WO2011125800A1 - Composition durcissable pour nano-impression, élément semi-conducteur, et procédé de nano-impression - Google Patents

Composition durcissable pour nano-impression, élément semi-conducteur, et procédé de nano-impression Download PDF

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WO2011125800A1
WO2011125800A1 PCT/JP2011/058139 JP2011058139W WO2011125800A1 WO 2011125800 A1 WO2011125800 A1 WO 2011125800A1 JP 2011058139 W JP2011058139 W JP 2011058139W WO 2011125800 A1 WO2011125800 A1 WO 2011125800A1
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group
curable composition
meth
fluorine atom
acrylate
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PCT/JP2011/058139
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Japanese (ja)
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匡史 岡本
幸生 西村
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Jsr株式会社
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    • 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
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C08L33/16—Homopolymers or copolymers of esters containing halogen atoms

Definitions

  • the present invention relates to a curable composition for nanoimprint, a semiconductor element obtained using the composition, and a nanoimprint method using the composition.
  • a finer processing technique In order to improve the integration degree and recording density of circuits such as semiconductor elements, a finer processing technique is required.
  • a photolithography technique using an exposure process can perform a fine processing of a large area at a time, but does not have a resolution below the wavelength of light. Accordingly, in recent years, photolithography technology using short-wavelength light of 193 nm (ArF), 157 nm (F 2 ), and 13.5 nm (EUV) has been developed. However, when the wavelength of light is shortened, the number of substances that can transmit light of the wavelength is limited.
  • a curable composition is applied on a substrate with a stamper in which a predetermined fine concavo-convex pattern is produced in advance by electron beam lithography or the like.
  • a nanoimprint method that presses against the shape-transfer layer formed by the above-described method and transfers the unevenness of the stamper to the shape-transfer layer (see Patent Documents 1 to 3 and Non-Patent Documents 1 and 2).
  • the present invention has been made based on the above circumstances, and an object thereof is to provide a curable composition for nanoimprinting and a nanoimprinting method which are excellent in releasability.
  • the invention made to solve the above problems is [A] polymerizable compound, [B] A curable composition for nanoimprints containing a fluorine atom-containing polymer and [C] a radical generator.
  • the curable composition for nanoimprinting of the present invention contains a [B] fluorine atom-containing polymer in addition to the [A] polymerizable compound and the [C] radical generator, it is excellent in releasability.
  • the nanoimprint curable composition contains a fluorine atom-containing [B] fluorine atom-containing polymer, thereby reducing the interaction between the shaped transfer layer formed from the nanoimprint curable composition and the stamper. This is thought to be possible.
  • the content of the fluorine atom-containing polymer is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymerizable compound [A].
  • the fluorine atom-containing polymer is effectively surface As a result, the mold releasability of the curable composition for nanoimprinting is improved.
  • the polystyrene-equivalent weight average molecular weight of the fluorine atom-containing polymer by gel permeation chromatography (GPC) is preferably 1,000 or more and 30,000 or less.
  • GPC gel permeation chromatography
  • the fluorine atom-containing polymer has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (B-1) and a structural unit represented by the following formula (B-2): It is preferable that the polymer which has is included.
  • R 1 and R 1 ′ are each independently a hydrogen atom, a methyl group or a trifluoromethyl group.
  • R 2 is a single bond or carbon.
  • R 3 is a hydrogen atom, a hydrocarbon group having a carbon number of 1 to 20, a hydroxyl group, a carboxyl group, or a cyano group, and m is an integer of 0 to 4.
  • the plurality of R 3 and R f2 may be the same or different.
  • R f1 of the structural unit represented by the above formula (B-1) and R f2 of the structural unit represented by the above formula (B-2) are preferably groups represented by the following formula (b) .
  • X is a single bond, —O—, —CO—, —COO—, —OCO— or —NH—, wherein R 4 is a single bond or a hydrocarbon having 1 to 20 carbon atoms.
  • P is an integer of 0 to 5.
  • R F is a (q + 1) -valent hydrocarbon group having 1 to 20 carbon atoms in which part or all of the hydrogen atoms are substituted with fluorine atoms.
  • R 5 is a hydrogen atom, a fluorine atom or a monovalent polar group, q is an integer of 1 to 5.
  • a plurality of X, R 4 and R 5 may be the same or different.
  • the semiconductor element of the present invention includes a cured film formed from the curable composition for nanoimprint.
  • the curable composition for nanoimprint as described above, it is possible to suppress the peeling of the shape transfer layer, and as a result, it is possible to form a cured film having an excellent pattern shape of the shape transfer layer. . Therefore, for example, the semiconductor device such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM provided with such a cured interlayer insulating film has improved electrical performance and the like.
  • the nanoprint method of the present invention comprises: (1) A step of forming a shape transfer layer using the curable composition for nanoimprint, (2) a step of pressing a stamper on the shape-transferred layer, (3) a step of exposing the shaped transfer layer while the stamper is in pressure contact; and (4) a step of peeling the stamper from the shaped transfer layer.
  • the stamper since the nanoimprint curable composition having excellent releasability is used, the stamper can be easily peeled from the shape transfer layer formed from the nanoimprint curable composition. In addition, it is possible to suppress the peeling of the shape transfer layer.
  • the curable composition for nanoimprinting and the nanoimprinting method of the present invention it is possible to form a shaped transfer layer having excellent releasability and to suppress the occurrence of peeling of the shaped transfer layer. be able to.
  • curable composition for nanoimprinting of the present invention contains [A] a polymerizable compound, [B] a fluorine atom-containing polymer, and [C] a radical generator. . Moreover, you may contain arbitrary components in the range which does not impair the effect of this invention. Hereinafter, each component will be described in detail.
  • the polymerizable compound is a compound having one or more polymerizable functional groups.
  • Specific examples of the polymerizable compound include radically polymerizable compounds.
  • Specific examples of the polymerizable functional group include a radical polymerizable group.
  • Examples of the radical polymerizable group include a group containing an ethylenically unsaturated bond (hereinafter, also referred to as “ethylenically unsaturated bond group”).
  • the ethylenically unsaturated bond group include a (meth) acryloyl group, a vinyl group, an allyl group, a styryl group, etc. Among them, a (meth) acryloyl group is preferable from the viewpoint of high polymerization reactivity. An acryloyl group is more preferable.
  • a polymeric compound may use 1 type (s) or 2 or more types.
  • radical polymerizable compound examples include compounds having one or more ethylenically unsaturated bond groups.
  • Examples of the compound having one ethylenically unsaturated bond group include: Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Alkyl (meth) acrylates such as lauryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate; Aryl (meth) acrylates such as benzyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, e
  • Examples of the compound having two or more ethylenically unsaturated bond groups include: Ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, tricyclodecanediyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) Isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO Modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, Opentyl glycol di
  • the compound which has one ethylenically unsaturated bond group, and the compound which has 2 or more ethylenically unsaturated bond groups A combination is preferred.
  • the polymerizable compound has an alicyclic structure such as tricyclodecanediyldimethylenedi (meth) acrylate or isoboronyl (meth) acrylate in view of curability of the curable composition (meth). Acrylates are preferred.
  • (meth) acrylates having an aromatic ring such as benzyl (meth) acrylate are preferable from the viewpoint of mold filling property and etching resistance of the curable composition.
  • the content of the polymerizable compound is usually 70% by mass or more, preferably 80% by mass or more, and more preferably 85% by mol or more based on the curable composition. [A] When the content of the polymerizable compound is within the above range, the curability of the curable composition can be improved. In addition, 1 type (s) or 2 or more types can be used for a [A] polymeric compound. In addition, it is preferable to use one or more compounds each having one polymerizable group and one or more compounds having two or more polymerizable groups.
  • the fluorine atom-containing polymer is a polymer containing a fluorine atom in its structure.
  • the curable composition improves the releasability and makes it difficult for the resist film to peel off.
  • the fluorine atom-containing polymer is represented by the structural unit represented by the above formula (B-1) (hereinafter also referred to as “structural unit (I)”) and the above formula (B-2). It is preferable to have at least one structural unit selected from the group consisting of structural units (hereinafter also referred to as “structural units (II)”).
  • R 1 and R 1 ′ are each independently a hydrogen atom, a methyl group or a trifluoromethyl group.
  • R 2 is a single bond or a hydrocarbon group having 1 to 20 carbon atoms.
  • R 3 is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group, a carboxyl group or a cyano group.
  • m is an integer of 0-4.
  • R f1 and R f2 are each independently a monovalent organic group having a fluorine atom.
  • R 1 and R 1 ′ are preferably a hydrogen atom or a methyl group.
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 2 include a methylene group, an ethylene group, an n-propylene group, an i-propylene group, a methylethylene group, an n-butylene group, and 1-methylpropylene.
  • a divalent chain hydrocarbon group such as a group, 1-dimethylethylene group, n-heptylene group, n-hexylene group, n-octylene group, n-decylene group, n-dodecylene group;
  • a divalent alicyclic hydrocarbon group in which two hydrogen atoms are removed from an alicyclic hydrocarbon such as cyclobutane, cyclopentane, cyclohexane, cyclooctane, cyclodecane, dicyclopentane, tricyclodecane, tetracyclododecane, adamantane, etc.
  • Divalent aromatic hydrocarbon groups such as a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group; Examples thereof include a divalent hydrocarbon group in which two or more of the above hydrocarbon groups are bonded.
  • R 2 is preferably a single bond or a chain hydrocarbon group, more preferably a single bond, a methylene group or an i-propylene group.
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 3 include, for example, Monovalent such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc.
  • a chain hydrocarbon group Monovalent alicyclic hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group; And monovalent aromatic hydrocarbon groups such as phenyl group, tolyl group, naphthyl group, anthranyl group, phenanthonyl group, benzyl group and phenethyl group.
  • Monovalent alicyclic hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group
  • monovalent aromatic hydrocarbon groups such as phenyl group, tolyl group, naphthyl group, anthranyl group, phenanthonyl group, benzy
  • Examples of the monovalent organic group having a fluorine atom represented by R f1 and R f2 include a group in which part or all of the hydrogen atoms of the hydrocarbon group exemplified as R 3 are substituted with a fluorine atom. Can be mentioned.
  • Rf1 and Rf2 group represented by the said Formula (b) is preferable.
  • X is a single bond, —O—, —CO—, —COO—, —OCO— or —NH—.
  • R 4 is a single bond or a hydrocarbon group having 1 to 20 carbon atoms.
  • p is an integer of 0 to 5.
  • R F is a (q + 1) -valent hydrocarbon group having 1 to 20 carbon atoms in which part or all of the hydrogen atoms are substituted with fluorine atoms.
  • R 5 is a hydrogen atom, a fluorine atom or a monovalent polar group.
  • q is an integer of 1 to 5.
  • X when R 4 and R 5 are a plurality each of a plurality of X, R 4 and R 5 may be respectively the same or different.
  • X is preferably a single bond.
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 4 include the same hydrocarbon groups exemplified as R 2 .
  • P is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
  • Examples of the (q + 1) -valent hydrocarbon group in which part or all of the hydrogen atoms represented by R F are substituted with fluorine atoms When q is 1, for example, a fluoromethylene group, a difluoromethylene group, a trifluoromethylmethylene group, a ditrifluoromethylmethylene group and the like can be mentioned. When q is 2, for example, a fluoromethanetriyl group, a difluoroethanetriyl group and the like can be mentioned.
  • Examples of the polar group represented by R 5 include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, and an alkoxy group.
  • q is preferably 1 or 2, and more preferably 1.
  • Examples of the group represented by the formula (b) include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1,1,1-trifluoro-i-propyl group, and a 1,1,1-trifluoro group.
  • 1,1,1,3,3,3-hexafluoro-i-propyl group 1,1,1,3,3,3-hexafluoro-2-hydroxy-i -Propyl group, 1,1,1,3,3,3-hexafluoro-2-cyano-i-propyl group, 1,1,1,3,3,3-hexafluoro-2-methoxy-i-propyl Group, 1,1,1,3,3,3-hexafluoro-2-carboxy-i-propyl group and the like.
  • 1,1,1,3,3,3-hexafluoro-2-hydroxy-i-propyl group and 1,1,1,3,3,3-hexafluoro-i-propyl group are preferable.
  • structural unit (I) examples include those described in paragraphs [0214] to [0215] of JP2007-304537A, those described in paragraph [0085] of JP2008-088343, Examples thereof include those described in paragraphs [0149] and [0159] to [0161] of JP 2010-32994, and structural units derived from monomers described in paragraph [0029] of International Publication No. 2007/116664.
  • structural unit (II) include those described in paragraphs [0162] to [0163] of JP 2010-32994 A, for example.
  • the fluorine atom-containing polymer is preferably a polymer having the structural unit (I).
  • the R 2 is a single bond
  • the R f1 is a group represented by the formula (b)
  • R F is a fluorinated chain hydrocarbon group
  • R 5 is a hydrogen atom or a hydroxyl group
  • q is 1.
  • the fluorine atom-containing polymer may have other structural units not containing fluorine.
  • the structural unit derived from the compound which has one ethylenically unsaturated bond mentioned above as a [A] polymeric compound is mentioned.
  • structural units derived from (meth) acrylates having an alicyclic skeleton are preferred.
  • the content ratio of the structural unit having a fluorine atom in the fluorine atom-containing polymer is usually from 0.1 to 100% by mass, preferably from 1 to 100% by mass, preferably from 10 to 100%, based on all structural units. More preferred is mass%.
  • the fluorine atom content in the fluorine atom-containing polymer is preferably 1 mol% or more, more preferably 1 to 50 mol%, still more preferably 5 to 30 mol%.
  • the mold release property of the said curable composition is further excellent because a fluorine atom content rate is 1 mol% or more.
  • fluorine atom content means the number of moles of fluorine atoms relative to the number of moles of all atoms in the [B] fluorine atom-containing polymer.
  • the content of the fluorine atom-containing polymer is usually 0.1 to 100 parts by weight, more preferably 0.1 to 20 parts by weight, with respect to 100 parts by weight of the polymerizable compound [A]. 0.1 to 10 parts by mass is more preferable.
  • the fluorine atom-containing polymer is effectively on the surface side. As a result, the releasability of the nanoimprint curable composition is improved.
  • the fluorine atom-containing polymer can be synthesized according to a conventional method such as radical polymerization.
  • a method in which a solution containing a monomer and a radical initiator is dropped into a reaction solvent or a solution containing a monomer to cause a polymerization reaction A method in which a solution containing a monomer and a solution containing a radical initiator are separately dropped into a reaction solvent or a solution containing a monomer to cause a polymerization reaction;
  • a plurality of types of solutions containing each monomer and a solution containing a radical initiator are separately added to a reaction solvent or a solution containing a monomer and synthesized by a method such as a polymerization reaction.
  • the monomer amount in the dropped monomer solution is 30 mol with respect to the total amount of monomers used for polymerization. % Or more is preferable, 50 mol% or more is more preferable, and 70 mol% or more is particularly preferable.
  • the reaction temperature in these methods may be appropriately determined depending on the initiator type. Usually, it is 30 ° C to 180 ° C, preferably 40 ° C to 160 ° C, and more preferably 50 ° C to 140 ° C.
  • the dropping time varies depending on the reaction temperature, the type of initiator, the monomer to be reacted, etc., but is usually 30 minutes to 8 hours, preferably 45 minutes to 6 hours, more preferably 1 hour to 5 hours. .
  • the total reaction time including the dropping time varies depending on the conditions as in the dropping time, but is usually from 30 minutes to 8 hours, preferably from 45 minutes to 7 hours, and more preferably from 1 hour to 6 hours.
  • radical initiator used in the polymerization examples include azobisisobutyronitrile (AIBN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2 -Cyclopropylpropionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and the like. These initiators can be used alone or in admixture of two or more.
  • the polymerization solvent is not limited as long as it is a solvent other than a solvent that inhibits polymerization (nitrobenzene having a polymerization inhibiting effect, mercapto compound having a chain transfer effect, etc.) and can dissolve the monomer.
  • Examples of the solvent used for the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; Halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene; Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate; Ketones such as acetone, 2-butanone, 4-methyl-2-p
  • the polymer obtained by the polymerization reaction is preferably recovered by a reprecipitation method. That is, after completion of the polymerization reaction, the polymer is recovered as a powder by introducing the polymerization solution into a reprecipitation solvent.
  • a reprecipitation solvent alcohols or alkanes can be used alone or in admixture of two or more.
  • the polymer can be recovered by removing low-molecular components such as monomers and oligomers by a liquid separation operation, a column operation, an ultrafiltration operation, or the like.
  • the polystyrene-equivalent weight average molecular weight (hereinafter also referred to as “Mw”) of the fluorine atom-containing polymer by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1,000 or more and 100,000 or less. 1,000 to 70,000 is more preferable, 1,000 to 50,000 is more preferable, and 1,000 to 30,000 is particularly preferable. By setting Mw within the above range, it is considered that surface uneven distribution of the [B] fluorine atom-containing polymer in the shaped transfer layer formed from the curable composition for nanoimprinting is likely to occur. The mold release property of the curable composition is improved.
  • the ratio (Mw / Mn) of Mw to the polystyrene-equivalent number average molecular weight (hereinafter also referred to as “Mn”) by GPC of the fluorine atom-containing polymer is usually 1 or more and 7 or less, and 1 or more. 5 or less is preferable and 1 or more and 3 or less are more preferable.
  • Mw and Mn of this specification use GPC columns (Tosoh Corporation, G2000HXL, 2 G3000HXL, 1 G4000HXL), flow rate of 1.0 ml / min, elution solvent tetrahydrofuran, column temperature of 40 ° C. The value measured by GPC using monodisperse polystyrene as a standard under conditions.
  • the radical generator is a substance that initiates a polymerization reaction by a polymerizable group of the polymerizable compound [A] by generating a radical.
  • Examples of the radical generator include a photo radical generator and a thermal radical generator.
  • thermal radical generator examples include benzophenone, benzyl dimethyl ketal, ⁇ -hydroxy ketones, ⁇ -amino ketones, oxime esters, acylphosphine oxide compounds, 2- (dimethylamino) -2-[(4- Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane, and the like.
  • ⁇ -hydroxyketones, ⁇ -aminoketones and acylphosphine oxide compounds are preferable, and acylphosphine oxide compounds are particularly preferable.
  • the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.
  • Examples of the ⁇ -hydroxy ketones include 1-hydroxy-cyclohexyl-phenyl ketone and 2-hydroxy-2-methyl-1-phenyl-propan-1-one.
  • Examples of ⁇ -aminoketones include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1 and the like.
  • photo radical generator examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), and 2,2′-azobis- (4-methoxy).
  • -2,4-dimethylvaleronitrile 2,2'-azobis- (2-methylbutyronitrile), 1,1'-azobis- (cyclohexane-1-carbonitrile), dimethyl-2,2'-azobis Azo compounds such as (2-methylpropionate);
  • Organic peroxides such as benzoyl peroxide, lauroyl peroxide, tert-butyl peroxypivalate, 1,1′-bis- (tert-butylperoxy) cyclohexane; hydrogen peroxide and the like.
  • it is good also as a redox type [C] radical generator combining the said organic peroxide and a reducing agent.
  • radical generators for example, biimidazole compounds described in JP 2007-293306 A, oxime type radical generators, benzoin compounds, acetophenone compounds described in JP 2008-89744 A, for example.
  • the content of the radical generator is preferably 1 to 30 parts by mass, preferably 1 to 25 parts by mass with respect to 100 parts by mass in total of the [A] polymerizable compound and the [B] fluorine atom-containing polymer. More preferred is 1 to 20 parts by mass. [C] By setting the content of the radical generator in the above range, no foreign matter is generated, storage stability is improved, and the shape-transferred layer is sufficiently cured.
  • the curable composition for nanoimprints preferably contains no organic solvent, but may contain an organic solvent as long as the effects of the present invention are not impaired.
  • the content of the organic solvent is preferably 2,000 parts by mass or less with respect to 100 parts by mass in total of [A] polymerizable compound, [B] fluorine atom-containing polymer and [C] radical generator. More preferred is 1,000 parts by mass or less.
  • organic solvent examples include alcohols such as methanol and ethanol; Ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; Aromatic hydrocarbons such as toluene and x
  • the nanoimprint curable composition includes, as other optional components, for example, a mold release agent, a silane coupling agent, an antioxidant, an ultraviolet absorber, a light stabilizer, an antiaging agent, a plasticizer, and an adhesion promoter.
  • a mold release agent for example, a silane coupling agent, an antioxidant, an ultraviolet absorber, a light stabilizer, an antiaging agent, a plasticizer, and an adhesion promoter.
  • Colorants inorganic particles, elastomer particles, photoacid growth agents, photobase generators, basic compounds, flow regulators, antifoaming agents, dispersants, and the like.
  • release agent examples include conventionally known release agents, for example, silicone release agents, solid waxes such as polyethylene wax, amide wax, and tetrafluoroethylene powder, fluorine-based, phosphate ester-based compounds, and the like.
  • the silicone mold release agent is a mold release agent having an organopolysiloxane structure as a basic structure, and examples thereof include unmodified or modified silicone oil, polysiloxane containing trimethylsiloxysilicate, and silicone acrylic resin.
  • the content of the release agent is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the curable composition.
  • silane coupling agent examples include vinyl silanes such as vinyltrichlorosilane, vinyltris ( ⁇ -methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane; ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropyl Acrylic silanes such as methyldimethoxysilane; epoxy silanes such as ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane; N— ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropyltrimethoxysilane
  • the content of the silane coupling agent is preferably 10 parts by mass or less with respect to 100 parts by mass of the curable composition.
  • the antioxidant is, fading by light irradiation, and ozone (is x, an integer) active oxygen, NO x, SO x is to suppress fading by various gases such.
  • antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, and thiocyanic acid. Examples thereof include salts, thiourea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like.
  • antioxidants examples include Irganox 1010, 1035, 1076, 1222 (manufactured by Ciba Geigy), Antigene P, 3C, FR, and Sumilizer S (manufactured by Sumitomo Chemical). It is done.
  • the content of the antioxidant is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the curable composition.
  • Examples of commercially available ultraviolet absorbers include Tinuvin P, 234, 320, 326, 327, 328, 213 (manufactured by Ciba Geigy), Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350, 400 (above, manufactured by Sumitomo Chemical).
  • the content of the ultraviolet absorber is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the curable composition.
  • the above light stabilizer examples include, for example, Tinuvin 292, 144, 622LD (above, manufactured by Ciba Geigy), Sanol LS-770, 765, 292, 2626, 1114, 744 (above, Sankyo) Kasei Kogyo) and the like.
  • the content of the light stabilizer is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the curable composition.
  • anti-aging agents examples include Antigene W, S, P, 3C, 6C, RD-G, FR, AW (above, manufactured by Sumitomo Chemical Co., Ltd.) and the like.
  • the content of the anti-aging agent is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the curable composition.
  • plasticizer examples include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, dimethyl adipate, diethyl adipate, di ( n-butyl) adipate, dimethyl suberate, diethyl suberate, di (n-butyl) suberate and the like.
  • the content of the plasticizer is preferably 0.1 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the curable composition. The following is more preferable.
  • adhesion promoter examples include benzimidazoles and polybenzimidazoles, lower hydroxyalkyl-substituted pyridine derivatives, nitrogen-containing heterocyclic compounds, urea or thiourea, organic phosphorus compounds, 8-oxyquinoline, 4-hydroxypteridine, 1 , 10-phenanthroline, 2,2′-bipyridine derivatives, benzotriazoles, organic phosphorus compounds and phenylenediamine compounds, 2-amino-1-phenylethanol, N-phenylethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-ethylethanolamine and its derivatives, benzothiazole derivatives and the like.
  • the content of the adhesion promoter is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and 0.1 to 5% by mass with respect to 100 parts by mass of the curable composition. Is more preferable. By making content of the said adhesion promoter into the said range, the effect of an adhesion promoter can fully be exhibited.
  • Examples of the basic compound include amines; nitrogen-containing heterocyclic compounds such as quinoline and quinolidine; basic alkali metal compounds; basic alkaline earth metal compounds.
  • amines are preferable from the viewpoint of compatibility with the photopolymerizable monomer, such as octylamine, naphthylamine, xylenediamine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, dimethylaniline, quinuclidine, tributylamine, tributylamine, and the like.
  • Examples include octylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine, hexamethylenetetramine, and triethanolamine.
  • the viscosity of the nanoimprint curable composition was measured using an E-type viscometer VISCONIC ED type (manufactured by Tokimec).
  • the viscosity at 25 ° C. of the nanoimprint curable composition is preferably 0.1 to 100 mPa ⁇ s, more preferably 0.5 to 50 mPa ⁇ s, still more preferably 0.5 to 40 mPa ⁇ s, ⁇ 30 mPa ⁇ s is particularly preferred.
  • the substrate coating suitability and the mechanical strength of the film are improved, and the occurrence of unevenness on the surface during coating can be suppressed, It can suppress that the said curable composition flows out of a board
  • the viscosity of the curable composition is 100 mPa ⁇ s or less, it is suitable for application using an inkjet. Further, even when a mold having a fine concavo-convex pattern is used, the curable composition can easily flow into the cavity of the concave portion of the mold, and the generation of bubble defects is suppressed because the air is difficult to be taken in. Also, the generation of residues after curing is suppressed.
  • the semiconductor element of this invention is equipped with the cured film formed from the said curable composition for nanoimprints.
  • the curable composition for nanoimprint as described above, it is possible to suppress the peeling of the shape transfer layer, and as a result, it is possible to form a cured film having an excellent pattern shape of the shape transfer layer. . Therefore, for example, the semiconductor device such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM provided with such a cured interlayer insulating film has improved electrical performance and the like.
  • the nanoimprinting method of the present invention includes (1) a step of forming a shaped transfer layer using the curable composition for nanoimprint (hereinafter also referred to as “(1) step”), and (2) the shaped transfer layer.
  • a step of pressure-contacting the stamper hereinafter also referred to as “(2) step”
  • a step of exposing the shape-transferred layer with the stamper being pressed hereinafter also referred to as “(3) step”
  • a step of peeling the stamper from the shape-transferred layer hereinafter, also referred to as “(4) step”.
  • a process is a process of forming a to-be-shaped transfer layer, for example on the board
  • FIG. 1 is a schematic view showing an example of a state after the shape transfer layer 2 is formed on the substrate 1.
  • a silicon wafer As the substrate, a silicon wafer is usually used, but other known substrates for semiconductor devices such as aluminum, titanium-tungsten alloy, aluminum-silicon alloy, aluminum-copper-silicon alloy, silicon oxide, silicon nitride, etc. It can be used by arbitrarily selecting from the existing ones.
  • the component constituting the shape transfer layer is the above-described curable composition for nanoimprint.
  • this curable composition for nanoimprints can contain a curing accelerator.
  • the curing accelerator include a radiation-sensitive curing accelerator and a thermosetting accelerator.
  • a radiation sensitive curing accelerator is preferable.
  • the radiation-sensitive curing accelerator can be appropriately selected depending on the structural unit constituting the curable composition for nanoimprint, and specifically includes a photoacid generator, a photobase generator, a photoradical generator, a photosensitizer, and the like. Can be mentioned.
  • a radiation sensitive hardening accelerator may be used individually by 1 type, and may use 2 or more types together.
  • the curable composition for nanoimprint is, for example, an inkjet method, a dip coating method, an air knife coating method, a curtain coating method, a wire barcode method, a gravure coating method, an extrusion coating method, a spin coating method, a slit scanning method, etc.
  • the shape transfer layer can be formed by coating.
  • the film thickness of the shape-transferring layer varies depending on the application used, but is, for example, 0.01 to 5.0 ⁇ m.
  • FIG. 2 is a schematic view showing an example of a state in which a stamper is pressed against the shape transfer layer. As shown in FIG. 2, the concave / convex pattern of the stamper 3 is formed in the shaped transfer layer 2 by pressing the stamper 3 against the shaped transfer layer 2 formed in step (1).
  • the stamper needs to be made of a light transmissive material. Specifically, a film made of a light transparent resin such as glass, quartz, PMMA, polycarbonate resin, a transparent metal vapor deposited film, polydimethylsiloxane, etc. And flexible films, photocured films, metal films, and the like.
  • a light transparent resin such as glass, quartz, PMMA, polycarbonate resin, a transparent metal vapor deposited film, polydimethylsiloxane, etc.
  • flexible films photocured films, metal films, and the like.
  • the pressure at the time of pressure welding is not particularly limited, but is usually 0.1 to 100 MPa, preferably 0.1 to 50 MPa, more preferably 0.1 to 30 MPa, and further preferably 0.1 to 20 MPa.
  • the time for pressure contact is not particularly limited, but is usually 1 to 600 seconds, preferably 1 to 300 seconds, more preferably 1 to 180 seconds, and further preferably 1 to 120 seconds.
  • the step (3) is a step of exposing the shape transfer layer while the stamper is pressed.
  • FIG. 3 is a schematic diagram showing an example of a state in which the shape transfer layer is exposed while the stamper is pressed.
  • radicals are generated from the [C] radical generator contained in the curable composition for nanoimprinting by exposing the shape-transferred layer 3.
  • the to-be-shaped transfer layer which consists of the said curable composition for nanoimprint hardens
  • the concavo-convex pattern By transferring the concavo-convex pattern, it can be used as, for example, a film for an interlayer insulating film of a semiconductor element such as LSI, system LSI, DRAM, SDRAM, RDRAM, or D-RDRAM, a resist film when manufacturing the semiconductor element, etc. .
  • the shape transfer layer 3 is cured by exposure to become a shape transfer layer 5.
  • the exposure source is not particularly limited.
  • electromagnetic waves such as UV light, visible light, ultraviolet light, far ultraviolet light, and X-rays
  • radiation such as charged particle beams such as electron beams (including ArF excimer laser (wavelength 193 nm) or KrF excimer laser (wavelength 248 nm)).
  • electron beams including ArF excimer laser (wavelength 193 nm) or KrF excimer laser (wavelength 248 nm)).
  • the exposure may be performed on the entire surface of the shape-transferring layer, or may be performed only on a partial region.
  • thermosetting when the shape-transferred layer has thermosetting properties, heat curing may be further performed.
  • the heating atmosphere and the heating temperature are not particularly limited. For example, heating can be performed at 40 to 200 ° C. under an inert atmosphere or under reduced pressure. Heating can be performed using a hot plate, an oven, a furnace, or the like.
  • the peeling process is a process of peeling the stamper 3 from the shape transfer layer 5.
  • FIG. 4 is a schematic diagram illustrating an example of a state after the stamper is peeled from the shape transfer layer.
  • the peeling process may be performed in any way, and various conditions for peeling are not particularly limited. That is, for example, the substrate 1 may be fixed and the stamper may be moved away from the substrate 1 to be peeled off, or the stamper may be fixed and the substrate 1 moved away from the stamper to be peeled off. Both may be peeled by pulling in the opposite direction.
  • a release agent can be used in the nanoimprint method. That is, before the step (2), a release agent attaching step for attaching the release agent to the surface of the stamper having the uneven pattern may be performed.
  • a release agent When using a release agent, the type is not particularly limited.
  • a mold release agent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • a silicon release agent is particularly preferable.
  • Specific examples of the silicon release agent include polydimethylsiloxane, acrylic silicone graft polymer, acrylic siloxane, and arylsiloxane.
  • Step (5) The step is a step of removing the remaining concave portion of the shape transfer layer by etching.
  • FIG. 5 is a schematic diagram illustrating an example of a state after etching. As shown in FIG. 5, by performing an etching process, an unnecessary portion can be removed from the pattern shape of the shape transfer layer, and a desired resist pattern 10 can be formed.
  • etching method It does not specifically limit as an etching method, It can form by performing a conventionally well-known method, for example, dry etching.
  • a conventionally known dry etching apparatus can be used for the dry etching.
  • the source gas at the time of dry etching is appropriately selected according to the elemental composition of the film to be etched, but includes an oxygen atom gas such as O 2 , CO, CO 2 , an inert gas such as He, N 2 , Ar, A chlorine-based gas such as Cl 2 or BCl 3 , a gas of H 2 or NH 3 , or the like can be used.
  • these gases may be used individually by 1 type, and can also be mixed and used.
  • Pentyl) ester 195.4 g, compound (M-4) (methacrylic acid (1,1,1,3,3,3-hexafluoro-2-propyl) ester) 104.6 g, and methyl ethyl ketone 575.0 g. Charged and purged with nitrogen for 30 minutes. After purging with nitrogen, the inside of the flask was heated to 80 ° C. while stirring with a magnetic stirrer. And the said polymerization initiator solution prepared beforehand was dripped over 5 minutes using the dropping funnel, and it was made to age
  • the lower layer solution was recovered.
  • the recovered lower layer solution is substituted with 4-methyl-2-pentanol, and this solution is washed with distilled water and again substituted with 4-methyl-2-pentanol, and a solution containing the polymer (B-2) It was.
  • the solid content concentration of this polymer (B-2) solution was measured by weighing 0.3 g of this solution into an aluminum pan and heating on a hot plate at 140 ° C. for 1 hour. It was calculated from the difference in mass. This solid content concentration was used for the preparation of the composition for forming the upper layer film and the yield calculation.
  • Mw of the obtained polymer (B-2) was 10,200, Mw / Mn was 1.65, and the yield was 65%.
  • a structural unit derived from the compound (M-3) in the polymer (B-2) (a structural unit represented by the following formula (U-3)): a structural unit derived from the compound (M-4) ( The content ratio of the structural unit represented by the following formula (U-4) was 60.5: 39.5 (mol%).
  • the reaction was continued for another 3 hours, and the reaction solution was cooled to 30 ° C. or lower to obtain a polymerization reaction solution.
  • the resulting polymerization reaction liquid was adjusted by adding methyl ethyl ketone to 120 g, transferred to a separatory funnel together with 40 g of methanol and 240 g of n-hexane, and after stirring sufficiently, the lower layer was separated.
  • the lower layer was mixed with 30 g of methanol and 160 g of n-hexane, transferred to a separatory funnel, and then the lower layer was separated.
  • the solvent in the lower layer obtained here was distilled off, and the resulting white powder was vacuum dried at 50 ° C.
  • polymer (B-3) was a polymer having a structural unit represented by the following formula (U-3), and Mw was 11,800 and Mw / Mn was 2.3.
  • Viscosity (mPa ⁇ s) The viscosity at 25 ° C. was measured using an E-type viscometer VISCONIC ED type (manufactured by Tokimec).
  • a slide glass subjected to UV ozone cleaning and mold release treatment was prepared.
  • UV ozone cleaning was performed by using UV SURFACE PROCESSOR PM9011-B (manufactured by Sen Special Light Source Co., Ltd.) and performing UV irradiation of about 5 J / cm 2 .
  • DURASURF HD-1101Z manufactured by Harves was used as a mold release agent.
  • the composition of the present invention was spotted on a silicon wafer by 1.0 to 3.0 ⁇ L using a micropipette, and the above treatment of the slide glass was performed.
  • a glass slide was applied from above so that the applied surface was in contact with the composition, and the composition was cured by UV irradiation at 100 mJ / cm 2 while applying a press load of about 100 N to prepare a sample.
  • These were created using a nanoimprint apparatus EUN-4200 (manufactured by Engineering System Co., Ltd.).
  • the jig was pressed against the silicon wafer only using the tensile tester SDW-S UNIVERSAL TESTING MACHINE (manufactured by Imada Seisakusho). The pressure was lowered under the condition of about 10 mm / min, and the value obtained by dividing the pressure when the silicon wafer was peeled by the application area of the composition was calculated as the release force. The smaller the release force, the better the release property.
  • Example 1 [A] 42 parts of a polymerizable compound (A-1), 49 parts of (A-2), [B] 2 parts of a polymer (B-1) as a fluorine atom-containing polymer, and [C] as a radical generator (C-1) 7 parts were mixed to prepare a nanoimprint curable composition (J-1) of Example 1.
  • the viscosity at 25 ° C. of the curable composition for nanoimprint (J-1) was 10 mPa ⁇ s.
  • the release force was as small as 2.5 kPa.
  • Example 2 In Example 1, the same procedure as in Example 1 was conducted, except that 2 parts of the polymer (B-2) was used instead of 2 parts of the polymer (B-1) as the [B] fluorine atom-containing polymer.
  • the curable composition for nanoimprinting of Example 2 (J-2) was prepared.
  • the viscosity at 25 ° C. of the curable composition for nanoimprint (J-2) was 9 mPa ⁇ s.
  • the release force was as small as 2.8 kPa.
  • Example 3 In Example 1, the same procedure as in Example 1 was performed except that 2 parts of the polymer (B-3) was used instead of 2 parts of the polymer (B-1) as the [B] fluorine atom-containing polymer.
  • the curable composition for nanoimprinting of Example 3 (J-3) was prepared.
  • the viscosity at 25 ° C. of the curable composition for nanoimprint (J-3) was 9 mPa ⁇ s.
  • the release force was as small as 2.8 kPa.
  • Example 1 a curable composition for nanoimprint (CJ-1) of Comparative Example 1 was prepared in the same manner as in Example 1 except that [B] the fluorine atom-containing polymer was not blended.
  • the viscosity at 25 ° C. of the curable composition for nanoimprint (CJ-1) was 9 mPa ⁇ s.
  • the release force was 4.7 kPa.
  • Example 4 First, using a coater / developer (trade name “CLEAN TRACK ACT8”, manufactured by Tokyo Electron), an organic underlayer film (trade name “NFC CT08”, manufactured by JSR) having a thickness of 300 nm is formed on the surface of an 8-inch silicon wafer. did. Subsequently, after forming an inorganic intermediate film (trade name “NFC SOG08”, manufactured by JSR) having a film thickness of 45 nm, the substrate was divided into four to obtain experimental substrates. Thereafter, about 50 ⁇ L of the nano-imprint curable composition (J-1) of Example 1 was spotted on the center of the experimental substrate and placed on a work stage of a simple imprint apparatus (EUN-4200, manufactured by Engineering System).
  • a quartz template (NIM-PH350, manufactured by NTT-ATN) in which a release agent (trade name “HD-1100Z”, manufactured by Daikin Kasei) is applied in advance by a predetermined method is used, and silicone rubber (thickness 0.2 mm) is used.
  • the adhesive layer was attached to a quartz exposure head of a simple imprint apparatus.
  • the exposure head was lowered, the template and the experimental substrate were brought into close contact with each other via the curable composition for nanoimprint, and then UV exposure was performed for 15 seconds. .
  • the exposure stage was raised, and the template was peeled off from the cured shape transfer layer to form a pattern. When peeled, there was no residue on the template and the pattern did not collapse. Therefore, it can be said that this curable composition for nanoimprint is excellent in releasability.
  • the curable composition for nanoimprinting of the present invention can be suitably used for nanoimprinting used for improving the degree of integration and recording density of circuits such as semiconductor elements.

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Abstract

L'invention concerne une composition durcissable pour nano-impression, qui contient (A) un composé polymérisable, (B) un polymère contenant des atomes de fluor, et (C) un générateur de radicaux. Il est préférable que la teneur en polymère contenant des atomes de fluor (B) soit de 0,1-10 parties en masse (inclus) pour 100 parties en masse du composé polymérisable (A). Il est préférable que le poids moléculaire moyen en poids du polymère contenant des atomes de fluor (B) en terme de polystyrène tel que déterminé par chromatographie par perméation de gel soit de 1000-30 000 (inclus). Il est enfin préférable que le polymère contenant des atomes de fluor (B) contienne un polymère qui comporte au moins un motif structural choisi dans le groupe constitué par les motifs structuraux représentés par la formule (B-1) et les motifs structuraux représentés par la formule (B-2).
PCT/JP2011/058139 2010-03-31 2011-03-30 Composition durcissable pour nano-impression, élément semi-conducteur, et procédé de nano-impression WO2011125800A1 (fr)

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WO2019208613A1 (fr) * 2018-04-27 2019-10-31 セントラル硝子株式会社 Composition durcissable et procédé de production de motif

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JP2013239535A (ja) * 2012-05-14 2013-11-28 Toyo Gosei Kogyo Kk 光インプリント方法
WO2019208613A1 (fr) * 2018-04-27 2019-10-31 セントラル硝子株式会社 Composition durcissable et procédé de production de motif

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