyo Co., Ltd.), Optomer SP-152 Asahi Denka Kogyo Co., Ltd.), Optomer SP-170 (Asahi Denka Kogyo Co., Ltd.), Optmer SP-171 (Asahi Denka Kogyo Co., Ltd.), Optomer SP-172 (Asahi Denka Kogyo Co., Ltd.), UVE-1014 ( General Electronics Co., Ltd.), CD-1012 (Sartomer Co., Ltd.), Sun-Aid SI-60L (Sanshin Chemical Co., Ltd.), Sun-Aid SI-80L (Sanshin Chemical Co., Ltd.), Sun-Aid SI-100L (Sanshin Chemical Industry) , Sun Aid SI-110 (manufactured by Sanshin Chemical Industry Co., Ltd.), Sun Aid SI-180 (manufactured by Sanshin Chemical Industry Co., Ltd.) CI-2064 (manufactured by Nippon Soda Co., Ltd.), CI2639 (manufactured by Nippon Soda Co., Ltd.), CI-2624 (manufactured by Nippon Soda Co., Ltd.), CI-2481 (manufactured by Nippon Soda Co., Ltd.), Uvacure 1590 (Daicel UCB), Uvacure 1591 (Daicel UCB) ), RHODORSILPhotoInItiator 2074 (Rhone-Poulein), UVI-6990 (Union Carbide), BBI-103 (Midori Chemical), MPI-103 (Midori Chemical), TPS-103 (Midori Chemical) , MDS-103 (manufactured by Midori Chemical), DTS-103 (manufactured by Midori Chemical), DTS-103 (manufactured by Midori Chemical), NAT-103 (manufactured by Midori Chemical), NDS-103 (manufactured by Midori Chemical) , CYRAURE UVI 6990 (Union Carbide Japan) and the like. These polymerization initiators can be applied alone, but can also be used in combination of two or more. In addition, it can also be applied in combination with known polymerization accelerators and sensitizers.

  In addition, the resin composition of the present invention may contain a surfactant for enhancing the adhesion with the support member. Moreover, you may add additives, such as a polymerization inhibitor, as needed.

  The buffer layer of the present invention is not particularly limited as long as it is an elastic body that is elastically deformed at room temperature. The role of the buffer layer is placed between the hard support member and the pattern layer, so that when there is a foreign object or protrusion, it is elastically deformed together with the pattern layer, preventing damage to the fine uneven pattern on the surface of the pattern layer, and transferring. It plays a role of minimizing the defective area. In addition, even when undulation is present on the surface of the transfer substrate, it plays a role of following the undulations on the surface of the pattern layer. For this reason, the buffer layer of the present invention uses a material whose elastic modulus is lower than that of the pattern layer and whose thickness is thick. Further, when the microstructure is used for optical nanoimprinting, a material that transmits light having a wavelength of 365 nm or more is used.

  Specific buffer layer materials include fluorine rubber, fluorosilicone rubber, acrylic rubber, hydrogenated nitrile rubber, ethylene propylene rubber, chlorosulfonated polystyrene rubber, epichlorohydrin rubber, butyl rubber, urethane rubber, polycarbonate (PC) / acrylonitrile butadiene. Styrene (ABS) alloy, polysiloxane dimethylene terephthalate (PCT) / polyethylene terephthalate (PET), copolymerized polybutylene terephthalate (PBT) / polycarbonate (PC) alloy, polytetrafluoroethylene (PTFE), fluorinated ethylene propylene heavy Combined (FEP), polyarylate, polyamide (PA) / acrylonitrile butadiene styrene (ABS) alloy, modified epoxy resin, modified polyolefin, etc. It is shown. In addition, epoxy resin, unsaturated polyester resin, epoxy isocyanate resin, maleimide resin, maleimide epoxy resin, cyanate ester resin, cyanate ester epoxy resin, cyanate ester maleimide resin, phenol resin, diallyl phthalate resin, urethane resin, Various resins such as cyanamide resin and maleimide cyanamide resin and polymer materials obtained by combining two or more of these may be used, but are not limited thereto.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise indicated, “parts” and “%” used below are all based on weight.

  FIG. 1 is a schematic cross-sectional view showing a method for manufacturing a microstructure of the present invention. Hereinafter, a method for replicating the microstructure and the Ni replica mold of the present invention will be described.

  First, 10 parts of an organic component OXT221 (manufactured by Toagosei Co., Ltd.) having an oxetanyl group, 10 parts of a bisphenol AD type epoxy resin EPOMIK R710 (manufactured by Mitsui Chemicals) as an organic component having an epoxy group, and Adekaoptomer SP-152 as a cationic polymerizable catalyst 0.6 parts (manufactured by Asahi Denka Kogyo Co., Ltd.) were blended to prepare a resin composition for the pattern layer.

  Next, a quartz plate 1 having a thickness of 50 mm □ and a thickness of 3 mm was prepared (a) as a support base material by coupling the surface with KBM603 (manufactured by Shin-Etsu Silicone). The resin composition 2 used as a pattern layer was dripped on the coupling process surface of this support base material 1 (b). Next, in a state where the quartz master mold 3 in which a line pattern having a width of 200 nm, a pitch of 400 nm, and a height of 200 nm is formed on the surface subjected to the release treatment by OPTOOL DSX (manufactured by Daikin Industries) is pressed against the resin composition 2. Irradiation with ultraviolet rays having a wavelength of 365 nm was performed for 500 s (c). Next, the master mold was peeled off from the cured resin composition to form the pattern layer 4 to produce the microstructure 5 of the present invention (d). Next, an electroless Ni plating 6 having a thickness of 300 nm was formed on the surface of the microstructure by an electroless plating method at a bath temperature of 50 ° C. (e). Next, 100 μm of Ni was formed by electric Ni plating (f). The Ni plating was peeled from the fine structure to produce a Ni replica mold (g).

  The pattern shape of the manufactured Ni replica mold was measured with an atomic force microscope (manufactured by Beco), and an error from the master mold was evaluated. Moreover, Tg of the pattern layer was evaluated by DSC. The results are shown in Table 1. A high-precision Ni replica having a Tg of 50 ° C. and a dimensional error in the height direction of 1% or less was obtained.

  First, 10 parts of an organic component OXT101 having an oxetanyl group (manufactured by Toagosei Co., Ltd.), 10 parts of a polyfunctional epoxy resin EHPE3150CE (Daicel Chemical) as an organic component having an epoxy group, and Adekaoptomer SP-152 (Asahi Denka) as a cationic polymerizable catalyst (Industry Co., Ltd.) 0.6 parts was prepared to prepare a resin composition for the pattern layer. Using this resin composition, Ni replicas were formed in the same manner as in Example 1.

  Moreover, Tg of the pattern layer was evaluated by DSC. The results are shown in Table 1. A high-precision Ni replica having a Tg of 50 ° C. and a dimensional error in the height direction of 1% or less was obtained.

  First, 10 parts of an organic component OXT221 having an oxetanyl group (manufactured by Toagosei Co., Ltd.), 10 parts of a polyfunctional epoxy resin EHPE3150CE (Daicel Chemical) as an organic component having an epoxy group, and Adekaoptomer SP-152 (Asahi Denka) (Industry Co., Ltd.) 0.6 parts was prepared to prepare a resin composition for the pattern layer. Using this resin composition, Ni replicas were formed in the same manner as in Example 1.

  Moreover, Tg of the pattern layer was evaluated by DSC. The results are shown in Table 1. A high-precision Ni replica having a Tg of 50 ° C. and a dimensional error in the height direction of 1% or less was obtained.

  First, 10 parts of an organic component RAPI-CURE DPE-3 (manufactured by ISP Japan) having a vinyl ether group, 1 part of funcryl FA-513M (manufactured by Hitachi Chemical) as an organic component having a dicyclopentenyl group, and a cationically polymerizable catalyst, Adekaoptomer SP-152 (manufactured by Asahi Denka Kogyo Co., Ltd.) (0.6 part) was prepared to prepare a resin composition for the pattern layer. Using this resin composition, Ni replicas were formed in the same manner as in Example 1.

  Moreover, Tg of the pattern layer was evaluated by DSC. The results are shown in Table 1. A high-precision Ni replica having a Tg of 50 ° C. and a dimensional error in the height direction of 1% or less was obtained.

  FIG. 2 is a schematic cross-sectional view showing a method for manufacturing a microstructure of the present invention. Hereinafter, a method for manufacturing the microstructure of the present invention will be described.

  First, 10 parts of an organic component OXT221 (manufactured by Toagosei Co., Ltd.) having an oxetanyl group, 10 parts of a bisphenol AD type epoxy resin EPOMIK R710 (manufactured by Mitsui Chemicals) as an organic component having an epoxy group, and Adekaoptomer SP-152 as a cationic polymerizable catalyst 0.6 parts (manufactured by Asahi Denka Kogyo Co., Ltd.) were blended to prepare a resin composition for the pattern layer. In addition, 100 parts of urethane acrylate oligomer UV3500BA (manufactured by Nippon Synthetic Chemical Co., Ltd.), 10 parts of glycidyl methacrylate Light Eltel G (manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts of photoreaction initiator Darocure 1173 (manufactured by Ciba Specialty Chemicals Co., Ltd.) are prepared, and a buffer layer The raw material was produced.

  Next, as a supporting base material, a quartz plate 1 having a surface of 50 mm □ and a thickness of 3 mm was prepared by coupling the surface with KBM5103 (manufactured by Shin-Etsu Silicone), and a buffer layer raw material 8 was applied (a). This buffer layer raw material 8 was pressed and flattened by a flat plate 9 treated with OPTOOL DSX, and irradiated with ultraviolet light of 365 nm for 200 s (b). The buffer layer has a Tg of room temperature or lower, and the elastic modulus at room temperature is smaller than that of the pattern layer. Next, the flat plate was peeled off from the cured buffer layer 10, and the resin composition 2 serving as a pattern layer was dropped onto the buffer layer 10 (c). Next, in a state where the quartz master mold 3 in which a line pattern having a width of 200 nm, a pitch of 400 nm, and a height of 200 nm is formed on the surface subjected to the release treatment by OPTOOL DSX (manufactured by Daikin Industries) is pressed against the resin composition 2. Irradiation with ultraviolet rays having a wavelength of 365 nm was performed for 500 s (d). Next, the master mold was peeled off from the cured resin composition to form the pattern layer 4 to produce the microstructure 5 of the present invention (d). After this pattern layer portion was subjected to oxygen plasma treatment, release treatment was performed using OPTOOL DSX (manufactured by Daikin Industries) to form a release layer 11.

  Next, an optical nanoimprint resin PAK-01 (manufactured by Toyo Gosei Co., Ltd.) 14 is applied to the transfer substrate 12 on which the pseudo protrusions 13 having a diameter of 1 μmφ and a height of 1 μm are formed, and the microstructure manufactured in this example is obtained. The resin replica stamper 15 was pressed at a pressure of 1 MPa, irradiated with ultraviolet rays 15 having a wavelength of 365 nm for 500 s, and then peeled off to perform pattern transfer. Thereafter, the pattern defect area D on the transfer substrate was measured, and the presence or absence of breakage of the resin replica stamper was observed. The results are listed in Table 1. The defective area D was 100 μm or less, and it was confirmed that the pattern surface of the resin replica stamper was not damaged.

  A resin replica stamper was produced in the same manner as in Example 5. At that time, EG6301 (manufactured by Toray Dow Co., Ltd.) was used as a buffer layer material, and the buffer layer was formed by potting and then heat curing at 150 ° C./1 h. The buffer layer has a Tg of room temperature or lower, and the elastic modulus at room temperature is smaller than that of the pattern layer. Furthermore, in order to give adhesiveness to the buffer layer surface, surface treatment was performed with a primer D3 (manufactured by Toray Dow).

  Next, pattern transfer was performed in the same manner as in Example 5, and the pattern defect area D on the transfer substrate was measured, and the presence or absence of breakage of the resin replica stamper was observed. The results are listed in Table 1. The defective area D was 100 μm or less, and it was confirmed that the pattern surface of the resin replica stamper was not damaged.

  A resin replica stamper was produced in the same manner as in Example 5. At that time, the resin composition for forming the pattern layer was the resin composition used in Example 2.

  Next, pattern transfer was performed in the same manner as in Example 5, and the pattern defect area D on the transfer substrate was measured, and the presence or absence of breakage of the resin replica stamper was observed. The results are listed in Table 1. The defective area D was 100 μm or less, and it was confirmed that the pattern surface of the resin replica stamper was not damaged.

  A resin replica stamper was produced in the same manner as in Example 5. At that time, the resin composition for forming the pattern layer was the resin composition used in Example 3.

  Next, pattern transfer was performed in the same manner as in Example 5, and the pattern defect area D on the transfer substrate was measured, and the presence or absence of breakage of the resin replica stamper was observed. The results are listed in Table 1. The defective area D was 100 μm or less, and it was confirmed that the pattern surface of the resin replica stamper was not damaged.

[Comparative Example 1]
After forming a fine structure by the same method as in Example 1, a Ni replica stamper was produced. At that time, a radical polymerizable acrylate resin was used as a resin composition for the pattern layer.

  Moreover, Tg of the pattern layer was evaluated by DSC. The results are shown in Table 1. A Ni replica having a Tg of 40 ° C. and a dimensional error of 5% in the height direction was obtained.

[Comparative Example 2]
After forming a fine structure by the same method as in Example 1, a Ni replica stamper was produced. At that time, only 10 parts of bisphenol AD type epoxy resin EPOMIK R710 (manufactured by Mitsui Chemicals) as an organic component having an epoxy group and 0.6 part of Adekaoptomer SP-152 (manufactured by Asahi Denka Kogyo Co., Ltd.) as a cationic polymerizable catalyst. The resin composition of the pattern layer was prepared.

  Moreover, Tg of the pattern layer was evaluated by DSC. The results are shown in Table 1. The Tg of the pattern layer was 50 ° C. or higher. However, a Ni replica having a dimensional error in the height direction of 10% or more was obtained.

[Comparative Example 3]
Pattern transfer was performed under the same conditions as in Example 5 using a quartz mold having the same fine irregularities as in Example 5. As a result, the vicinity of the pseudo protrusion on the surface of the quartz mold pattern was damaged. Further, the transfer failure area D occurred over several mm.

The process schematic diagram explaining 1 Example of this invention. The process schematic diagram explaining 1 Example of this invention. The pattern transfer schematic diagram using the microstructure of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Support member 2 Resin composition 3 Master mold 4 Pattern layer 5 Fine structure 6 Electroless Ni film 7 Ni replica 8 Buffer layer raw material 9 Flat plate 10 Buffer layer 11 Release layer 12 Transfer substrate 13 Pseudo protrusion 14 Photocurable resin 15 Resin replica stamper

Claims (20)

  In a microstructure comprising a support member and a pattern layer having a fine concavo-convex pattern formed on the surface, the pattern layer is composed mainly of two or more organic components having different functional groups, and a cationic polymerizable catalyst. A microstructure comprising a resin obtained by curing a resin composition, wherein the support member and the pattern layer transmit light having a wavelength of 365 nm or more.   2. The microstructure according to claim 1, wherein the organic component in the resin composition has a functional group of any one of an epoxy group, an oxetanyl group, and a vinyl ether group.   3. The microstructure according to claim 2, wherein the resin composition does not contain a solvent component.   The microstructure according to claim 2, wherein the organic component in the resin composition has two or more functional groups in one organic component. The microstructure according to claim 2, wherein one of the organic components in the resin composition is an organic component having the following structure.

  The microstructure according to claim 1, wherein the cationic polymerizable catalyst is a cationic polymerizable catalyst that initiates curing by ultraviolet rays.   2. The microstructure according to claim 1, wherein the pattern layer has a glass transition temperature of 50 ° C. or more.   2. The fine structure according to claim 1, wherein a release layer is formed on a surface of the fine concavo-convex pattern of the pattern layer.   In a microstructure including a support member, a buffer layer, and a pattern layer having a fine uneven pattern formed on the surface, the buffer layer is disposed between the support member and the pattern layer, and the pattern The layer is composed of a resin obtained by curing a resin composition containing two or more organic components having different functional groups as a main component and containing a cationic polymerizable catalyst, and the support member, the buffer layer, and the pattern layer have wavelengths. A fine structure which transmits light of 365 nm or more.   10. The microstructure according to claim 9, wherein the organic component in the resin composition has a functional group of any one of an epoxy group, an oxetanyl group, and a vinyl ether group.   The microstructure according to claim 10, wherein the resin composition does not contain a solvent component.   The microstructure according to claim 9, wherein the organic component in the resin composition has two or more functional groups in one organic component. 10. The microstructure according to claim 9, wherein one of the organic components in the resin composition is an organic component having the following structure.

  10. The fine structure according to claim 9, wherein the cationic polymerizable catalyst is a cationic polymerizable catalyst that initiates curing by ultraviolet rays.   The microstructure according to claim 9, wherein the elastic modulus of the buffer layer is smaller than the elastic modulus of the pattern layer.   The microstructure according to claim 9, wherein the thickness of the buffer layer is larger than the thickness of the pattern layer.   The microstructure according to claim 9, wherein the pattern layer has a glass transition temperature of 60 ° C or higher.   10. The microstructure according to claim 9, wherein a release layer is formed on a surface of a fine uneven pattern of the pattern layer. 11. In the manufacturing method of the fine shape structure composed of the support member and the pattern layer in which the fine uneven pattern is formed on the surface,
Applying a resin composition comprising two or more organic components having different functional groups and a cationic polymerizable catalyst on the support member;
A step of pressing a master mold having fine irregularities formed on the resin composition;
Curing the resin composition while pressing the master mold; and
Peeling the master mold from the cured resin composition;
A method for producing a fine structure characterized by comprising: In the manufacturing method of the fine structure according to claim 19,
After forming a buffer layer on the support member, there is a step of applying a resin composition comprising two or more organic components having different functional groups and a cationic polymerizable catalyst on the buffer layer Manufacturing method of structure.

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