US20140349086A1 - Photo-curable composition and patterning method using the same - Google Patents

Photo-curable composition and patterning method using the same Download PDF

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Publication number
US20140349086A1
US20140349086A1 US14/357,542 US201214357542A US2014349086A1 US 20140349086 A1 US20140349086 A1 US 20140349086A1 US 201214357542 A US201214357542 A US 201214357542A US 2014349086 A1 US2014349086 A1 US 2014349086A1
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Prior art keywords
photo
curable composition
ether
meth
acrylate
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US14/357,542
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Toshiki Ito
Chieko Mihara
Kanae Kawahata
Motoki Okinaka
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Canon Inc
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Canon Inc
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Publication of US20140349086A1 publication Critical patent/US20140349086A1/en
Assigned to CANON KABUSHIKI KAISHA reassignment CANON KABUSHIKI KAISHA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OKINAKA, MOTOKI, MIHARA, CHIEKO, ITO, TOSHIKI, KAWAHATA, Kanae
Priority to US16/719,647 priority Critical patent/US11332597B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0014—Shaping of the substrate, e.g. by moulding
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0017—Etching of the substrate by chemical or physical means
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]

Definitions

  • the present invention relates to a photo-curable composition and a patterning method using the photo-curable composition.
  • a UV nanoimprint method is a patterning method of pressing a mold having a fine textured pattern on its surface against a substrate coated with a resist (photo-curable composition) to transfer the textured pattern to the resist film on the substrate.
  • demolding force It is important in the UV nanoimprint method to decrease the force with which the mold is released from cured resist, that is, demolding force. This is because a large demolding force may cause defects in the pattern or may cause the substrate to rise from the stage, resulting in low alignment precision.
  • a known photo-curable composition for use in photo-nanoimprint contains at least one polymerizable monomer, a polymerization initiator, and a fluorinated surfactant.
  • PTL 1 also discloses the use of a fluorinated surfactant in which a perfluoroalkyl chain is bonded to a hydrocarbon chain or a fluorinated surfactant in which a perfluoroalkyl chain is bonded to an ethoxy chain, a methoxy chain, or siloxane.
  • PTL 2 discloses that the resulting photo-cured film is water-repellent and preferably has a water contact angle in the range of 75 to 98 degrees.
  • a fluorinated material may be added to a composition to impart water repellency to a surface of a photo-cured film and decrease demolding force.
  • the addition of a known fluorinated material alone does not necessarily provide an interface between a mold surface and a photo-cured film surface that contributes to a decreased demolding force, and still results in a large demolding force.
  • the present invention provides a photo-curable composition that requires a small demolding force in a patterning method.
  • the present invention also provides a patterning method that requires a small demolding force.
  • a photo-curable composition contains a polymerizable monomer (A), a polymerization initiator (B), and a fluorine-containing surfactant (C), wherein a photo-cured product of the composition has a water contact angle of 74 degrees or less.
  • a patterning method includes placing the photo-curable composition on a substrate to be processed, bringing the photo-curable composition into contact with a mold, irradiating the photo-curable composition with light, and releasing the photo-curable composition from the mold after the irradiation.
  • the present invention provides a photo-curable composition that requires a small demolding force.
  • the present invention also provides a patterning method that requires a small demolding force.
  • FIGS. 1A to 1F are cross-sectional views illustrating a patterning method.
  • the term “patterning method”, as used herein, includes a UV imprint method.
  • the UV imprint method is preferably defined as a method for forming a pattern having a size in the range of 1 nm to 10 mm, more preferably approximately 10 nm to 100 ⁇ m.
  • a technique of forming a nanoscale (1 to 100 nm) pattern (textured structure) is generally referred to as photo-nanoimprint.
  • the present invention includes photo-nanoimprint.
  • a photo-curable composition according to an embodiment of the present invention contains a polymerizable monomer (A), a polymerization initiator (B), and a fluorine-containing surfactant (C).
  • the photo-curable composition may contain another additive component.
  • the fluorine-containing surfactant (C) may have a polar functional group at one end.
  • the amount of fluorine-containing surfactant (C) is controlled such that a photo-cured product of a photo-curable composition according to an embodiment of the present invention has a water contact angle of 74 degrees or less.
  • a photo-cured film is water-repellent and has a high water contact angle in the range of 75 to 98 degrees.
  • a photo-curable composition requires a small demolding force when its photo-cured product has a water contact angle of 74 degrees or less.
  • a composition according to an embodiment of the present invention requires a small demolding force when the contact angle is 74 degrees or less, it is surmised that the fluorine-containing surfactant (C) segregates on a surface of the photo-cured product, and a terminal functional group of the surfactant imparts hydrophilicity to the photo-cured product.
  • the functional group is attached to a mold surface, a thin film of the fluorine-containing surfactant (C) may be formed at the interface between the mold and the resist and thereby decreases demolding force.
  • the terminal functional group has a high polarity, this probably facilitates the formation of a polar bond with the mold surface and the formation of the thin film.
  • the fluorine-containing surfactant (C) has a perfluoroalkyl chain (C-a) on one end and a polar functional group (C-c) on the other end, and the perfluoroalkyl chain is linked to the polar functional group through a poly(alkylene oxide) chain (C-b1) and/or an alkyl chain (C-b2), it is surmised that the polar functional group (C-c) forms a polar bond with the mold surface, and a thin film of the fluorine-containing surfactant (C) formed at the interface between the mold and the resist can decrease demolding force.
  • perfluoroalkyl chain (C-a) examples include, but are not limited to, fluorine-substituted linear alkyl groups having 1 to 20 carbon atoms, such as a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, a perfluorooctyl group, a perfluorononyl group, and a perfluorodecyl group.
  • the number of carbon atoms may be seven or less.
  • polar functional group (C-c) examples include, but are not limited to, alkylhydroxy groups, a carboxy group, a thiol group, an amino group, a pyridyl group, a silanol group, and a sulfo group.
  • poly(alkylene oxide) chain (C-b1) examples include, but are not limited to, polyethylene oxide) chains having a repeating unit number in the range of 1 to 100 and poly(propylene oxide) chains having a repeating unit number in the range of 1 to 100.
  • alkyl chain (C-b2) examples include, but are not limited to, alkyl groups having 1 to 100 carbon atoms and a linear or ring structure.
  • the (C-a) and the (C-b1), the (C-a) and the (C-b2), the (C-b1) and the (C-c), or the (C-b2) and the (C-c) may be linked through a divalent linking group.
  • the divalent linking group include, but are not limited to, alkylene groups, a phenylene group, a naphthylene group, ester groups, ether groups, thioether groups, a sulfonyl group, a secondary amino group, a tertiary amino group, an amide group, and a urethane group.
  • the fluorine-containing surfactant (C) may be at least one compound having the following general formula (1):
  • n is an integer in the range of 1 to 100.
  • the fluorine-containing surfactant (C) may be used alone or in combination.
  • the fluorine-containing surfactant (C) may constitute 0.001% by weight to 5% by weight, preferably 0.002% by weight to 4% by weight, more preferably 0.005% by weight to 3% by weight, of the amount of polymerizable monomer (A). As described above, the amount of fluorine-containing surfactant (C) is controlled such that a photo-cured product of a photo-curable composition according to an embodiment of the present invention has a water contact angle of 74 degrees or less.
  • the photo-cured product may have a water contact angle of 74 degrees or less and 1 degree or more, preferably 10 degrees or more.
  • the photo-cured product may have a water contact angle of 70 degrees or less, or 71 degrees or more and 74 degrees or less.
  • a photo-cured product may be prepared by applying a photo-curable composition according to an embodiment of the present invention to a substrate by coating, such as spin coating, and irradiating the photo-curable composition with light in an inert atmosphere, such as a nitrogen gas atmosphere, to form a photo-cured film.
  • the water contact angle may be measured with a commercially available contact angle meter, such as a fully-automatic contact angle meter CA-W (manufactured by Kyowa Interface Science Co., Ltd.).
  • the water contact angle of a photo-cured film in the present invention is defined as the angle between a surface of the photo-cured film and a tangent line at the intersection of 1 ⁇ l of pure water on the photo-cured film and the photo-cured film.
  • the water contact angle may be the mean value of a plurality of measurements at different positions on a sample.
  • the polymerizable monomer of a photo-curable composition according to an embodiment of the present invention may be a radical-polymerizable monomer or a cation-polymerizable monomer.
  • the radical-polymerizable monomer may be a compound having at least one acryloyl or methacryloyl group.
  • the cation-polymerizable monomer may be a compound having at least one vinyl ether group, epoxy group, or oxetanyl group.
  • Examples of a monofunctional (meth)acryl compound having one acryloyl or methacryloyl group include, but are not limited to, phenoxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate, 4-phenylphenoxyethyl (meth)acrylate, 3-(2-phenylphenyl)-2-hydroxypropyl (meth)acrylate, EO-modified p-cumylphenol (meth)acrylate, 2-bromophenoxyethyl (meth)acrylate, 2,4-dibromophenoxyethyl (meth)acrylate, 2,4,6-tribromophenoxyethyl (meth)acrylate, EO-modified phenoxy (meth)acrylate, PO-modified
  • the monofunctional (meth)acryl compound may be, but is not limited to, the following product: Aronix M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, or M156 (manufactured by Toagosei Co., Ltd.), MEDOL 10, MIBDOL 10, CHDOL 10, MMDOL 30, MEDOL 30, MIBDOL 30, CHDOL 30, LA, IBXA, 2-MTA, HPA, or Viscoat #150, #155, #158, #190, #192, #193, #220, #2000, #2100, or #2150 (manufactured by Osaka Organic Chemical Industry Ltd.), Light Acrylate BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, PO-A, P-200A, NP-4EA, or NP-8EA, or epoxy ester M-600A (manufactured by Kyoeisha Chemical Co
  • Examples of a polyfunctional (meth)acryl compound having at least two acryloyl or methacryloyl groups include, but are not limited to, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO,PO-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethylene glycol di(meth)acrylate, tetra(ethylene glycol) di(meth)acrylate, polyethylene glycol) di(meth)acrylate, poly(propylene glycol) di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(
  • the polyfunctional (meth)acryl compound may be, but is not limited to, the following product: Yupimer UV SA1002 or SA2007 (manufactured by Mitsubishi Chemical Corp.), Viscoat #195, #230, #215, #260, #335HP, #295, #300, #360, #700, GPT, or 3PA (manufactured by Osaka Organic Chemical Industry Ltd.), Light Acrylate 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP-4PA, TMP-A, PE-3A, PE-4A, or DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.), Kayarad PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, or -120, HX-620, D-310, or D-330 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M208, M210, M215, M220, M240, M
  • radical-polymerizable monomers may be used alone or in combination.
  • (meth)acrylate refers to an acrylate and its corresponding methacrylate.
  • (meth)acryloyl group refers to an acryloyl group and its corresponding methacryloyl group.
  • EO denotes ethylene oxide
  • an EO-modified compound has a block structure of an ethylene oxide group.
  • PO denotes propylene oxide
  • a PO-modified compound has a block structure of a propylene oxide group.
  • Examples of a compound having one vinyl ether group include, but are not limited to, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexylmethyl vinyl ether, 4-methylcyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxy poly(ethylene glycol) vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyeth
  • Examples of a compound having at least two vinyl ether groups include, but are not limited to, divinyl ethers, such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, poly(ethylene glycol) divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ethers, and bisphenol F alkylene oxide divinyl ethers; and polyfunctional vinyl ethers, such as trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide
  • Examples of a compound having one epoxy group include, but are not limited to, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monoxide, 1,2-epoxidedecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, and 3-vinylcyclohexene oxide.
  • Examples of a compound having at least two epoxy groups include, but are not limited to, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolak resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinylepoxycyclo
  • Examples of a compound having one oxetanyl group include, but are not limited to, 3-ethyl-3-hydroxymethyloxetane, 3-(meta)allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, [1-(3-ethyl-3-oxetanylmethoxy)ethyl]phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl)ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl)ether, isobornyl (3-ethyl-3-oxetanylmethyl)ether
  • Examples of a compound having at least two oxetanyl groups include, but are not limited to, polyfunctional oxetanes, such as 3,7-bis(3-oxetanyl)-5-oxa-nonane, 3,3′-(1,3-(2-methylenyl)propanediyl bis(oxymethylene))bis-(3-ethyloxetane), 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl)ether, tri(ethylene glycol) bis(3-
  • EO denotes ethylene oxide
  • PO denotes propylene oxide
  • a PO-modified compound has a block structure of a propylene oxide group.
  • hydrogenated refers to the addition of hydrogen atoms to a C ⁇ C double bond, for example, of a benzene ring.
  • the polymerization initiator (B) When the polymerizable monomer (A) is a radical-polymerizable monomer, the polymerization initiator (B) generates a radical by the action of light (infrared rays, visible light, ultraviolet light, far-ultraviolet light, X-rays, charged particle beams, such as an electron beam, or radioactive rays). When the polymerizable monomer (A) is a cation-polymerizable monomer, the polymerization initiator (B) generates an acid by the action of light.
  • light infrared rays, visible light, ultraviolet light, far-ultraviolet light, X-rays, charged particle beams, such as an electron beam, or radioactive rays.
  • the polymerization initiator (B) When the polymerizable monomer (A) is a cation-polymerizable monomer, the polymerization initiator (B) generates an acid by the action of light.
  • radical generator examples include, but are not limited to,
  • 2,4,5-triarylimidazole dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, and 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazole dimer;
  • 2,4,5-triarylimidazole dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, and 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazole dimer;
  • benzophenone and benzophenone derivatives such as N,N′-tetramethyl-4,4′-diaminobenzophenone (Michler's ketone), N,N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, and 4,4′-diaminobenzophenone;
  • aromatic ketone derivatives such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanon-1-one;
  • quinones such as 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone;
  • benzoin ether derivatives such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether;
  • benzoin and benzoin derivatives such as methylbenzoin, ethylbenzoin, and propylbenzoin;
  • benzyl derivatives such as benzyl dimethyl ketal
  • acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9′-acridinyl)heptane
  • acetophenone and acetophenone derivatives such as 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, and 2,2-dimethoxy-2-phenylacetophenone;
  • thioxanthone and thioxanthone derivatives such as diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone;
  • the photo-induced radical generator may be, but is not limited to, the following product: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, or -1850, or CG24-61, or Darocur 1116 or 1173 (manufactured by Ciba Japan K.K.), Lucirin TPO, LR8893, or LR8970 (manufactured by BASF), or Ebecryl P36 (manufactured by UCB).
  • Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, or -1850, or CG24-61 or Darocur 1116 or 1173 (manufactured by Ciba Japan K.K.), Lucirin TPO, LR8893, or LR8970 (manufactured by BASF), or Ebecryl P36 (manufactured by UC
  • Examples of a compound used as a polymerization initiator that produces an acid by the action of light include, but are not limited to, onium salt compounds, sulfone compounds, sulfonate ester compounds, sulfonimide compounds, and diazomethane compounds.
  • onium salt compounds include, but are not limited to, iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, ammonium salts, and pyridinium salts.
  • Specific examples of the onium salt compounds include, but are not limited to, bis(4-t-butylphenyl)iodonium perfluoro-n-butane sulfonate, bis(4-t-butylphenyl)iodonium trifluoromethane sulfonate, bis(4-t-butylphenyl)iodonium 2-trifluoromethylbenzene sulfonate, bis(4-t-butylphenyl)iodonium pyrene sulfonate, bis(4-t-butylphenyl)iodonium n-dodecylbenzene sulfonate, bis(4-t-butylphenyl)iodonium
  • sulfone compounds include, but are not limited to, ⁇ -ketosulfones, ⁇ -sulfonylsulfones, and ⁇ -diazo compounds thereof.
  • Specific examples of the sulfone compounds include, but are not limited to, phenacyl phenyl sulfone, mesityl phenacyl sulfone, bis(phenylsulfonyl)methane, and 4-trisphenacyl sulfone.
  • sulfonate ester compounds include, but are not limited to, alkyl sulfonate esters, haloalkyl sulfonate esters, aryl sulfonate esters, and iminosulfonates.
  • Specific examples of the sulfonate ester compounds include, but are not limited to, ⁇ -methylolbenzoin perfluoro-n-butane sulfonate, ⁇ -methylolbenzoin trifluoromethane sulfonate, and a-methylolbenzoin 2-trifluoromethylbenzene sulfonate.
  • sulfonimide compounds include, but are not limited to, N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylmide, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylmide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]heptan-5,6-oxy-2,3-dicarboxylmide, N-(trifluoromethylsulfonyloxy)naphthylimide, N-(10-camphorsulfonyloxy)
  • diazomethane compounds include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, methylsulfonyl p-toluenesulfonyldiazomethane, (cyclohexylsulfonyl)(1,1-dimethylethylsulfonyl)diazomethane, and bis(1,1-dimethylethylsulfonyl)diazomethane.
  • These acid generators may be used alone or in combination.
  • the polymerization initiator (B) component constitutes 0.01% by weight or more and 10% by weight or less, preferably 0.1% by weight or more and 7% by weight or less, of the amount of polymerizable monomer (A). Less than 0.01% by weight may result in a decreased curing rate and low reaction efficiency. On the other hand, more than 10% by weight may result in poor mechanical characteristics of a cured product of the photo-curable composition.
  • a photo-curable composition according to an embodiment of the present invention may contain other additive components, such as a sensitizer, an antioxidant, a solvent, and/or a polymer component, for each purpose without losing the advantages of the present invention.
  • the sensitizer can promote polymerization reaction and improve reaction conversion.
  • the sensitizer may be a hydrogen donor or a sensitizing dye.
  • the hydrogen donor can react with an initiator radical generated from the polymerization initiator (B) or a propagating radical to form a more reactive radical.
  • the hydrogen donor can be added when the polymerization initiator (B) is a photo-induced radical generator.
  • hydrogen donor examples include, but are not limited to, amine compounds, such as N-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzylisothiuronium-p-toluene sulfinate, triethylamine, dimethylaminoethyl methacrylate, triethylenetetramine, 4,4′-bis(dialkylamino)benzophenone, ethyl N,N-dimethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, pentyl-4-dimethylaminobenzoate, triethanolamine, and N-phenylglycine; and mercapto compounds, such as 2-mercapto-N-phenylbenzoimidazole and mercaptopropionate.
  • amine compounds such as N-butylamine, di-n-butylamine, tri-n-but
  • the sensitizing dye is excited by absorbing light having a particular wavelength and acts on the polymerization initiator (B).
  • act on refers to energy transfer or electron transfer from the excited sensitizing dye to the polymerization initiator (B).
  • the sensitizing dye include, but are not limited to, anthracene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, phenothiazine derivatives, camphorquinone derivatives, acridine dyes, thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, and pyrylium salt dyes.
  • the sensitizer may be used alone or in combination.
  • the sensitizer in a photo-curable composition according to an embodiment of the present invention preferably constitutes 0% to 20% by weight, more preferably 0.1% by weight to 5.0% by weight, still more preferably 0.2% by weight to 2.0% by weight, of the amount of polymerizable monomer (A).
  • the sensitizer content is 0.1% by weight or more, the effects of the sensitizer can be more effectively produced.
  • the sensitizer content is 5.0% by weight or less, a photo-cured product can have a sufficiently high molecular weight, and deterioration in solubility or storage stability can be prevented.
  • a photo-curable composition may be mixed and dissolved at a temperature in the range of 0° C. to 100° C.
  • a photo-curable composition according to an embodiment of the present invention preferably has a viscosity in the range of 1 to 100 cP, more preferably 5 to 50 cP, still more preferably 6 to 20 cP, at 23° C. in the absence of solvent.
  • a viscosity of more than 100 cP may result in a long filling time of the composition in a micropatterned depressed portion on a mold or patterning defects because of insufficient filling in a stamping step described below.
  • a viscosity of less than 1 cP may result in uneven coating in a coating step described below or the outflow of the composition from a mold in the stamping step described below.
  • a photo-curable composition according to an embodiment of the present invention preferably has a surface tension in the range of 5 to 70 mN/m, more preferably 7 to 35 mN/m, still more preferably 10 to 32 mN/m, at 23° C. in the absence of solvent.
  • a surface tension of less than 5 mN/m results in a long filling time of the composition in recessed and raised portions on a mold in a contact step described below.
  • a surface tension of more than 70 mN/m results in poor surface smoothness.
  • a photo-curable composition may be passed through a filter having a pore size in the range of 0.001 to 5.0 ⁇ m. The filtration may be performed in multiple steps or multiple times. A filtered liquid may be filtered again.
  • the material of the filter may be, but is not limited to, polyethylene resin, polypropylene resin, fluoropolymer, or nylon resin.
  • the concentration of metal impurities in a photo-curable composition according to an embodiment of the present invention is preferably 10 ppm or less, more preferably 100 ppb or less.
  • a patterning method involves a placing step of placing a photo-curable composition on a substrate to be processed ( FIG. 1A ), a mold contact step of bringing the photo-curable composition into contact with a mold ( FIG. 1B ), a photoirradiation step of irradiating the photo-curable composition with light while the photo-curable composition is in contact with the mold ( FIG. 1C ), and a demolding step of releasing the photo-curable composition from the mold ( FIG. 1D ).
  • the photo-curable composition may be irradiated with light through the mold.
  • the method may further involve an exposure step of etching part of a film of the photo-curable composition remaining in depressed portions after the demolding step to expose a surface of the substrate in the depressed portions ( FIG. 1E ).
  • the placing step of placing a photo-curable composition on a substrate to be processed is a coating step.
  • a photo-curable composition according to an embodiment of the present invention is applied to a substrate to be processed.
  • the substrate to be processed may be a substrate, such as a silicon wafer.
  • the substrate to be processed may also be a substrate for semiconductor devices made of aluminum, a titanium-tungsten alloy, an aluminum-silicon alloy, an aluminum-copper-silicon alloy, silicon oxide, or silicon nitride.
  • the substrate to be processed may be a substrate subjected to surface treatment, such as silane coupling treatment, silazane treatment, or the formation of an organic film, to improve adhesion to the photo-curable composition.
  • the photo-curable composition may be applied by an ink jet method, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spin coating method, or a slit scanning method.
  • the film thickness of the photo-curable composition depends on the application and is in the range of 0.01 to 100.0 ⁇ m, for example.
  • recessed and raised portions (micropattern) on a surface of the mold are filled with the photo-curable composition.
  • the mold is made of an optically transparent material, for example, glass, quartz, an optically transparent resin, such as PMMA or polycarbonate resin, a transparent metallized film, a soft film, such as a polydimethylsiloxane film, a photo-cured film, or a metal film.
  • an optically transparent material for example, glass, quartz, an optically transparent resin, such as PMMA or polycarbonate resin, a transparent metallized film, a soft film, such as a polydimethylsiloxane film, a photo-cured film, or a metal film.
  • a surface of the mold in contact with the photo-curable composition may be hydrophilic so as to facilitate the formation of a polar bond with the fluorine-containing surfactant (C).
  • a mold for use in a patterning method according to an embodiment of the present invention may be subjected to surface treatment so as to improve the releasability of a photo-curable composition from the mold.
  • the surface treatment may involve the use of a silane coupling agent, such as a silicone or fluorinated coupling agent, for example, a commercially available coating-type mold-release agent, such as Optool DSX manufactured by Daikin Industries, Ltd.
  • the contact pressure is generally, but not limited to, in the range of 0.1 Pa to 100 MPa, preferably 0.1 Pa to 50 MPa, more preferably 0.1 Pa to 30 MPa, still more preferably 0.1 Pa to 20 MPa.
  • the contact time is generally, but not limited to, in the range of 1 to 600 seconds, preferably 1 to 300 seconds, more preferably 1 to 180 seconds, still more preferably 1 to 120 seconds.
  • a patterning method according to an embodiment of the present invention may be performed in the atmosphere, under reduced pressure, or in an inert gas atmosphere.
  • inert gas include, but are not limited to, nitrogen, carbon dioxide, helium, argon, various chlorofluorocarbons, and mixtures thereof.
  • the pressure may be in the range of 0.0001 to 10 atm.
  • Use of reduced pressure or an inert gas atmosphere can eliminate the effects of oxygen or water on the photo-curing reaction.
  • the photo-curable composition is irradiated with light while the photo-curable composition is in contact with the mold.
  • the photo-curable composition in recessed and raised portions on the mold surface is cured.
  • the light is not particularly limited, depends on the sensitive wavelength of a photo-curable composition according to an embodiment of the present invention, and may be ultraviolet light having a wavelength in the range of approximately 150 to 400 nm, X-rays, or an electron beam
  • Various photosensitive compounds sensitive to ultraviolet light are easily available as the polymerization initiator (B).
  • Examples of ultraviolet light sources include, but are not limited to, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, low-pressure mercury lamps, deep-UV lamps, carbon arc lamps, chemical lamps, metal halide lamps, xenon lamps, KrF excimer lasers, ArF excimer lasers, and F 2 excimer lasers. These light sources may be used alone or in combination.
  • the photo-curable composition may be entirely or partly irradiated with light.
  • the photo-curable composition may further be cured with heat.
  • the heating atmosphere and the heating temperature of heat curing are not particularly limited and may be an inert atmosphere or under reduced pressure and in the range of 40° C. to 200° C. Heating may be performed with a hot plate, an oven, or a furnace.
  • the photo-curable composition is removed from the mold.
  • the reverse pattern of the recessed and raised portions on the mold surface is transferred to a cured product of the photo-curable composition.
  • the demolding method is not particularly limited, and various conditions are also not particularly limited.
  • a substrate to be processed may be fixed while a mold may be moved away from the substrate to be processed, or a mold may be fixed while a substrate to be processed may be moved away from the mold, or a substrate to be processed and a mold may be moved in the opposite directions.
  • a patterning method may involve the use of a coating-type mold-release agent. More specifically, a coating-type mold-release agent layer may be formed on a patterned surface of a mold before the stamping step.
  • coating-type mold-release agent examples include, but are not limited to, silicon mold-release agents, fluorinated mold-release agents, polyethylene mold-release agents, polypropylene mold-release agents, paraffinic mold-release agents, montan mold-release agents, and carnauba mold-release agents.
  • the mold-release agent may be used alone or in combination.
  • part of a film of the photo-curable composition remaining in depressed portions is etched to expose a surface of the substrate in the depressed portions.
  • the etching method is not particularly limited and may be a conventional method, such as dry etching.
  • a known dry etching apparatus may be used in dry etching.
  • the source gas for dry etching depends on the elementary composition of a film to be etched and may be an oxygen-containing gas, such as O 2 , CO, or CO 2 , an inert gas, such as He, N 2 , or Ar, a chlorine gas, such as Cl 2 or BCl 3 , H 2 , or NH 3 . These source gases may be used alone or in combination.
  • a pattern formed in the exposure step can be used as a film for an interlayer insulating film of a semiconductor element, such as LSI, system LSI, DRAM, SDRAM, RDRAM, or D-RDRAM, or a resist film in the manufacture of a semiconductor element.
  • a semiconductor element such as LSI, system LSI, DRAM, SDRAM, RDRAM, or D-RDRAM, or a resist film in the manufacture of a semiconductor element.
  • the exposed portions in the exposure step may be subjected to etching or ion implantation to form a circuit structure based on the photo-curable composition pattern on the substrate to be processed.
  • a circuit board for a semiconductor element can be manufactured through these steps.
  • the photo-curable composition pattern may be removed from the substrate or may be left as a member for constituting the element.
  • the substrate may be used as an optical element having a textured pattern on its surface. More specifically, the substrate may be provided as an article that includes a substrate and a cured product of the photo-curable composition on the substrate.
  • a 300-mL reactor was charged with hexa(ethylene glycol) (PEG6) (26.5 g, 93.9 mmol, 1.0 eq.), carbon tetrachloride (CCl 4 ) (36.1 g, 235 mmol, 2.5 eq.), and tetrahydrofuran (THF) (106 mL) in a nitrogen atmosphere and was cooled to ⁇ 30° C.
  • PEG6 hexa(ethylene glycol)
  • CCl 4 carbon tetrachloride
  • THF tetrahydrofuran
  • the suspension was concentrated, and city water (300 mL) and ethyl acetate (300 mL) were added to the resulting residue to separate the residue into two layers. An aqueous layer was extracted with ethyl acetate (200 mL ⁇ 2). An organic layer was washed with city water (400 mL) and saturated saline (400 mL) and was dried over anhydrous magnesium sulfate. The solution was concentrated to yield a brown liquid (59.1 g).
  • C-1 fluorine-containing surfactant
  • hexa(ethylene glycol) mono-1H,1H-perfluoroheptyl ether F(CF 2 ) 6 CH 2 (OCH 2 CH 2 ) 6 OH, 19.2 g, 31.2 mmol, yield 33%)
  • a mixed solution was prepared by using 100 parts by weight of 1,6-hexanediol diacrylate (manufactured by Osaka Organic Chemical Industry Ltd.) as the (A) component, 3 parts by weight of Irgacure 369 (manufactured by Ciba Japan K.K.) as the (B) component, and 0.125 parts by weight of the fluorine-containing surfactant (C-1) as the (C) component.
  • the mixed solution was passed through a 0.2 ⁇ m tetrafluoroethylene filter to yield a photo-curable composition (a-1) according to Example 1.
  • the surface tension of the photo-curable composition (a-1) was 31.5 mN/m as measured with an automatic surface tensiometer CBVP-A3 (manufactured by Kyowa Interface Science Co., Ltd.).
  • the viscosity of the photo-curable composition (a-1) was 6.4 cP as measured with a cone-and-plate viscometer RE-85L (manufactured by Toki Sangyo Co., Ltd.).
  • a film of the photo-curable composition (a-1) having a thickness of approximately 1 ⁇ m was formed on a silicon wafer by a spin coating method.
  • a photo-cured film was prepared by irradiating the film of the photo-curable composition (a-1) with light from a UV light source EX250 (manufactured by Hoya Candeo Optronics Corp.) equipped with a 250-W ultrahigh-pressure mercury lamp in a nitrogen atmosphere through an interference filter VPF-50C-10-25-36500 (manufactured by Sigmakoki Co., Ltd.).
  • the illuminance on the film was 25 mW/cm at a wavelength of 365 nm.
  • the photoirradiation time was 100 seconds.
  • the contact angle of 1 ⁇ l of pure water on the photo-cured film of the photo-curable composition (a-1) was 69 degrees as measured with a fully-automatic contact angle meter CA-W (manufactured by Kyowa Interface Science Co., Ltd.).
  • a 40 ⁇ 40 mm quartz mold having no surface treatment and no pattern was stamped onto the silicon wafer.
  • An UV light source EXECURE 3000 (manufactured by Hoya Candeo Optronics Corp.) equipped with a 200-W mercury xenon lamp was used as an irradiation light source.
  • An interference filter VPF-50C-10-25-36500 (manufactured by Sigmakoki Co., Ltd.) was placed between the light source and the quartz mold. The illuminance directly under the quartz mold was 1 mW/cm 2 at a wavelength of 365 nm.
  • the photoirradiation step was performed for 60 seconds.
  • the quart mold was raised at 0.5 mm/s.
  • the demolding force was measured with a compact tension/compression load cell LUR-A-200NSA1 (manufactured by Kyowa Electronic Instruments Co., Ltd.). The average demolding force of four measurements under the same conditions was 149 N.
  • a photo-curable composition (a-2) was prepared in the same manner as in Example 1 except that 0.5 parts by weight of the fluorine-containing surfactant (C-1) was used as the (C) component.
  • the surface tension and the viscosity of the photo-curable composition (a-2) were 25.5 mN/m and 6.4 cP, respectively, as measured in the same manner as in Example 1.
  • a photo-cured film of the photo-curable composition (a-2) prepared in the same manner as in Example 1 had a water contact angle of 64 degrees.
  • the average demolding force of the photo-curable composition (a-2) was 128 N as measured in the same manner as in Example 1.
  • a photo-curable composition (a-3) was prepared in the same manner as in Example 1 except that 2.0 parts by weight of the fluorine-containing surfactant (C-1) was used as the (C) component.
  • the surface tension and the viscosity of the photo-curable composition (a-3) were 21.0 mN/m and 6.5 cP, respectively, as measured in the same manner as in Example 1.
  • a photo-cured film of the photo-curable composition (a-3) prepared in the same manner as in Example 1 had a water contact angle of 29 degrees.
  • the average demolding force of the photo-curable composition (a-3) was 88 N as measured in the same manner as in Example 1.
  • a mixed solution was prepared from the (A) component: 61.6 parts by weight of isobornyl acrylate (IB-XA manufactured by Kyoeisha Chemical Co., Ltd.), 10 parts by weight of (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate (MEDOL-10 manufactured by Osaka Organic Chemical Industry Ltd.), and 22.4 parts by weight of hexanediol diacrylate (Viscoat #230 manufactured by Osaka Organic Chemical Industry Ltd.), the (B) component: 3 parts by weight of Irgacure 369 (manufactured by Ciba Japan K.K.), and the (C) component: 2.2 parts by weight of pentadeca(ethylene glycol) mono-1H,1H,2H,2H-perfluorooctyl ether (F(CF 2 ) 6 CH 2 CH 2 (OCH 2 CH 2 ) 15 OH, manufactured by DIC).
  • the mixed solution was passed through a 0.2
  • the surface tension and the viscosity of the photo-curable composition (a-4) were 24.9 mN/m and 7.1 cP, respectively, as measured in the same manner as in Example 1.
  • a photo-cured film of the photo-curable composition (a-4) prepared in the same manner as in Example 1 had a water contact angle of 64 degrees.
  • the average demolding force of the photo-curable composition (a-4) was 99 N as measured in the same manner as in Example 1.
  • a photo-curable composition (a-5) was prepared in the same manner as in Example 4 except that the (C) component was 1.3 parts by weight of eicosa(ethylene glycol) mono-1H,1H,2H,2H-perfluorooctyl ether (F(CF 2 ) 6 CH 2 CH 2 (OCH 2 CH 2 ) 20 OH, manufactured by DIC).
  • the surface tension and the viscosity of the photo-curable composition (a-5) were 27.2 mN/m and 7.0 cP, respectively, as measured in the same manner as in Example 1.
  • a photo-cured film of the photo-curable composition (a-5) prepared in the same manner as in Example 1 had a water contact angle of 72 degrees.
  • the average demolding force of the photo-curable composition (a-5) was 118 N as measured in the same manner as in Example 1.
  • a mixed solution was prepared from the (A) component: 61.6 parts by weight of isobornyl acrylate (IB-XA manufactured by Kyoeisha Chemical Co., Ltd.), 10 parts by weight of (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate (MEDOL-10 manufactured by Osaka Organic Chemical Industry Ltd.), and 22.4 parts by weight of hexanediol diacrylate (Viscoat #230 manufactured by Osaka Organic Chemical Industry Ltd.), the (B) component: 3 parts by weight of 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651 manufactured by BASF), and the (C) component: 1.1 parts by weight of pentadeca(ethylene glycol) mono-1H,1H,2H,2H-perfluorooctyl ether (F(CF 2 ) 6 CH 2 CH 2 (OCH 2 CH 2 ) 15 OH, manufactured by DIC).
  • IB-XA iso
  • the mixed solution was passed through a 0.2 ⁇ m tetrafluoroethylene filter to yield a photo-curable composition (a-6) according to Example 6.
  • the surface tension and the viscosity of the photo-curable composition (a-6) were 26.1 mN/m and 6.6 cP, respectively, as measured in the same manner as in Example 1.
  • a photo-cured film of the photo-curable composition (a-6) prepared in the same manner as in Example 1 had a water contact angle of 58 degrees.
  • the light source was an ultrahigh-pressure mercury lamp.
  • An interference filter was placed between the light source and a quartz mold. Light having a wavelength of 313 ⁇ 5 nm can selectively pass through the interference filter.
  • the illuminance directly under the quartz mold was 38.5 mW/cm 2 at a wavelength of 313 nm.
  • a 26 ⁇ 33 mm quartz mold having no surface treatment and no pattern was brought into contact with the silicon wafer.
  • a photo-curable composition (a-7) was prepared in the same manner as in Example 6 except that the (C) component was 2.2 parts by weight of pentadeca(ethylene glycol) mono-1H,1H,2H,2H-perfluorooctyl ether (F(CF 2 ) 6 CH 2 CH 2 (OCH 2 CH 2 ) 15 OH, manufactured by DIC).
  • the (C) component was 2.2 parts by weight of pentadeca(ethylene glycol) mono-1H,1H,2H,2H-perfluorooctyl ether (F(CF 2 ) 6 CH 2 CH 2 (OCH 2 CH 2 ) 15 OH, manufactured by DIC).
  • the surface tension and the viscosity of the photo-curable composition (a-7) were 23.9 mN/m and 6.7 cP, respectively, as measured in the same manner as in Example 1.
  • a photo-cured film of the photo-curable composition (a-7) prepared in the same manner as in Example 1 had a water contact angle of 9 degrees.
  • the average demolding force of the photo-curable composition (a-7) was 49.1 N as measured in the same manner as in Example 6. This demolding force was lower than that in Comparative Example 3 described below.
  • a photo-curable composition (a-8) was prepared in the same manner as in Example 6 except that the (B) component was 3 parts by weight of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (Irgacure 907 manufactured by BASF).
  • the surface tension and the viscosity of the photo-curable composition (a-8) were 26.5 mN/m and 6.7 cP, respectively, as measured in the same manner as in Example 1.
  • a photo-cured film of the photo-curable composition (a-8) prepared in the same manner as in Example 1 had a water contact angle of 42 degrees.
  • the average demolding force of the photo-curable composition (a-8) was 55.3 N as measured in the same manner as in Example 6. This demolding force was lower than that in Comparative Example 3 described below.
  • a photo-curable composition (b-1) was prepared in the same manner as in Example 1 except that no (C) component was added.
  • the surface tension and the viscosity of the photo-curable composition (b-1) were 35.9 mN/m and 6.3 cP, respectively, as measured in the same manner as in Example 1.
  • a photo-cured film of the photo-curable composition (b-1) prepared in the same manner as in Example 1 had a water contact angle of 79 degrees.
  • the average demolding force of the photo-curable composition (b-1) was 158 N as measured in the same manner as in Example 1, which was larger than Examples 1 to 3.
  • a photo-curable composition (b-2) was prepared in the same manner as in Example 4 except that no (C) component was added.
  • the surface tension and the viscosity of the photo-curable composition (b-2) were 31.5 mN/m and 6.8 cP, respectively, as measured in the same manner as in Example 1.
  • a photo-cured film of the photo-curable composition (b-2) prepared in the same manner as in Example 1 had a water contact angle of 81 degrees.
  • the average demolding force of the photo-curable composition (b-2) was 143 N as measured in the same manner as in Example 1, which was larger than Examples 4 and 5.
  • a photo-curable composition (b-3) was prepared in the same manner as in Example 6 except that no (C) component was added.
  • the surface tension and the viscosity of the photo-curable composition (b-3) were 28.1 mN/m and 6.4 cP, respectively, as measured in the same manner as in Example 1.
  • a photo-cured film of the photo-curable composition (b-3) prepared in the same manner as in Example 1 had a water contact angle of 94 degrees.
  • the average demolding force of the photo-curable composition (b-3) was 56.5 N as measured in the same manner as in Example 6, which was larger than Examples 6 to 8.

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US20150210790A1 (en) * 2012-09-24 2015-07-30 Canon Kabushiki Kaisha Photocurable composition and method of manufacturing film using the composition
US10293543B2 (en) 2013-06-26 2019-05-21 Canon Kabushiki Kaisha Method of producing a patterned film
US10338467B2 (en) 2013-09-18 2019-07-02 Canon Kabushiki Kaisha Method of producing film
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US10386717B2 (en) 2013-06-26 2019-08-20 Canon Kabushiki Kaisha Imprint method and apparatus
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Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI471693B (zh) * 2011-11-10 2015-02-01 Canon Kk 光可固化組成物，及使用彼之圖案化方法
JP5932501B2 (ja) * 2012-06-06 2016-06-08 キヤノン株式会社 硬化性組成物、及びこれを用いるパターン形成方法
KR101811116B1 (ko) 2013-05-09 2017-12-20 캐논 가부시끼가이샤 화합물, 광경화성 조성물, 및 광경화성 조성물을 사용하여 패턴 형상을 갖는 막, 광학 부품, 회로 기판, 전자 부품을 제조하는 방법, 및 경화물
JP6221537B2 (ja) * 2013-09-12 2017-11-01 大日本印刷株式会社 光硬化性樹脂組成物およびそれを用いたパターン形成方法
KR101932418B1 (ko) * 2013-11-22 2018-12-26 소켄 케미칼 앤드 엔지니어링 캄파니, 리미티드 임프린트용 광경화성 수지 조성물, 반사 방지 필름
JP6584074B2 (ja) * 2014-02-26 2019-10-02 キヤノン株式会社 光硬化性組成物、硬化物、これを用いた、パターン形状を有する膜の製造方法、光学部品の製造方法、回路基板の製造方法、電子部品の製造方法
JP6114221B2 (ja) 2014-03-26 2017-04-12 富士フイルム株式会社 光インプリント用硬化性組成物、パターン形成方法およびパターン
JP6643802B2 (ja) 2014-05-09 2020-02-12 キヤノン株式会社 硬化性組成物、その硬化物、硬化物の製造方法、光学部品の製造方法、回路基板の製造方法、および電子部品の製造方法
WO2016048116A1 (ko) * 2014-09-26 2016-03-31 주식회사 엘지화학 자외선 경화형 잉크 조성물, 이를 이용한 디스플레이 기판의 베젤 패턴의 제조방법 및 이에 의하여 제조된 베젤 패턴
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US10414925B2 (en) 2014-09-26 2019-09-17 Lg Chem, Ltd. UV-curable ink composition, method for producing bezel pattern of display substrate using same, and bezel pattern produced thereby
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5607913A (en) * 1993-07-22 1997-03-04 The Procter & Gamble Company Acidic liquid detergent compositions for bathrooms
US20070272825A1 (en) * 2004-01-23 2007-11-29 Molecular Imprints, Inc. Composition to Reduce Adhesion Between a Conformable Region and a Mold
US20080093582A1 (en) * 2004-05-20 2008-04-24 Daikin Industries, Ltd. Branched Surfactant Having Fluoroalkyl Group And Hydrocarbon Group
US20080145525A1 (en) * 2006-12-13 2008-06-19 Xing-Cai Guo Release layer and resist material for master tool and stamper tool
JP2010206189A (ja) * 2009-02-05 2010-09-16 Agc Seimi Chemical Co Ltd 光硬化性組成物および表面に微細パターンを有する成形体の製造方法

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0425513A (ja) * 1990-05-21 1992-01-29 Mitsubishi Materials Corp 親水性光硬化性組成物
JPH093358A (ja) * 1995-06-19 1997-01-07 Mitsubishi Rayon Co Ltd 被覆材組成物およびそれの硬化被膜を表面に有する合成樹脂成形品ならびにその製造方法
JP3937663B2 (ja) * 1999-10-07 2007-06-27 大日本インキ化学工業株式会社 微小立体成形用活性エネルギー線硬化性組成物
JP4401049B2 (ja) * 2000-12-11 2010-01-20 旭硝子株式会社 硬化性組成物、硬化被膜および被覆基材
US20040009426A1 (en) * 2002-06-05 2004-01-15 Fuji Photo Film Co., Ltd. Infrared photosensitive composition and image recording material for infrared exposure
TWI257506B (en) 2003-11-18 2006-07-01 Ind Tech Res Inst Photosensitive material for non-substrate liquid crystal display
JP2006110997A (ja) * 2004-09-16 2006-04-27 Asahi Glass Co Ltd 転写体の製造方法、光硬化性組成物、および微細構造体の製造方法
WO2006114958A1 (ja) 2005-04-21 2006-11-02 Asahi Glass Company, Limited 光硬化性組成物、微細パターン形成体およびその製造方法
US7695895B2 (en) 2005-07-20 2010-04-13 Toppan Printing Co., Ltd. Alkali-developable photosensitive color composition
JP4770354B2 (ja) * 2005-09-20 2011-09-14 日立化成工業株式会社 光硬化性樹脂組成物及びこれを用いたパターン形成方法
KR101457254B1 (ko) * 2007-09-28 2014-10-31 아사히 가라스 가부시키가이샤 광경화성 조성물, 미세 패턴 형성체의 제조 방법 및 광학 소자
JP2010017936A (ja) * 2008-07-10 2010-01-28 Fujifilm Corp ナノインプリント用硬化性組成物および硬化物
US8361546B2 (en) * 2008-10-30 2013-01-29 Molecular Imprints, Inc. Facilitating adhesion between substrate and patterned layer
CN102239197A (zh) 2008-12-05 2011-11-09 旭硝子株式会社 光固化性组合物及表面具有微细图案的成形体的制造方法
JP5481861B2 (ja) * 2009-01-09 2014-04-23 日立化成株式会社 光硬化性樹脂組成物、これを用いたパターン形成方法及び微細構造体
JP5491931B2 (ja) * 2010-03-30 2014-05-14 富士フイルム株式会社 ナノインプリント方法およびモールド製造方法
WO2012017530A1 (ja) 2010-08-04 2012-02-09 旭硝子株式会社 光硬化性組成物および表面に微細パターンを有する成形体の製造方法
TWI471693B (zh) * 2011-11-10 2015-02-01 Canon Kk 光可固化組成物，及使用彼之圖案化方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5607913A (en) * 1993-07-22 1997-03-04 The Procter & Gamble Company Acidic liquid detergent compositions for bathrooms
US20070272825A1 (en) * 2004-01-23 2007-11-29 Molecular Imprints, Inc. Composition to Reduce Adhesion Between a Conformable Region and a Mold
US20080093582A1 (en) * 2004-05-20 2008-04-24 Daikin Industries, Ltd. Branched Surfactant Having Fluoroalkyl Group And Hydrocarbon Group
US20080145525A1 (en) * 2006-12-13 2008-06-19 Xing-Cai Guo Release layer and resist material for master tool and stamper tool
JP2010206189A (ja) * 2009-02-05 2010-09-16 Agc Seimi Chemical Co Ltd 光硬化性組成物および表面に微細パターンを有する成形体の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Machine translation of Fujie et al., JP2010206189 *

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US20150004790A1 (en) * 2012-02-09 2015-01-01 Canon Kabushiki Kaisha Photocured product and method for producing the same
US9704710B2 (en) * 2012-02-09 2017-07-11 Canon Kabushiki Kaisha Photocured product and method for producing the same
US10535519B2 (en) 2012-02-09 2020-01-14 Canon Kabushiki Kaisha Photocurable composition, method for forming a pattern, and method for producing a photocured product
US20150210790A1 (en) * 2012-09-24 2015-07-30 Canon Kabushiki Kaisha Photocurable composition and method of manufacturing film using the composition
US9541826B2 (en) * 2012-09-24 2017-01-10 Canon Kabushiki Kaisha Photocurable composition and method of manufacturing film using the composition
US10293543B2 (en) 2013-06-26 2019-05-21 Canon Kabushiki Kaisha Method of producing a patterned film
US10386717B2 (en) 2013-06-26 2019-08-20 Canon Kabushiki Kaisha Imprint method and apparatus
US10456974B2 (en) * 2013-06-26 2019-10-29 Canon Kabushiki Kaisha Photocurable composition, methods for producing film, optical component, circuit board, and electronic component by using the same, and cured product
US10338467B2 (en) 2013-09-18 2019-07-02 Canon Kabushiki Kaisha Method of producing film
US10935884B2 (en) 2017-03-08 2021-03-02 Canon Kabushiki Kaisha Pattern forming method and methods for manufacturing processed substrate, optical component and quartz mold replica as well as coating material for imprint pretreatment and set thereof with imprint resist
DE202018102407U1 (de) 2018-04-30 2019-07-31 Tridonic Jennersdorf Gmbh Flexibles optisches Bauelement mit strukturierter Oberfläche

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