WO2019188882A1 - インプリント用硬化性組成物、離型剤、硬化物、パターン形成方法およびリソグラフィー方法 - Google Patents
インプリント用硬化性組成物、離型剤、硬化物、パターン形成方法およびリソグラフィー方法 Download PDFInfo
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- WO2019188882A1 WO2019188882A1 PCT/JP2019/012323 JP2019012323W WO2019188882A1 WO 2019188882 A1 WO2019188882 A1 WO 2019188882A1 JP 2019012323 W JP2019012323 W JP 2019012323W WO 2019188882 A1 WO2019188882 A1 WO 2019188882A1
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- carbon atoms
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- aliphatic hydrocarbon
- hydrocarbon group
- curable composition
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Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
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- 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
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- 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
- C08F22/00—Homopolymers and 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
- C08F22/10—Esters
- C08F22/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
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- 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
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- 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
- C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
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- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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- G—PHYSICS
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- 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
- G03F7/0041—Photosensitive materials providing an etching agent upon exposure
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- G—PHYSICS
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- 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
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- G—PHYSICS
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- 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
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
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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
- G03F7/004—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
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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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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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
- G03F9/00—Registration or positioning of originals, masks, frames, photographic sheets or textured or patterned surfaces, e.g. automatically
- G03F9/70—Registration or positioning of originals, masks, frames, photographic sheets or textured or patterned surfaces, e.g. automatically for microlithography
- G03F9/7003—Alignment type or strategy, e.g. leveling, global alignment
- G03F9/7042—Alignment for lithographic apparatus using patterning methods other than those involving the exposure to radiation, e.g. by stamping or imprinting
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
Definitions
- the present invention relates to a curable composition for imprints, a release agent, a cured product, a pattern formation method, and a lithography method.
- the imprint method is a technique for transferring a fine pattern to a material by pressing a mold (generally called a mold or a stamper) on which a pattern is formed.
- a mold generally called a mold or a stamper
- a nanoimprint technique for forming a nano-order level fine pattern has attracted attention.
- methods called a thermal imprint method and an optical imprint method have been proposed based on the transfer method.
- a fine pattern is formed by pressing a mold onto a thermoplastic resin heated to a glass transition temperature (hereinafter sometimes referred to as “Tg”) or higher, and releasing the mold after cooling.
- Tg glass transition temperature
- This method can select various materials, but it also has problems that high pressure is required during pressing and that it is difficult to form a fine pattern due to thermal shrinkage.
- the mold is released after photocuring in a state where the mold is pressed against the curable composition for imprints. Or the form which apply
- imprinting is performed on the uncured product by light irradiation, it is not necessary to heat at high pressure and high temperature, and a fine pattern can be easily formed.
- a mold made of a light-transmitting material such as quartz is pressed after a curable composition for imprinting is applied on a substrate (adhesion treatment is performed if necessary).
- the curable composition for imprints is cured by light irradiation in a state where the mold is pressed, and then the mold is released to produce a cured product to which the target pattern is transferred.
- Examples of the method for applying the curable composition for imprints on the substrate include a spin coating method and an ink jet method.
- the ink jet method is an application method that has attracted attention in recent years from the viewpoint that the loss of the curable composition for imprints is small.
- the curable composition for imprints used for NIL can resolve an ultrafine pattern of 20 nm or less, like an extreme ultraviolet (EUV) resist, and is highly etched as a mask when finely processing an object to be processed. Tolerance is required.
- throughput productivity
- suitability for nanoimprinting such as pattern filling properties (reduction of filling time) and mold releasability (reduction of release time) is also required.
- Patent Documents 1 to 8 are known as disclosing curable compositions for imprints that can be applied to the imprint method described above.
- Patent Documents 1 to 3 phenylethylene glycol diacrylate is used as an acrylate monomer having high etching resistance.
- Patent Document 4 a polyfunctional acrylate containing at least one of an alicyclic structure and an aromatic ring structure is used.
- Patent Documents 5 and 6 an acrylate monomer containing silicon is used in order to improve etching resistance.
- Patent Document 7 discloses an imprint material comprising a composition that defines physical properties in a liquid state and a solid state, and includes a surfactant and a polymerizable component, and an initiator that responds to a stimulus in order to change viscosity in response to the surfactant. Is disclosed.
- Patent Document 8 in consideration of the filling rate into the mold and the releasability, an internally added release agent that is not unevenly distributed at the gas-liquid interface of the curable composition is employed.
- Patent Document 9 a polymerizable compound containing a hydrocarbon group is employed in order to improve the releasability.
- the imprint method has been increasingly developed recently. Along with this, the required characteristics have become much stricter, and characteristics according to various needs have been demanded at a high level. One of them is releasability from the mold.
- the imprint method as described above, after the curable composition for imprint is applied to a substrate or a mold, the imprint curable composition is molded by pressing both of them and then cured. Thereafter, the mold is released from the cured product of the curable composition for imprints (also referred to as a cured film or an imprint layer) to obtain a cured product having a desired pattern.
- the adhesive force between the substrate and the cured product is not sufficiently high, a part or all of the cured product is peeled off together with the mold at the time of mold peeling. Therefore, a mold release agent or a specific polymerizable compound is used to accurately release the mold from the mold in a state where the cured product is adhered to the substrate side.
- the curable composition for imprints is required to form a pattern faithful to the mold. Therefore, the filling property to a mold is calculated
- the mold filling property tends to be inferior.
- An object of the present invention is to solve such a problem, and is a curable composition for imprints, a release agent, a cured product, a pattern forming method, and a pattern forming method capable of achieving both releasability and filling properties.
- An object is to provide a lithography method.
- the above problem can be solved by adopting a specific release agent for the curable composition for imprints. Specifically, the above problem has been solved by the following means ⁇ 1>, preferably ⁇ 2> to ⁇ 18>.
- a curable composition for imprints comprising a photopolymerization initiator and a release agent represented by the following formula (I) or formula (II): : Monofunctional polymerizable compound (1) linear alkyl group having 8 or more carbon atoms (2) branched alkyl group having 10 or more carbon atoms (3) linear alkyl group having 1 or more carbon atoms or branched alkyl group having 3 or more carbon atoms Aliphatic ring, aromatic ring or aromatic heterocyclic ring substituted with an alkyl group: release agent A 1- (B 1 ) x 1- (D 1 ) y 1- (E 1 ) z 1 -F 1 : Formula (I) In formula (I), A 1 is a carbon containing a linear aliphatic hydrocarbon group having 4 to 11 carbon atoms, a branched aliphatic hydrocarbon group having 5 to 18 carbon atoms, or a cyclic structure
- a 2 is a carbon containing a linear aliphatic hydrocarbon group having 4 to 11 carbon atoms, a branched aliphatic hydrocarbon group having 5 to 18 carbon atoms, or a cyclic structure having 5 or 6 carbon atoms.
- a 2 includes a release agent in which a linear aliphatic hydrocarbon group having 4 to 9 carbon atoms and F 2 is a linear aliphatic hydrocarbon group having 4 to 9 carbon atoms, ⁇ 1>
- a 1 is a linear aliphatic hydrocarbon group having 4 to 9 carbon atoms, a branched aliphatic hydrocarbon group having 5 to 18 carbon atoms, or a cyclic structure having 5 or 6 carbon atoms.
- a 2 is a carbon containing a linear aliphatic hydrocarbon group having 4 to 9 carbon atoms, a branched aliphatic hydrocarbon group having 5 to 18 carbon atoms, or a cyclic structure having 5 or 6 carbon atoms.
- F 2 represents a hydrogen atom, a linear aliphatic hydrocarbon group having 4 to 9 carbon atoms, a branched aliphatic hydrocarbon group having 5 to 18 carbon atoms, or carbon
- the imprint curability according to any one of ⁇ 1 to 6, which is an aliphatic hydrocarbon group having 5 to 11 carbon atoms containing a cyclic structure of 5 or 6, and y2 is an integer of 5 to 20 Composition.
- ⁇ 8> The curable composition for imprints according to any one of ⁇ 1> to ⁇ 7>, wherein the release agent has a weight average molecular weight of 300 to 1,000.
- composition for imprints according to any one of ⁇ 1> to ⁇ 8>, wherein the content of the release agent is 0.5% by mass or more and 7.0% by mass or less in the nonvolatile component.
- Composition. ⁇ 10> The imprint according to any one of ⁇ 1> to ⁇ 9>, wherein the polymerizable compound contained in the curable composition for imprints exhibits a surface tension of 33 mN / m or more at 23 ° C.
- Curable composition. ⁇ 11> The viscosity of the polymerizable compound contained in the curable composition for imprints is 20 mPa ⁇ s or less, and the solvent content in the composition is 3% by mass or less of the curable composition for imprints.
- ⁇ 12> The curable composition for imprints according to any one of ⁇ 1> to ⁇ 11>, wherein the surface tension at 23 ° C. of the curable composition for imprints is from 28 mN / m to 38 mN / m. .
- a mold release agent represented by the following formula (I) or formula (II); A 1- (B 1 ) x 1- (D 1 ) y 1- (E 1 ) z 1 -F 1 : Formula (I)
- a 1 is a carbon containing a linear aliphatic hydrocarbon group having 4 to 9 carbon atoms, a branched aliphatic hydrocarbon group having 5 to 18 carbon atoms, or a cyclic structure having 5 or 6 carbon atoms.
- a 2 is a carbon containing a linear aliphatic hydrocarbon group having 4 to 9 carbon atoms, a branched aliphatic hydrocarbon group having 5 to 18 carbon atoms, or a cyclic structure having 5 or 6 carbon atoms.
- ⁇ 14> The release agent according to ⁇ 13>, which is for a curable composition for imprints.
- ⁇ 15> A cured product obtained by curing the curable composition for imprints according to any one of ⁇ 1> to ⁇ 12>.
- ⁇ 16> The cured product according to ⁇ 15>, wherein the cured product is provided on a silicon substrate.
- the curable composition for imprints according to any one of ⁇ 1> to ⁇ 12> is applied onto a substrate or a mold, and the curable composition for imprints is applied to the mold and the above A pattern forming method including irradiating with light sandwiched between substrates.
- ⁇ 18> The pattern formation method according to ⁇ 17>, wherein the pattern includes any one of a line, a hole, and a pillar having a size of 20 nm or less.
- a curable composition for imprints a release agent, a cured product, a pattern forming method, and a lithography method that can achieve both excellent release properties and good filling properties.
- imprint preferably refers to pattern transfer having a size of 1 nm to 10 mm, and more preferably refers to pattern transfer having a size (nanoimprint) of approximately 10 nm to 100 ⁇ m.
- group (atomic group) in this specification the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent.
- the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- light includes not only light in a wavelength region such as ultraviolet, near ultraviolet, far ultraviolet, visible, infrared, and electromagnetic waves, but also radiation.
- radiation include microwaves, electron beams, extreme ultraviolet rays (EUV), and X-rays.
- Laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used.
- the light may be monochromatic light (single wavelength light) that has passed through an optical filter, or may be light having a plurality of different wavelengths (composite light).
- the atmospheric pressure at the time of measuring the boiling point in the present invention is 1013.25 hPa (1 atm) unless otherwise specified.
- the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
- the curable composition for imprints of the present invention is characterized by containing a specific polymerizable compound, a photopolymerization initiator, and a release agent represented by the following formula (I) or formula (II). Details of the present invention will be described below.
- the curable composition for imprints of the present invention has a monofunctional polymerizable compound having any one of the following structures (1) to (3) (hereinafter sometimes referred to as “specific monofunctional polymerizable compound”). ).
- a linear alkyl group having 8 or more carbon atoms (2) a branched alkyl group having 10 or more carbon atoms (3) a linear alkyl group having 1 or more carbon atoms or a branched alkyl group having 3 or more carbon atoms substituted,
- An alicyclic ring, an aromatic ring or an aromatic heterocyclic ring that is, an alicyclic ring substituted with a linear alkyl group having 1 or more carbon atoms or a branched alkyl group having 3 or more carbon atoms, or a linear alkyl group having 1 or more carbon atoms
- an aromatic ring substituted with a branched alkyl group having 3 or more carbon atoms, or a straight chain alkyl group having 1 or more carbon atoms or an aromatic heterocyclic ring substituted with a branched alkyl group having 3 or more carbon atoms
- Linear alkyl group having 8 or more carbon atoms The linear alkyl group having 8 or more carbon atoms is more preferably one having 10 or more carbon atoms, further preferably 11 or more carbon atoms, and still more preferably 12 or more carbon atoms. Moreover, 20 or less carbon atoms are preferable, 18 or less carbon atoms are more preferable, 16 or less carbon atoms are more preferable, and 14 or less carbon atoms are still more preferable.
- the branched alkyl group having 10 or more carbon atoms is preferably one having 10 to 20 carbon atoms, more preferably 10 to 16 carbon atoms, still more preferably 10 to 14 carbon atoms, More preferably, the number of carbon atoms is 10 to 12.
- the branched alkyl group is more preferably a straight-chain alkyl group having 1 or more carbon atoms.
- the straight chain alkyl group having 1 or more carbon atoms preferably has 4 or more carbon atoms, and more preferably 6 or more carbon atoms.
- the branched alkyl group preferably has 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more.
- the carbon number of the linear alkyl group having 1 or more carbon atoms is preferably 14 or less, more preferably 12 or less, and still more preferably 10 or less.
- the alicyclic ring, aromatic ring or aromatic heterocyclic ring may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring. In the case of a condensed ring, the number of rings is preferably 2 or 3.
- the ring is preferably a 3- to 8-membered ring, more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring.
- Specific examples of the ring include an example of the ring Cz described later.
- the structure (3) is preferably a structure represented by the following formula (A1).
- Ar 1 is an aromatic ring, preferably having 6 to 22 carbon atoms, more preferably 6 to 18 and even more preferably 6 to 10. Specifically, a benzene ring or a naphthalene ring is preferable. Ar 1 may have a substituent T as long as the effects of the present invention are exhibited.
- R B is a linear alkyl group or branched alkyl group as defined in (3), and their preferable ranges are also the same. * Represents a bonding position.
- the molecular weight of the specific monofunctional polymerizable compound is preferably 50 or more, more preferably 100 or more, and further preferably 150 or more.
- the molecular weight is preferably 1000 or less, more preferably 800 or less, still more preferably 300 or less, and even more preferably 270 or less.
- the boiling point of the specific monofunctional polymerizable compound is preferably 85 ° C. or higher, more preferably 110 ° C. or higher, and further preferably 130 ° C. or higher. By setting the boiling point to the above lower limit or more, volatility can be suppressed.
- the upper limit of the boiling point is not particularly defined, but for example, the boiling point can be 350 ° C. or lower. It is preferable that at least a part of the specific monofunctional polymerizable compound is liquid at 23 ° C., and that 15% by mass or more of the polymerizable compound contained in the curable composition for imprints is liquid at 23 ° C. preferable.
- the kind of the polymerizable group that the specific monofunctional polymerizable compound has is not particularly defined, examples thereof include an ethylenically unsaturated group and an epoxy group, and an ethylenically unsaturated group is preferable.
- a (meth) acryloyl group is preferable, and an acryloyl group is more preferable.
- the type of atom constituting the specific monofunctional polymerizable compound is not particularly defined, but is preferably composed of only an atom selected from a carbon atom, an oxygen atom, a hydrogen atom and a halogen atom. More preferably, it is composed only of atoms selected from atoms and hydrogen atoms.
- the specific monofunctional polymerizable compound is preferably a compound in which a linear or branched hydrocarbon chain having 4 or more carbon atoms and a polymerizable group are bonded directly or via a linking group.
- a compound in which any one of the groups 3) and a polymerizable group are directly bonded is more preferable.
- the linking group include —O—, —C ( ⁇ O) —, —CH 2 —, or a combination thereof.
- the monofunctional polymerizable compound used in the present invention includes (1) a linear alkyl (meth) acrylate in which a linear alkyl group having 8 or more carbon atoms and a (meth) acryloyloxy group are directly bonded. preferable.
- the specific monofunctional polymerizable compound is preferably a compound represented by the following formula (I-1).
- R 12 represents any one of the structures (1) to (3).
- R 11 represents a hydrogen atom or a methyl group.
- L 11 represents a single bond or a linking group L described later, and represents a single bond, an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms) or an alkenylene group (2 to 24 is preferable, 2 to 12 is more preferable, and 2 to 6 is more preferable.
- R 12 and L 11 may combine with or without a linking group L to form a ring.
- R 12 and L 11 may have the substituent T.
- a plurality of the substituents T may be bonded to form a ring, may be bonded to R 12 , or may be bonded to L 11 to form a ring. When there are a plurality of substituents T, they may be the same or different.
- the preferable range of the alicyclic ring, aromatic ring or aromatic heterocyclic ring in the structure (3) of R 12 includes the following rings aCy, hCy and fCy, and these are collectively referred to as ring Cz.
- R 12 has the structure of (3), it is preferably a group represented by the formula (A1).
- the alicyclic fCy preferably has 3 to 22 carbon atoms, more preferably 4 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms.
- Specific examples thereof include cyclopropane ring, cyclobutane ring, cyclobutene ring, cyclopentane ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, cyclooctane ring, dicyclopentadiene ring, tetrahydrodicyclopentadiene ring, octahydronaphthalene ring, Examples include a decahydronaphthalene ring, a hexahydroindane ring, a bornane ring, a norbornane ring, a norbornene ring, an isobornane ring, a tricyclodecane ring, a tetracyclodode
- the aromatic ring aCy preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms.
- Specific examples of the aromatic ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenalene ring, fluorene ring, acenaphthylene ring, biphenylene ring, indene ring, indane ring, triphenylene ring, pyrene ring, chrysene ring, perylene ring. And tetrahydronaphthalene ring.
- the aromatic ring may have a structure in which a plurality of aromatic rings are connected, and examples thereof include a biphenyl ring and a bisphenyl ring.
- the aromatic heterocycle hCy preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 5 carbon atoms.
- thiophene ring examples include thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, isoindole ring, indole.
- the above-mentioned specific monofunctional polymerizable compound ((1), (2) or other polymerizable compound having a saturated aliphatic group having a relatively large carbon number, or (3) A combination of a polymerizable compound having an aromatic ring or aromatic heterocycle having a saturated aliphatic substituent such as A) and a release agent having a site defined by A 1 or A 2 , to the gas-liquid interface
- A a polymerizable compound having an aromatic ring or aromatic heterocycle having a saturated aliphatic substituent such as A
- a release agent having a site defined by A 1 or A 2
- the content of the specific monofunctional polymerizable compound used in the curable composition for imprints, when included, is preferably 6% by mass or more, more preferably 8% by mass or more, and more preferably 10% by mass or more. More preferably, 12 mass% or more is still more preferable.
- the content is more preferably 60% by mass or less, and may be 55% by mass or less.
- only one specific monofunctional polymerizable compound may be included, or two or more specific monofunctional polymerizable compounds may be included. When 2 or more types are included, the total amount is preferably within the above range.
- the curable composition for imprints may contain other monofunctional polymerizable compounds in addition to the specific monofunctional polymerizable compound.
- the curable composition for imprints preferably contains a polyfunctional polymerizable compound together with the specific monofunctional polymerizable compound.
- the polyfunctional polymerizable compound is not particularly defined, but preferably includes at least one of an alicyclic ring, an aromatic ring and an aromatic heterocyclic ring, and includes at least one of an aromatic ring and an aromatic heterocyclic ring. Is more preferable.
- a compound containing at least one of an alicyclic ring, an aromatic ring and an aromatic heterocyclic ring may be referred to as a ring-containing polyfunctional polymerizable compound.
- the molecular weight of the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is preferably 1000 or less, more preferably 800 or less, further preferably 500 or less, and further preferably 350 or less.
- the upper limit of the molecular weight is not particularly defined, but can be, for example, 200 or more.
- the number of polymerizable groups contained in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is 2 or more, preferably 2 to 7, more preferably 2 to 4, more preferably 2 or 3. 2 is more preferable.
- the type of polymerizable group possessed by the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is not particularly defined, but examples thereof include ethylenically unsaturated groups and epoxy groups. preferable.
- ethylenically unsaturated group a (meth) acryloyl group is preferable, and an acryloyl group is more preferable.
- Two or more polymerizable groups may be contained in one molecule, or two or more polymerizable groups of the same type may be contained.
- the type of atoms constituting the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is not particularly defined, but is composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms and halogen atoms. It is preferable that it is composed only of atoms selected from a carbon atom, an oxygen atom and a hydrogen atom.
- the ring contained in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints may be monocyclic or condensed, but is preferably monocyclic.
- the number of rings is preferably 2 or 3.
- the ring is preferably a 3- to 8-membered ring, more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring.
- the ring may be an alicyclic ring, an aromatic ring or an aromatic heterocyclic ring, but is preferably an aromatic ring or an aromatic heterocyclic ring, more preferably an aromatic ring.
- Specific examples of the ring include an example of the ring Cz.
- the number of rings in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints may be one or two or more, but preferably one or two, more preferably one. . In the case of a condensed ring, one condensed ring is considered.
- the structure of the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is (polymerizable group)-(single bond or divalent linking group)-(divalent group having a ring)-(single bond). Or a divalent linking group)-(polymerizable group).
- the linking group is preferably an alkylene group, more preferably an alkylene group having 1 to 3 carbon atoms.
- the ring-containing polyfunctional polymerizable compound used in the curable composition for imprints is preferably represented by the following formula (I-2).
- Q is an alicyclic ring (preferably having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, still more preferably 3 to 6 carbon atoms) or an aromatic ring (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 10 represents a 1 + q-valent group having at least one selected from 10) and an aromatic heterocyclic ring (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 5 carbon atoms).
- R 21 and R 22 each independently represents a hydrogen atom or a methyl group.
- L 21 and L 22 each independently represent a single bond or a linking group L described later.
- Q and L 21 or L 22 may combine with or without a linking group L to form a ring.
- Q, L 21 and L 22 may have the substituent T.
- a plurality of substituents T may be bonded to form a ring, may be bonded to Q, or may be bonded to L 21 or L 22 to form a ring.
- When there are a plurality of substituents T they may be the same or different.
- the preferred range of the alicyclic ring, aromatic ring or aromatic heterocyclic ring in Q is the same as that of the ring Cz.
- q is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.
- Q has a structure in which a plurality of alicyclic rings, a plurality of aromatic rings, a plurality of aromatic heterocyclic rings, an alicyclic ring and an aromatic ring, an alicyclic ring and an aromatic heterocyclic ring, and an aromatic ring and an aromatic heterocyclic ring are connected. You may do it.
- Examples of the structure in which the aromatic rings are linked include structures of the following formulas AR-1 and AR-2.
- Ar 3 to Ar 6 are each independently an aromatic ring, an aromatic heterocyclic ring, or an alicyclic ring, and a preferable example thereof includes a ring Cz.
- A is a linking group, and examples of the linking group L include -CH 2- , -O-, -S-, -SO 2- , and -C which may be substituted with a halogen atom (particularly a fluorine atom).
- a divalent group selected from the group consisting of (CH 3 ) 2 — is preferable.
- Ar 3 to Ar 6 may have a substituent T.
- substituents T When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to the rings Ar 3 to Ar 6 in the formula through or without a linking group L to form a ring. Further, the substituent T may be bonded to the linking group A or the following linking groups L 21 and L 22 via the linking group L or not to form a ring. * Represents a bonding position with L 21 and L 22 .
- n3 to n6 are each independently an integer of 1 to 3, preferably 2 or 3, and more preferably 1. However, n3 + n4 and n5 + n6 are respectively 1 + q.
- Examples of the polyfunctional polymerizable compound used in the curable composition for imprints include the following first group and second group. However, it goes without saying that the present invention is not limited to these examples.
- the first group is more preferable.
- the curable composition for imprints may contain a polyfunctional polymerizable compound other than the ring-containing polyfunctional polymerizable compound.
- a polyfunctional polymerizable compound other than the ring-containing polyfunctional polymerizable compound.
- compounds represented by the following formula (I-3) are preferable.
- L 30 is a group having a linear or branched alkane structure (preferably having 1 to 12 carbon atoms, more preferably 1 to 6), or a group having a linear or branched alkene structure (preferably having 2 to 12 carbon atoms). 6 is more preferable), and represents a 1 + r valent group having at least one selected from a group having a linear or branched alkyne structure (preferably having 2 to 12 carbon atoms, more preferably 2 to 6).
- R 25 and R 26 each independently represents a hydrogen atom or a methyl group.
- L 25 and L 26 each independently represent a single bond or a linking group L described later.
- L 30 and L 25 or L 26 may combine with or without a linking group L to form a ring.
- L 25 , L 26 and L 30 may have the substituent T.
- a plurality of substituents T may be bonded to form a ring, or may be bonded to another linking group to form a ring. When there are a plurality of substituents T, they may be the same or different.
- r is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.
- a linking group having a hetero atom (O, S, NR N ) may intervene in L 30 .
- the number of intervening linking groups having a hetero atom is preferably one per 1 to 6 carbon atoms of L 30 .
- Examples of other polyfunctional polymerizable compounds used in the curable composition for imprints include polyfunctional polymerizable compounds having no ring among the polymerizable compounds described in JP-A No. 2014-170949. Is included herein. More specifically, for example, the following compounds are exemplified.
- the polyfunctional polymerizable compound is preferably contained in an amount of 30% by mass or more, more preferably 45% by mass or more, and 50% by mass or more, 55% by mass with respect to the total polymerizable compound in the curable composition for imprints. It may be the above.
- the upper limit value is preferably less than 95% by mass, more preferably 90% by mass or less, and may be 85% by mass or less and 70% by mass or less.
- the mass ratio of the ring-containing polyfunctional polymerizable compound to the other polyfunctional polymerizable compound is 30 to 90: ring-containing polyfunctional polymerizable compound: other polyfunctional polymerizable compound.
- the curable composition for imprints may contain only one type of polyfunctional polymerizable compound or two or more types. When 2 or more types are included, the total amount is preferably within the above range.
- 85% by mass or more of the composition is preferably a polymerizable compound, more preferably 90% by mass or more is a polymerizable compound, and 93% by mass or more. More preferably, it is a polymerizable compound.
- substituent T examples include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 1 to 6 carbon atoms), and a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms). 3 to 6 are more preferable), an arylalkyl group (preferably 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms, more preferably 7 to 11 carbon atoms), and an alkenyl group (preferably 2 to 24 carbon atoms are preferable 2 to 12 carbon atoms).
- an alkyl group preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 1 to 6 carbon atoms
- a cycloalkyl group preferably having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms. 3 to 6 are more preferable
- an arylalkyl group preferably 7 to 21 carbon atoms, more preferably
- a cycloalkenyl group (3 to 24 carbon atoms are preferable, 3 to 12 are more preferable, and 3 to 6 are more preferable), a hydroxyl group, an amino group (0 to 0 carbon atoms).
- acyl group preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 3 carbon atoms
- an acyloxy group preferably 2 to 12 carbon atoms are preferable 2 to 2 carbon atoms. 6 is more preferred, 2 to 3 are more preferred), aryloyl groups (preferably 7 to 23 carbons, 7 to 19 are more preferred, and 7 to 11 are more preferred), and aryloyloxy groups (having 7 to 23 carbons are preferred).
- 7 to 19 are more preferable, and 7 to 11 are more preferable.
- Carbamoyl group (1 to 12 carbon atoms is preferable, 1 to 6 is more preferable, 1 to 3 is more preferable), and sulfamoyl group (0 to 0 carbon atoms are preferable).
- a sulfo group preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms
- a heterocyclic group preferably 1 to 12 carbon atoms are preferable 1 to 8 carbon atoms
- RN represents a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, and still more preferably a methyl group).
- the alkyl moiety and alkenyl moiety contained in each substituent may be linear or branched, and may be linear or cyclic.
- the substituent T may further have a substituent T.
- the alkyl group may be a halogenated alkyl group, or may be a (meth) acryloyloxyalkyl group, an aminoalkyl group, or a carboxyalkyl group.
- the substituent is a group capable of forming a salt such as a carboxyl group or an amino group, the group may form a salt.
- the linking group L is a linear or branched alkylene group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 1 to 6 carbon atoms), an arylene group (preferably 6 to 22 carbon atoms, 6 to 18 carbon atoms). And more preferably 6 to 10), -O-, -S-, -SO 2- , -CO-, -NR N- , and combinations thereof.
- the alkylene group may have the substituent T.
- the alkylene group may be a fluorinated alkylene group having a fluorine atom.
- the number of atoms contained in the linking group L is preferably 1 to 24, more preferably 1 to 12, and still more preferably 1 to 6.
- the curable composition for imprints of the present invention contains a release agent represented by the following formula (I) or formula (II).
- a 1 is a linear aliphatic hydrocarbon group having 4 to 11 (preferably 4 to 9) carbon atoms, a branched aliphatic hydrocarbon having 5 to 18 (preferably 6 to 16) carbon atoms.
- a 2- (B 2 ) x 2- (D 2 ) y 2- (E 2 ) z 2 -F 2 Formula (II)
- a 2 is a linear aliphatic hydrocarbon group having 4 to 11 (preferably 4 to 9) carbon atoms, a branched aliphatic hydrocarbon having 5 to 18 (preferably 6 to 16) carbon atoms.
- hydrocarbon groups (A 1 , A 2 )
- the release agent has specific hydrocarbon groups A 1 and A 2
- the release agent is appropriately present at the gas-liquid interface, so that the excess of the hydrophobic polymerizable compound having the hydrocarbon chain at the interface is present. Prevents segregation and suppresses deterioration of filling properties due to segregation of hydrophobic components.
- the polymerizable compound has a straight-chain alkyl group having 8 or more carbon atoms that has a high segregation ability at the gas-liquid interface, it functions particularly effectively.
- the linear aliphatic hydrocarbon group has 4 to 11 carbon atoms, preferably 5 or more carbon atoms, more preferably 6 or more carbon atoms.
- the branched aliphatic hydrocarbon group has 5 to 18 carbon atoms, preferably 6 or more carbon atoms, more preferably 7 or more carbon atoms, still more preferably 8 or more carbon atoms, and may have 9 or more carbon atoms. Moreover, carbon number 17 or less is preferable and carbon number 16 or less may be sufficient.
- the aliphatic hydrocarbon group having 5 to 11 carbon atoms including a cyclic structure having 5 or 6 carbon atoms may consist of only a cyclic structure, or a cyclic structure and a linear or branched aliphatic hydrocarbon group. May be.
- the cyclic structure is a 5-membered or 6-membered alicyclic ring.
- the cyclic structure may be a single ring or a condensed ring.
- the aliphatic hydrocarbon group having 5 to 11 carbon atoms including a cyclic structure having 5 or 6 carbon atoms is preferably a group represented by the following formula (A2).
- Ar 2 is an aromatic ring, preferably having 6 to 22 carbon atoms, more preferably 6 to 18 and even more preferably 6 to 10. Specifically, a benzene ring or a naphthalene ring is preferable. Ar 2 may have a substituent as long as the effects of the present invention are achieved.
- R A is preferably a linear aliphatic hydrocarbon group having 4 to 11 carbon atoms (particularly preferably 4 to 9) or a branched aliphatic hydrocarbon group having 5 to 18 carbon atoms (particularly preferably 6 to 16 carbon atoms).
- L A is a single bond or an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1-6, more preferably 1-3). * Represents a bonding position.
- a 1 and A 2 are saturated hydrocarbon groups and preferably have no substituent. If the number of carbon atoms of A 1 and A 2 is less than the above lower limit, the hydrophobicity is weak and the surface energy of the mold cannot be reduced sufficiently, resulting in a decrease in mold release. On the other hand, when the above upper limit is exceeded, the hydrophobicity is too strong, the wettability of the mold surface is lowered, and the filling property is deteriorated. Note that the range of the carbon number between the straight chain and the branched chain is different because the branched aliphatic hydrocarbon group has a lower surface energy reducing ability than the straight chain, and therefore requires a larger number of carbon atoms. .
- a 1 and A 2 do not have a fluorine atom. By not having fluorine atoms, it is possible to prevent excessive reduction of the surface energy of the mold surface and to improve the releasability without lowering the filling property. Furthermore, A 1 and A 2 are preferably composed only of carbon atoms and hydrogen atoms. By being composed only of carbon atoms and hydrogen atoms, the surface energy can be appropriately reduced.
- the linking group may or may not be contained in the release agent. Therefore, x1, x2, z1 and z2 in the formula are preferably 0 or 1, and x1, x2, z1 and z2 are preferably 0.
- B 1 , B 2 , E 1 , and E 2 are each a divalent linking group in which the linking site with A 1 , F 1 , A 2 , and F 2 is not an aliphatic hydrocarbon group.
- the coupling group which has ring structures other than an aliphatic hydrocarbon is mentioned.
- Examples of the ring structure constituting the linking group include an aromatic ring, an aromatic ring having 6 to 18 carbon atoms (more preferably 6 to 10 carbon atoms) such as a benzene ring and a naphthalene ring, a thiophene ring, a furan ring, and a pyrrole. Heterocycles such as a ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, and thiazole ring are preferred.
- group containing a polar functional group is illustrated.
- B 2 or E 2 when y2 is 0, it is preferred that B 2 or E 2 contains a polar functional group. That is, at least one of x2 and z2 is 1.
- B 2 or E 2 is a linking group containing a polar functional group, an oxygen atom, a sulfur atom, a carbonyl group, —NR N —, a sulfonyl group, —SO 4 —, or a combination thereof is more preferable.
- the release agent preferably has an alkylene oxide structure from the viewpoint of adjusting the hydrophilicity / hydrophobicity ratio in the compound.
- the alkylene oxide structure is preferably a structure consisting only of a linear alkylene group (preferably an ethylene group) and an oxygen atom.
- Specific examples of the alkylene oxide structure include methylene oxide, ethylene oxide, propylene oxide, butylene oxide and the like.
- the repeating numbers y1 and y2 of the alkylene oxide structure are each independently 0 or more, preferably 1 or more, more preferably 4 or more, and still more preferably 5 or more. Moreover, it is 30 or less, 25 or less are preferable and 20 or less are more preferable.
- y1 and y2 are particularly preferably integers of 5 to 20. If y1 and y2 are too small, the ratio of the hydrophobic group in the release agent compound is increased, the wettability with the mold is lowered, and the filling property may be deteriorated. On the other hand, if y1 and y2 are too large, the ratio of the hydrophobic group may be reduced, and the releasability may be deteriorated.
- the terminal group of the release agent is F 1 (polar functional group) or F 2 (hydrogen atom, straight chain aliphatic hydrocarbon group having 4 to 11 (preferably 4 to 9) carbon atoms, 5 to 18 carbon atoms. Or an aliphatic hydrocarbon group having 5 to 11 carbon atoms including a cyclic structure having 5 or 6 carbon atoms and having no fluorine atom).
- the polar functional group include a hydroxyl group, an amino group, a sulfonyl group-containing group, a sulfino group, a sulfonimidyl group-containing group, and a carboxyl group.
- a hydroxyl group, an amino group, a sulfonyl group-containing group (particularly a sulfonyl group, a sulfo group, or a sulfonamide group) and a carboxyl group are preferable.
- the sulfonyl group-containing group may be a sulfonyl group (—SO 2 R), a sulfonamide group (R—SO 2 —NH—), a sulfamoyl group (—SO 2 NH 2 ), or a sulfo group (—SO 3 H).
- the sulfonimide group-containing group is preferably —SO (NH) R.
- R represents an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 1 to 6 carbon atoms) or an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and 2 to 6 carbon atoms). More preferably) or an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms).
- a preferable range of F 2 is the same as that of A 1 .
- a 1 is preferably a linear aliphatic hydrocarbon group having 4 to 9 carbon atoms.
- a 2 is preferably a linear aliphatic hydrocarbon group having 4 to 9 carbon atoms, and F 2 is preferably a linear aliphatic hydrocarbon group having 4 to 9 carbon atoms.
- the formula (I) is preferably the following formula (I-1) or (I-2), more preferably the formula (I-1).
- L 1 represents a methylene group, an ethylene group, a propylene group, or a butylene group.
- R 1 represents a group having the same meaning as A 1, and the preferred range is also the same.
- n1 is the same number as y1, and a preferable range is also the same.
- R 2 represents a group having the same meaning as A 1, and the preferred range is also the same.
- a linking group containing a hetero atom (O, S, NH, etc.) in the chain of the aliphatic hydrocarbon group may be contained in a ratio of 1 or less per 2 carbon atoms.
- the formula (II) is preferably any of the following formulas (II-1) to (II-3), more preferably the formula (II-1).
- L 2 represents a methylene group, an ethylene group, a propylene group, or a butylene group.
- R 4 and R 5 each independently represent the same group as A 2, and the preferred range is also the same.
- n2 is the same number as y2, and the preferable range is also the same.
- R 6 and R 7 each independently represent a group having the same meaning as A 2, and the preferred range is also the same.
- R 8 and R 9 each independently represent the same group as A 2, and the preferred range is also the same.
- the molecular weight of the release agent is preferably a weight average molecular weight of 300 or more, more preferably 350 or more, still more preferably 400 or more, still more preferably 450 or more, and 500 or more. Even more preferably.
- the upper limit of the molecular weight is preferably 1,500 or less, more preferably 1000 or less, 950 or less, or 920 or less.
- the compounding amount of the release agent in the curable composition for imprints is preferably 0.5% by mass or more, more preferably 1.0% by mass or more in the nonvolatile component, and 2.0 More preferably, it is at least mass%. Moreover, it is preferable that it is 7.0 mass% or less in a non-volatile component, It is more preferable that it is 5.0 mass% or less, It is further more preferable that it is 4.0 mass% or less. When the amount of the release agent is not less than the above lower limit value, the releasability is effectively exhibited, and when it is not more than the upper limit value, the filling property is improved and the roughness of the pattern surface can be effectively suppressed.
- the curable composition for imprints may contain only one type of release agent or two or more types. When 2 or more types are included, the total amount is preferably within the above range.
- mold release agent examples include compounds C-1 to C-15 exemplified in the examples described later, and the following compounds C-31 to C-37 can also be exemplified.
- the curable composition for imprints of the present invention contains a photopolymerization initiator.
- a photopolymerization initiator used in the present invention any compound can be used as long as it is a compound that generates an active species that polymerizes the above-described polymerizable compound by light irradiation.
- a photoinitiator a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is more preferable.
- radical photopolymerization initiator used in the present invention for example, a commercially available initiator can be used. As these examples, for example, those described in paragraph No. 0091 of JP-A-2008-105414 can be preferably used. Of these, acetophenone compounds, acylphosphine oxide compounds, and oxime ester compounds are particularly preferred from the viewpoints of curing sensitivity and absorption characteristics.
- Specific examples include the following photopolymerization initiators.
- a photoinitiator may be used individually by 1 type, it is also preferable to use 2 or more types together. When using 2 or more types together, it is more preferable to use 2 or more types of radical photopolymerization initiators together.
- the content of the photopolymerization initiator used in the present invention is preferably 0.01 to 15% by mass, more preferably 0.1 to 10% by mass, based on the total composition excluding the solvent. It is more preferably 5 to 7% by mass, and further preferably 1 to 5% by mass. When using 2 or more types of photoinitiators, the total amount becomes the said range.
- the content of the photopolymerization initiator is 0.01% by mass or more, the sensitivity (fast curability), resolution, line edge roughness, and coating strength tend to be further improved, which is preferable.
- content of a photoinitiator is 15 mass% or less, it exists in the tendency for a light transmittance, coloring property, handleability, etc. to improve more, and it is preferable.
- the curable composition for imprints used in the present invention may contain other components without departing from the spirit of the present invention.
- Other components include surfactants, sensitizers, antioxidants, polymerization inhibitors (eg, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical), ultraviolet absorbers And solvents.
- Each of these compounds may contain only 1 type, and may contain 2 or more types.
- the description in paragraphs 0061 to 0064 of JP 2014-170949 A can be referred to, and the contents thereof are incorporated in the present specification.
- the curable composition for imprints of the present invention preferably contains substantially no solvent. “Substantially free” means 3% by mass or less of the curable composition for imprints, preferably 1% by mass or less, and more preferably 0.5% by mass or less.
- the curable composition for imprints of the present invention does not necessarily contain a solvent, but may be optionally added when finely adjusting the viscosity of the composition.
- Solvents that can be preferably used in the curable composition of the present invention include those commonly used in curable compositions for imprints and photoresists, and dissolve and uniformly disperse the compounds used in the present invention. Any material can be used as long as it does not react with these components.
- the curable composition for imprints of the present invention does not substantially contain a component having a molecular weight of 2000 or more. “Substantially free” means 3% by mass or less of the nonvolatile component of the curable composition for imprints, preferably 1% by mass or less, and more preferably 0.5% by mass or less.
- the Onishi parameter of the curable composition for imprints of the present invention is preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3.9 or less, and 3.7 or less. Is more preferable, and it is still more preferable that it is 3.6 or less.
- the lower limit value of the Onishi parameter may be 3.0 or more, and may be 3.5 or more.
- the viscosity at 23 ° C. of the curable composition for imprints is preferably 20 mPa ⁇ s or less, and the solvent content is preferably 3% by mass or less of the curable composition for imprints.
- the viscosity is measured according to the method described in Examples described later.
- the curable composition for imprints has a surface tension of 33 mN / m or more at 23 ° C., wherein the composition containing only the polymerizable compound in the components contained in the imprint curable composition. It is preferable to show this.
- the surface tension is measured according to the method described in Examples described later.
- the curable composition for imprints of the present invention may be filtered before use.
- a polytetrafluoroethylene (PTFE) filter or a Nylon (nylon) filter can be used.
- the pore diameter during filtration is preferably 0.003 to 5.0 ⁇ m. Details of the filtration can be referred to the description in paragraph 0070 of JP2014-170949A, the contents of which are incorporated herein.
- the present invention also discloses a cured product obtained by curing the curable composition for imprints of the present invention.
- the cured product is preferably provided on a silicon substrate.
- the curable composition for imprints of the present invention is applied on a substrate or a mold, and the curable composition for imprints is sandwiched between the mold and the substrate. Including irradiation.
- a lower layer film, an adhesion film, or a primer film (liquid film) may be formed on the surface of the substrate, and the curable composition for imprints may be applied to the surface.
- the pattern formed by the pattern forming method of the present invention is also useful as an etching resist (lithographic mask).
- a pattern as an etching resist
- a micro-order fine pattern is formed.
- a nano-order fine pattern can be formed, and a pattern having a size of 25 nm or less, particularly 20 nm or less can be formed.
- the lower limit of the pattern size formed by the pattern forming method of the present invention is not particularly limited, but can be, for example, 10 nm or more.
- the pattern size means the thinnest dimension among the patterns formed by the pattern forming method of the present invention.
- a line pattern it is the line width of a pattern, and in the case of a pillar / hole pattern, it means the diameter of the pattern.
- a desired pattern is formed on the substrate by etching using an etching gas such as hydrogen fluoride in the case of wet etching or a mixed gas of CF 4 or CHF 3 / CF 4 / Ar in the case of dry etching. Can be formed.
- the pattern has particularly good etching resistance against dry etching. That is, the pattern obtained by the production method of the present invention is preferably used as a lithography mask.
- the description in paragraphs 0057 to 0071 of JP-A-2015-185798 can be referred to, and the contents thereof are incorporated in the present specification.
- the weight average molecular weight of the release agent was calculated using LC-MS (high performance liquid chromatograph mass spectrometer).
- the LC column used was TSKgel ODS-80Ts manufactured by TOSOH, and the eluent was H 2 O / MeOH (both dissolved in ammonium acetate).
- ESI-Posi was selected as the ionization method for MS.
- the weight average molecular weight Mw was calculated by grasping the molecular weight distribution from the MS spectrum. Note that MeOH is methanol.
- ⁇ Measurement of viscosity> The viscosity was measured by adjusting the temperature of the sample cup to 23 ° C. using an E-type rotational viscometer RE85L manufactured by Toki Sangyo Co., Ltd. and a standard cone rotor (1 ° 34 ′ ⁇ R24). The unit is mPa ⁇ s. Other details regarding the measurement conformed to JISZ8803: 2011. Two samples were prepared for each level and measured three times each. A total of 6 arithmetic average values were adopted as evaluation values.
- the curable composition for imprints was applied to a silicon wafer (silicon substrate) by an inkjet method using an inkjet printer DMP-2831 manufactured by FUJIFILM Dimatix as an inkjet apparatus, and then sandwiched between the molds in a helium atmosphere. .
- the ejection pattern by inkjet was arranged in a rhombus lattice, the interval was diagonal: 140 ⁇ m / 80 ⁇ m, and the ejection amount was 1 pL. After exposing on the condition of 100 mJ / cm ⁇ 2 > using the high pressure mercury lamp from the quartz mold side, the pattern was obtained by releasing the quartz mold.
- IJ Inkjet
- inkjet aptitude Evaluation of the IJ ejection performance was performed using an inkjet printer DMP-2831 manufactured by FUJIFILM Dimatix. While observing the state of discharge of the composition whose temperature was adjusted to 23 ° C. with a CCD camera (CSD image sensor camera), the discharge conditions such as discharge waveform and discharge voltage were optimized. Five discharge ports that performed the most stable discharge were selected, and the composition was discharged onto a silicon wafer at intervals of 100 ⁇ m (square array) (discharge area 5 mm square, 2500 dots). By exchanging the ink jet nozzle, the discharge amount was changed to 1 pL and 6 pL, and the examination was made.
- CCD camera CCD image sensor camera
- ⁇ Pattern formability> The pattern produced by the evaluation of the release force was observed and evaluated as follows. A: Good pattern transfer was confirmed over the entire surface. B: Pattern surface roughness or pattern omission was observed. C: Both pattern surface roughness and pattern omission were observed.
- a quartz mold (array: square array, pitch: 4 ⁇ m) having a concave structure with each opening having a radius of 1 ⁇ m and a depth of 2 ⁇ m was used.
- the curable composition for imprints was applied onto a silicon wafer by an inkjet method using an inkjet printer DMP-2831 manufactured by FUJIFILM Dimatix as an inkjet apparatus, and then sandwiched between the molds in a helium atmosphere.
- the state of filling the curable composition for imprint in the concave portion of the quartz mold was observed with a CCD camera, and the time required for completion of filling was measured.
- B 3 seconds or more and less than 5 seconds
- C 5 seconds or more and less than 10 seconds
- D 10 seconds or more
- the monofunctional polymerizable compound having any one of the structures (1) to (3) specified in the present invention and a release agent satisfying the formula (I) or the formula (II) are used. It was found that the curable composition for imprints can achieve both excellent mold release properties and good filling properties (Examples 1 to 19). It was also found that high performance can be obtained in ink jet aptitude and pattern formability.
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Abstract
Description
インプリント法としては、その転写方法から熱インプリント法、光インプリント法と呼ばれる方法が提案されている。熱インプリント法では、ガラス転移温度(以下、「Tg」ということがある)以上に加熱した熱可塑性樹脂にモールドをプレスし、冷却後にモールドを離型することにより微細パターンを形成する。この方法は多様な材料を選択できるが、プレス時に高圧を要すること、熱収縮等により微細なパターン形成が困難であるといった問題点も有する。
光インプリント法では、基板(必要に応じて密着処理を行う)上にインプリント用硬化性組成物を塗布後、石英等の光透過性素材で作製されたモールドを押し当てる。モールドを押し当てた状態で光照射によりインプリント用硬化性組成物を硬化し、その後モールドを離型することで目的のパターンが転写された硬化物が作製される。
基板上にインプリント用硬化性組成物を適用する方法としては、スピンコート法やインクジェット法が挙げられる。特にインクジェット法は、インプリント用硬化性組成物のロスが少ないといった観点から、近年注目される適用方法である。
一方、インプリント用硬化性組成物は、モールドに忠実なパターンを形成することが求められる。そのため、モールドへの充填性が求められる。しかしながら、一般的に離型剤や特定の重合性化合物を配合するとモールドへの充填性が劣る傾向にある。
本発明は、かかる課題を解決することを目的としたものであって、離型性と充填性の両立を可能とするインプリント用硬化性組成物、離型剤、硬化物、パターン形成方法およびリソグラフィー方法を提供することを目的とする。
光重合開始剤および
下記式(I)または式(II)で表される離型剤
を含む、インプリント用硬化性組成物;
:単官能重合性化合物
(1)炭素数8以上の直鎖アルキル基
(2)炭素数10以上の分岐アルキル基
(3)炭素数1以上の直鎖のアルキル基または炭素数3以上の分岐のアルキル基が置換した、脂環、芳香族環または芳香族複素環
:離型剤
A1-(B1)x1-(D1)y1-(E1)z1-F1 :式(I)
式(I)において、A1は炭素数4~11の直鎖の脂肪族炭化水素基、炭素数5~18の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基を表し、A1がフッ素原子を有することはなく、B1はA1との結合部位が脂肪族炭化水素基でない2価の連結基であり、x1は0または1であり、D1はアルキレンオキシド構造であり、E1はF1との結合部位が脂肪族炭化水素基でない2価の連結基であり、F1は極性官能基であり、y1は0~30の整数であり、z1は0または1である;
A2-(B2)x2-(D2)y2-(E2)z2-F2 :式(II)
式(II)において、A2は炭素数4~11の直鎖の脂肪族炭化水素基、炭素数5~18の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基を表し、A2がフッ素原子を有することはなく、B2はA2との結合部位が脂肪族炭化水素基でない2価の連結基であり、x2は0または1であり、D2はアルキレンオキシド構造であり、E2はF2との結合部位が脂肪族炭化水素基でない2価の連結基であり、F2は水素原子、炭素数4~11の直鎖の脂肪族炭化水素基、炭素数5~18の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基であり、F2がフッ素原子を有することはなく、y2は0~30の整数であり、z2は0または1である;但し、y2が0のときは、B2またはE2が極性官能基を含む。
<2> A1が炭素数4~9の直鎖の脂肪族炭化水素基である離型剤を含む、<1>に記載のインプリント用硬化性組成物。
<3> A2は炭素数4~9の直鎖の脂肪族炭化水素基、かつF2が炭素数4~9の直鎖の脂肪族炭化水素基である離型剤を含む、<1>に記載のインプリント用硬化性組成物。
<4> 上記極性官能基がヒドロキシル基、アミノ基、スルホニル基含有基、スルフィノ基、スルホンイミドイル基含有基およびカルボキシル基からなる群から選ばれる、<1>~<3>のいずれか1つに記載のインプリント用硬化性組成物。
<5> 上記y1およびy2がそれぞれ独立に5~20の整数である、<1>~<4>のいずれか1つに記載のインプリント用硬化性組成物。
<6> 上記x1およびx2が0である、<1>~<5>のいずれか1つに記載のインプリント用硬化性組成物。
<7> 式(I)において、A1は炭素数4~9の直鎖の脂肪族炭化水素基、炭素数5~18の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基を表し、y1は5~20の整数であるか、
式(II)において、A2は炭素数4~9の直鎖の脂肪族炭化水素基、炭素数5~18の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基を表し、F2は水素原子、炭素数4~9の直鎖の脂肪族炭化水素基、炭素数5~18の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基であり、y2は5~20の整数である、<1~6のいずれか1つに記載のインプリント用硬化性組成物。
<8> 上記離型剤の重量平均分子量が300~1000である、<1>~<7>のいずれか1つに記載のインプリント用硬化性組成物。
<9> 上記離型剤の含有量が不揮発性成分中0.5質量%以上7.0質量%以下である、<1>~<8>のいずれか1つに記載のインプリント用硬化性組成物。
<10> 上記インプリント用硬化性組成物に含まれる重合性化合物が、23℃において33mN/m以上の表面張力を示す、<1>~<9>のいずれか1つに記載のインプリント用硬化性組成物。
<11> 上記インプリント用硬化性組成物に含まれる重合性化合物の粘度が20mPa・s以下であり、かつ、組成物中の溶剤含有量がインプリント用硬化性組成物の3質量%以下である、<1>~<10>のいずれか1つに記載のインプリント用硬化性組成物。
<12> 上記インプリント用硬化性組成物の23℃における表面張力が28mN/m以上38mN/mである、<1>~<11>のいずれか1つに記載のインプリント用硬化性組成物。
<13> 下記式(I)または式(II)で表される離型剤;
A1-(B1)x1-(D1)y1-(E1)z1-F1 :式(I)
式(I)において、A1は炭素数4~9の直鎖の脂肪族炭化水素基、炭素数5~18の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基を表し、A1がフッ素原子を有することはなく、B1はA1との結合部位が脂肪族炭化水素基でない2価の連結基であり、x1は0または1であり、D1はアルキレンオキシド構造であり、E1はF1との結合部位が脂肪族炭化水素基でない2価の連結基であり、F1は極性官能基であり、y1は5~20の整数であり、z1は0または1である;
A2-(B2)x2-(D2)y2-(E2)z2-F2 :式(II)
式(II)において、A2は炭素数4~9の直鎖の脂肪族炭化水素基、炭素数5~18の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基を表し、A2がフッ素原子を有することはなく、B2はA2との結合部位が脂肪族炭化水素基でない2価の連結基であり、x2は0または1であり、D2はアルキレンオキシド構造であり、E2はF2との結合部位が脂肪族炭化水素基でない2価の連結基であり、F2は水素原子、炭素数4~9の直鎖の脂肪族炭化水素基、炭素数5~18の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基であり、F2がフッ素原子を有することはなく、y2は5~20の整数であり、z2は0または1である;但し、y2が0のときは、B2またはE2が極性官能基を含む。
<14> インプリント用硬化性組成物用である、<13>に記載の離型剤。
<15> <1>~<12>のいずれか1つに記載のインプリント用硬化性組成物を硬化してなる硬化物。
<16> 上記硬化物が、シリコン基板の上に設けられている、<15>に記載の硬化物。
<17> <1>~<12>のいずれか1つに記載のインプリント用硬化性組成物を、基板上またはモールド上に適用し、上記インプリント用硬化性組成物を、上記モールドと上記基板で挟んだ状態で光照射することを含むパターン形成方法。
<18> 上記パターンのサイズが20nm以下のライン、ホール、ピラーのいずれかの形状を含む<17>に記載のパターン形成方法。
<19> <17>または<18>に記載のパターン形成方法で得られたパターンをマスクとしてエッチングを行う、リソグラフィー方法。
本明細書において「~」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
本明細書において、「(メタ)アクリレート」は、アクリレートおよびメタクリレートを表し、「(メタ)アクリル」は、アクリルおよびメタクリルを表し、「(メタ)アクリロイル」は、アクリロイルおよびメタクリロイルを表す。「(メタ)アクリロイルオキシ」は、アクリロイルオキシおよびメタクリロイルオキシを表す。
本明細書において、「インプリント」は、好ましくは、1nm~10mmのサイズのパターン転写をいい、より好ましくは、およそ10nm~100μmのサイズ(ナノインプリント)のパターン転写をいう。
本明細書における基(原子団)の表記において、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
本明細書において、「光」には、紫外、近紫外、遠紫外、可視、赤外等の領域の波長の光や、電磁波だけでなく、放射線も含まれる。放射線には、例えばマイクロ波、電子線、極端紫外線(EUV)、X線が含まれる。また248nmエキシマレーザー、193nmエキシマレーザー、172nmエキシマレーザーなどのレーザー光も用いることができる。これらの光は、光学フィルタを通したモノクロ光(単一波長光)を用いてもよいし、複数の波長の異なる光(複合光)でもよい。
本発明における沸点測定時の気圧は、特に述べない限り、1013.25hPa(1気圧)とする。
本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
<<重合性化合物>>
<<<単官能重合性化合物>>>
本発明のインプリント用硬化性組成物は下記(1)~(3)のいずれかの構造を有する単官能重合性化合物(以下、これを「特定の単官能重合性化合物」と呼ぶことがある)を含有する。
(1)炭素数8以上の直鎖アルキル基
(2)炭素数10以上の分岐アルキル基
(3)炭素数1以上の直鎖のアルキル基または炭素数3以上の分岐のアルキル基が置換した、脂環、芳香族環または芳香族複素環(すなわち、炭素数1以上の直鎖のアルキル基または炭素数3以上の分岐のアルキル基が置換した脂環、炭素数1以上の直鎖のアルキル基または炭素数3以上の分岐のアルキル基が置換した芳香族環、あるいは炭素数1以上の直鎖のアルキル基または炭素数3以上の分岐のアルキル基が置換した芳香族複素環)
炭素数8以上の直鎖アルキル基は、炭素数10以上のものがより好ましく、炭素数11以上がさらに好ましく、炭素数12以上が一層好ましい。また、炭素数20以下が好ましく、炭素数18以下がより好ましく、炭素数16以下がさらに好ましく、炭素数14以下が一層好ましい。
(2)炭素数10以上の分岐アルキル基
上記炭素数10以上の分岐アルキル基は、炭素数10~20のものが好ましく、炭素数10~16がより好ましく、炭素数10~14がさらに好ましく、炭素数10~12が一層好ましい。
(3)炭素数1以上の直鎖のアルキル基または炭素数3以上の分岐のアルキル基が置換した脂環、炭素数1以上の直鎖のアルキル基または炭素数3以上の分岐のアルキル基が置換した芳香族環、あるいは炭素数1以上の直鎖の分岐のアルキル基または炭素数3以上の分岐のアルキル基が置換した芳香族複素
炭素数1以上の直鎖のアルキル基または炭素数3以上の分岐のアルキル基は、炭素数1以上の直鎖の直鎖のアルキル基がより好ましい。炭素数1以上の直鎖の直鎖のアルキル基の炭素数は4以上であることが好ましく、6以上であることがより好ましい。分岐のアルキル基の炭素数は4以上であることが好ましく、6以上であることがより好ましく、8以上であることがさらに好ましい。炭素数1以上の直鎖のアルキル基の炭素数は、14以下が好ましく、12以下がより好ましく、10以下がさらに好ましい。
脂環、芳香族環または芳香族複素環の環は、単環であっても縮環であってもよいが、単環であることが好ましい。縮環である場合は、環の数は、2つまたは3つが好ましい。環は、3~8員環が好ましく、5員環または6員環がより好ましく、6員環がさらに好ましい。環の具体例としては、後述する環Czの例が挙げられる。
特定の単官能重合性化合物の沸点は、85℃以上であることが好ましく、110℃以上がより好ましく、130℃以上がさらに好ましい。沸点を上記下限値以上とすることで、揮発性を抑制することができる。沸点の上限値については、特に定めるものでは無いが、例えば、沸点を350℃以下とすることができる。
特定の単官能重合性化合物の少なくとも一部は23℃で液体であることが好ましく、インプリント用硬化性組成物に含まれる重合性化合物の15質量%以上が23℃で液体であることがさらに好ましい。
脂環fCyとしては炭素数3~22が好ましく、4~18がより好ましく、6~10がさらに好ましい。その具体例としては、シクロプロパン環、シクロブタン環、シクロブテン環、シクロペンタン環、シクロヘキサン環、シクロヘキセン環、シクロヘプタン環、シクロオクタン環、ジシクロペンタジエン環、テトラヒドロジシクロペンタジエン環、オクタヒドロナフタレン環、デカヒドロナフタレン環、ヘキサヒドロインダン環、ボルナン環、ノルボルナン環、ノルボルネン環、イソボルナン環、トリシクロデカン環、テトラシクロドデカン環、アダマンタン環などが挙げられる。
芳香族環aCyとしては、炭素数6~22が好ましく、6~18がより好ましく、6~10がさらに好ましい。芳香族環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フェナレン環、フルオレン環、アセナフチレン環、ビフェニレン環、インデン環、インダン環、トリフェニレン環、ピレン環、クリセン環、ペリレン環、テトラヒドロナフタレン環などが挙げられる。なかでも、ベンゼン環またはナフタレン環が好ましく、ベンゼン環がより好ましい。芳香族環は複数が連結した構造を取っていてもよく、例えば、ビフェニル環、ビスフェニル環が挙げられる。
芳香族複素環hCyとしては、炭素数1~12が好ましく、1~6がより好ましく、1~5がさらに好ましい。その具体例としては、チオフェン環、フラン環、ピロール環、イミダゾール環、ピラゾール環、トリアゾール環、テトラゾール環、チアゾール環、オキサゾール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、イソインドール環、インドール環、インダゾール環、プリン環、キノリジン環、イソキノリン環、キノリン環、フタラジン環、ナフチリジン環、キノキサリン環、キナゾリン環、シンノリン環、カルバゾール環、アクリジン環、フェナジン環、フェノチアジン環、フェノキサジン環などが挙げられる。
本発明では特定の単官能重合性化合物を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。インプリント用硬化性組成物には、上記特定の単官能重合性化合物とともに、その他の単官能重合性化合物を含んでいてもよい。
インプリント用硬化性組成物には、上記のように、特定の単官能重合性化合物とともに、多官能重合性化合物を含んでいることが好ましい。多官能重合性化合物は、特に定めるものではないが、脂環、芳香族環および芳香族複素環の少なくとも1種を含むことが好ましく、芳香族環および芳香族複素環の少なくとも1種を含むことがより好ましい。脂環、芳香族環および芳香族複素環の少なくとも1種を含む化合物を、以下の説明において、環含有多官能重合性化合物ということがある。
インプリント用硬化性組成物に用いる環含有多官能重合性化合物における環の数は、1つであっても、2つ以上であってもよいが、1つまたは2つが好ましく、1つがより好ましい。尚、縮合環の場合は、縮合環を1つとして考える。
インプリント用硬化性組成物に用いる環含有多官能重合性化合物の構造は、(重合性基)-(単結合または2価の連結基)-(環を有する2価の基)-(単結合または2価の連結基)-(重合性基)で表されることが好ましい。ここで、連結基としては、アルキレン基がより好ましく、炭素数1~3のアルキレン基がさらに好ましい。
Qは、複数の脂環、複数の芳香族環、複数の芳香族複素環、脂環と芳香族環、脂環と芳香族複素環、芳香族環と芳香族複素環が連結した構造を有していてもよい。芳香族環が連結した構造としては、下記式AR-1またはAR-2の構造が挙げられる。
第1群
インプリント用硬化性組成物は、多官能重合性化合物を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。
本発明のインプリント用硬化性組成物は下記式(I)または式(II)で表される離型剤を含む。
A1-(B1)x1-(D1)y1-(E1)z1-F1 :式(I)
式(I)において、A1は炭素数4~11(好ましくは4~9)の直鎖の脂肪族炭化水素基、炭素数5~18(好ましくは6~16)の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11(環状構造の炭素数を含む)の脂肪族炭化水素基を表し、A1がフッ素原子を有することはなく、B1はA1との結合部位が脂肪族炭化水素基でない2価の連結基であり、x1は0または1であり、D1はアルキレンオキシド構造であり、E1はF1との結合部位が脂肪族炭化水素基でない2価の連結基であり、F1は極性官能基であり、y1は0~30の整数であり、z1は0または1である。
A2-(B2)x2-(D2)y2-(E2)z2-F2 :式(II)
式(II)において、A2は炭素数4~11(好ましくは4~9)の直鎖の脂肪族炭化水素基、炭素数5~18(好ましくは6~16)の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11(環状構造の炭素数を含む)の脂肪族炭化水素基を表し、A2がフッ素原子を有することはなく、B2はA2との結合部位が脂肪族炭化水素基でない2価の連結基であり、x2は0または1であり、D2はアルキレンオキシド構造であり、E2はF2との結合部位が脂肪族炭化水素基でない2価の連結基であり、F2は水素原子、炭素数4~11(好ましくは4~9)の直鎖の脂肪族炭化水素基、炭素数5~18(好ましくは6~16)の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11(環状構造の炭素数は含まない)の脂肪族炭化水素基であり、F2がフッ素原子を有することはなく、y2は0~30の整数であり、z2は0または1である;但し、y2が0のときは、B2またはE2が極性官能基を含む。
離型剤が特定の炭化水素基A1、A2を有することにより離型剤が適度に気液界面に存在するため、上記の炭化水素鎖を有する疎水的な重合性化合物の界面への過剰偏析を防ぎ、疎水的成分の偏析により充填性が悪化してしまうことを抑制する。重合性化合物が気液界面への偏析能が高い炭素数8以上の直鎖アルキル基を有する場合、特に効果的に機能する。
A1、A2において、直鎖の脂肪族炭化水素基は炭素数4~11であり、炭素数5以上が好ましく、炭素数6以上がより好ましい。また、炭素数9以下が好ましい。
分岐の脂肪族炭化水素基は、炭素数5~18であり、炭素数6以上が好ましく、炭素数7以上がより好ましく、炭素数8以上がさらに好ましく、炭素数9以上であってもよい。また、炭素数17以下が好ましく、炭素数16以下であってもよい。
炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基は、環状構造のみからなっていてもよいし、環状構造と直鎖または分岐の脂肪族炭化水素基からなっていてもよい。環状構造は、5員環または6員環の脂環である。また、環状構造は、単環であっても縮合環であってもよい。A1、A2において、炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基は、下記式(A2)で表される基であることが好ましい。
A1、A2の炭素数が上記の下限値を下回ると疎水性が弱いためモールドの表面エネルギーを充分に低減できず離型性が低下する。逆に上記の上限値を上回ると疎水性が強すぎてモールド表面の濡れ性が低下し充填性が悪化する。なお、直鎖と分岐で炭素数の範囲が異なるのは、分岐の脂肪族炭化水素基は直鎖に比べて表面エネルギーの低減能が低下するため、必要となる炭素数が大きくなるためである。なお、本明細書における離型剤に関するこのような作用記載は推定を含むものであり、これにより本発明がこれにより限定して解釈されるものではない。
A1、A2はフッ素原子を有することはない。フッ素原子を有さないことにより、モールド表面の過剰な低表面エネルギー化を防ぎ、充填性を下げることなく離型性を向上することが可能となる。さらに、A1、A2は、炭素原子および水素原子のみから構成されていることが好ましい。炭素原子および水素原子のみから構成されていることにより、適度に表面エネルギーを低下させることが可能となる。
連結基は、離型剤中に含まれていてもよいし、含まれていなくてもよい。したがって、式中のx1、x2、z1およびz2は、0または1であり、x1、x2、z1およびz2は、0であることが好ましい。
B1、B2、E1、E2は、それぞれ、A1、F1、A2、F2との連結部位が脂肪族炭化水素基でない2価の連結基である。
連結基の第一の実施形態としては、脂肪族炭化水素以外の環構造を有する連結基が挙げられる。連結基を構成する環構造としては、芳香環が挙げられ、ベンゼン環、ナフタレン環などの炭素数6~18(より好ましくは炭素数6~10)の芳香族環、チオフェン環、フラン環、ピロール環、ベンゾチオフェン環、ベンゾフラン環、ベンゾピロール環、トリアジン環、イミダゾール環、ベンゾイミダゾール環、トリアゾール環、チアジアゾール環、チアゾール環等のヘテロ環が好ましい。
連結基の第二の実施形態としては、極性官能基を含む基が例示される。
特に、式(II)では、y2が0のときは、B2またはE2が極性官能基を含むことが好ましい。すなわち、x2およびz2の少なくともいずれかは1である。B2またはE2が極性官能基を含む連結基の場合、酸素原子、硫黄原子、カルボニル基、-NRN-、スルホニル基、-SO4-またはこれらの組合せがより好ましい。
本離型剤は化合物内の親疎水性比を調整するという観点でアルキレンオキシド構造を有することが好ましい。アルキレンオキシド構造は、直鎖アルキレン基(好ましくはエチレン基)と酸素原子のみからなる構造であることが好ましい。
アルキレンオキシド構造の具体例としては、メチレンオキシド、エチレンオキシド、プロピレンオキシド、ブチレンオキシドなどが挙げられる。
アルキレンオキシド構造の繰り返し数y1およびy2は、それぞれ独立に、0以上であり、1以上が好ましく、4以上がより好ましく、5以上がさらに好ましい。また、30以下であり、25以下が好ましく、20以下がより好ましい。y1およびy2は特に5~20の整数であることが好ましい。y1およびy2が小さすぎると離型剤化合物中の疎水性基の比率が上昇しモールドとの濡れ性が低下して充填性が悪化することがある。逆にy1およびy2が大きすぎると疎水性基の比率が低下し離型性が悪化することがある。
本離型剤の末端基は、F1(極性官能基)またはF2(水素原子、炭素数4~11(好ましくは4~9)の直鎖の脂肪族炭化水素基、炭素数5~18の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基であり、フッ素原子を有することはない)である。
極性官能基の具体例としてはヒドロキシル基、アミノ基、スルホニル基含有基、スルフィノ基、スルホンイミドイル基含有基、カルボキシル基が挙げられる。特に、実用性の観点でヒドロキシル基、アミノ基、スルホニル基含有基(特にスルホニル基、スルホ基またはスルホンアミド基)、カルボキシル基が好ましい。スルホニル基含有基はスルホニル基(-SO2R)、スルホンアミド基(R-SO2-NH-)、スルファモイル基(-SO2NH2)、またはスルホ基(-SO3H)であることが好ましい。スルホンイミドイル基含有基は-SO(NH)Rであることが好ましい。Rはアルキル基(炭素数1~24が好ましく、1~12がより好ましく、1~6がさらに好ましい)、アルケニル基(炭素数2~24が好ましく、2~12がより好ましく、2~6がさらに好ましい)またはアリール基(炭素数6~22が好ましく、6~18がより好ましく、6~10がさらに好ましい)である。
F2の好ましい範囲は、A1と同様である。
R1はA1と同義の基を表し、好ましい範囲も同じである。
n1はy1と同じ数であり、好ましい範囲も同じである。
R2はA1と同義の基を表し、好ましい範囲も同じである。ただし、脂肪族炭化水素基の鎖中にヘテロ原子を含む連結基(O,S,NH等)を炭素原子2つに1つ以下の割合で含んでもよい。
R4およびR5はそれぞれ独立にA2と同義の基を表し、好ましい範囲も同じである。
n2はy2と同じ数であり、好ましい範囲も同じである。
R6およびR7はそれぞれ独立にA2と同義の基を表し、好ましい範囲も同じである。
R8およびR9はそれぞれ独立にA2と同義の基を表し、好ましい範囲も同じである。
インプリント用硬化性組成物は、離型剤を1種のみ含んでいても、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。
本発明のインプリント用硬化性組成物は、光重合開始剤を含む。
本発明で用いられる光重合開始剤としては、光照射により上述の重合性化合物を重合する活性種を発生する化合物であればいずれのものでも用いることができる。光重合開始剤としては、光ラジカル重合開始剤、光カチオン重合開始剤が好ましく、光ラジカル重合開始剤がより好ましい。
本発明で用いるインプリント用硬化性組成物は、上述の他、本発明の趣旨を逸脱しない範囲で、他の成分を含んでいてもよい。他の成分としては、界面活性剤、増感剤、酸化防止剤、重合禁止剤(例えば、4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン-1-オキシルフリーラジカル)、紫外線吸収剤、溶剤等が例示される。これらの化合物は、それぞれ、1種のみ含んでいてもよいし、2種以上含んでいてもよい。これらの詳細については、特開2014-170949号公報の段落0061~0064の記載を参酌でき、この内容は本明細書に組み込まれる。
このように、本発明のインプリント用硬化性組成物は、必ずしも、溶剤を含むものではないが、組成物の粘度を微調整する際などに、任意に添加してもよい。本発明の硬化性組成物に好ましく使用できる溶剤の種類としては、インプリント用硬化性組成物やフォトレジストで一般的に用いられている溶剤であり、本発明で用いる化合物を溶解および均一分散させるものであればよく、かつ、これらの成分と反応しないものであれば特に限定されない。本発明で用いることができる溶剤の例としては、特開2008-105414号公報の段落番号0088に記載のものが挙げられ、この内容は本明細書に組み込まれる。
また、本発明のインプリント用硬化性組成物は、分子量2000以上の成分を実質的に含まないことが好ましい。実質的に含まないとは、インプリント用硬化性組成物の不揮発性成分の3質量%以下であることをいい、1質量%以下が好ましく、0.5質量%以下がさらに好ましい。
本発明のインプリント用硬化性組成物の大西パラメータは5.0以下であることが好ましく、4.0以下であることがより好ましく、3.9以下であることがさらに好ましく、3.7以下であることが一層好ましく、3.6以下であることがより一層好ましい。大西パラメータを5.0以下とすることにより、エッチング耐性がより向上する傾向にある。
上記大西パラメータの下限値は、3.0以上であってもよく、さらには3.5以上であってもよい。
本発明のパターン形成方法は、本発明のインプリント用硬化性組成物を、基板上またはモールド上に適用し、上記インプリント用硬化性組成物を、上記モールドと上記基板で挟んだ状態で光照射することを含む。
また、基板の表面に、下層膜や密着膜、プライマ膜(液膜)を形成し、その表面にインプリント用硬化性組成物を適用してもよい。
その後、ウェットエッチングの場合にはフッ化水素等、ドライエッチングの場合にはCF4やCHF3/CF4/Ar混合ガス等のエッチングガスを用いてエッチングすることにより、基板上に所望のパターンを形成することができる。パターンは、特にドライエッチングに対するエッチング耐性が良好である。すなわち、本発明の製造方法で得られたパターンは、リソグラフィー用マスクとして好ましく用いられる。
パターン形成方法の詳細については、特開2015-185798号公報の段落0057~0071の記載を参酌することができ、この内容は本明細書に組み込まれる。
表1~3に示した各種化合物を混合し、さらに重合禁止剤として4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン-1-オキシルフリーラジカル(東京化成社製)を重合性化合物の合計量に対して200質量ppm(0.02質量%)となるように加えた。これを孔径0.02μmのNylonフィルタおよび孔径0.01μmのPTFEフィルタおよび孔径0.001μmのUPEフィルタでろ過して、インプリント用硬化性組成物を調製した。
離型剤の重量平均分子量をLC-MS(高速液体クロマトグラフ質量分析計)を用いて算出した。LCのカラムはTOSOH製TSKgel ODS-80Ts、溶離液はH2O/MeOH(共に酢酸アンモニウム溶解品)を使用した。MSのイオン化法はESI-Posiを選択した。MSスペクトルから分子量分布を把握することで、重量平均分子量Mwを算出した。なお、MeOHはメタノールのことである。
TOSOH製TSKgel ODS-80Ts、直径2.0 mm(内径)・150 mm
溶離液: A液: H2O (10 mM CH3COONH4)、B液: MeOH (10 mM CH3COONH4)
グラジエント条件: Bconc. 50% (0 min.) → 100% (20 min.) → 100% (40 min.)
流速: 0.2 mL/min.、注入量: 2 μL、カラム温度: 40 ℃
MSイオン化法: ESI positive
検出: 1TICモード、2SIMモード 標品から検出した2成分のピークで定量を実施
1m/z = 616, 664
[H(C3H6O)n+OH+NH4]+(n=10,11)由来
粘度は、東機産業(株)製のE型回転粘度計RE85L、標準コーン・ロータ(1°34’×R24)を用い、サンプルカップを23℃に温度調節して測定した。単位は、mPa・sで示した。測定に関するその他の詳細はJISZ8803:2011に準拠した。1水準につき2つの試料を作製し、それぞれ3回測定した。合計6回の算術平均値を評価値として採用した。
各組成物または化合物の表面張力は、協和界面科学(株)製、表面張力計SURFACE TENS-IOMETER CBVP-A3を用い、ガラスプレートを用いて23℃で行った。単位は、mN/mで示した。1水準につき2つの試料を作製し、それぞれ3回測定した。合計6回の算術平均値を評価値として採用した。
石英モールドとして、線幅20nm、深さ55nmのライン(Line)/スペース(Space)[L:S=1:1]を有する石英モールドを使用した。インクジェット装置として、FUJIFILM Dimatix社製インクジェットプリンター DMP-2831を用いてシリコンウェハ(シリコン基板)上に、上記インプリント用硬化性組成物をインクジェット法により適用後、ヘリウム雰囲気下で、上記モールドで挟んだ。インクジェットによる吐出パターンは、配列を菱形格子状とし、間隔を対角線:140μm/80μmとし、吐出量を1pLとした。石英モールド側から高圧水銀ランプを用いて、100mJ/cm2の条件で露光した後、石英モールドを離型することでパターンを得た。
A:F≦15N
B:15N<F≦18N
C:18N<F≦20N
D:F>20N
IJ吐出性の評価は、FUJIFILM Dimatix社製インクジェットプリンター DMP-2831を用いて行った。23℃に温度調整した組成物の吐出の様子をCCDカメラ(シーシーディーイメージセンサカメラ)で観察しながら、吐出波形、吐出電圧等の吐出条件を最適化した。最も安定した吐出を行った吐出口を5つ選択し、組成物をシリコンウェハ上に100μm間隔(正方配列)で吐出した(吐出面積5mm角、2500ドット)。インクジェットノズルを交換することで、吐出量を1pL、6pLに変更して検討した。
上記検討を5回連続で行った際のCCDカメラによる吐出状態の観察と、吐出液滴の正方配列からのずれを評価した。
A:全てのノズルが安定して吐出し、吐出領域全面で液滴配置のずれは見られなかった。
B:一部ノズルに飛翔曲がり、吐出口の汚れが見られ、一部で液滴配置のずれが発生した。
C:50%以上のノズルで飛翔曲がり、吐出口の汚れが見られ、吐出領域全域に渡って液滴配置のずれや液滴の抜けが見られた。
上記離型力の評価で作製したパターンを観察し、以下の通り評価した。
A:全面に渡って、良好なパターン転写を確認した。
B:パターン表面の荒れまたはパターン抜けがみられた。
C:パターン表面の荒れとパターン抜けの両方がみられた。
石英モールドとして、それぞれの開口部が半径1μmの円で、その深さが2μmの凹型構造を有する石英モールド(配列:正方配列、ピッチ:4μm)を使用した。インクジェット装置として、FUJIFILM Dimatix社製インクジェットプリンター DMP-2831を用いてシリコンウェハ上に上記インプリント用硬化性組成物をインクジェット法により適用後、ヘリウム雰囲気下で、上記モールドで挟んだ。
石英モールドの凹部のインプリント用硬化性組成物の充填の様子をCCDカメラにて観察し、充填の完了に要する時間を測定した。
A:3秒未満
B:3秒以上5秒未満
C:5秒以上10秒未満
D:10秒以上
これに対して、(1)~(3)のいずれかの構造を含まない単官能重合性化合物、または式(I)および式(II)の規定を満たさない離型剤を用いたものでは(比較例1~10)、離型性および充填性のいずれかの性能に劣り、これらを両立することはできなかった。
Claims (19)
- 下記(1)~(3)のいずれかの構造を有する単官能重合性化合物、
光重合開始剤および
下記式(I)または式(II)で表される離型剤
を含む、インプリント用硬化性組成物;
:単官能重合性化合物
(1)炭素数8以上の直鎖アルキル基
(2)炭素数10以上の分岐アルキル基
(3)炭素数1以上の直鎖のアルキル基または炭素数3以上の分岐のアルキル基が置換した、脂環、芳香族環または芳香族複素環
:離型剤
A1-(B1)x1-(D1)y1-(E1)z1-F1 :式(I)
式(I)において、A1は炭素数4~11の直鎖の脂肪族炭化水素基、炭素数5~18の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基を表し、A1がフッ素原子を有することはなく、B1はA1との結合部位が脂肪族炭化水素基でない2価の連結基であり、x1は0または1であり、D1はアルキレンオキシド構造であり、E1はF1との結合部位が脂肪族炭化水素基でない2価の連結基であり、F1は極性官能基であり、y1は0~30の整数であり、z1は0または1である;
A2-(B2)x2-(D2)y2-(E2)z2-F2 :式(II)
式(II)において、A2は炭素数4~11の直鎖の脂肪族炭化水素基、炭素数5~18の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基を表し、A2がフッ素原子を有することはなく、B2はA2との結合部位が脂肪族炭化水素基でない2価の連結基であり、x2は0または1であり、D2はアルキレンオキシド構造であり、E2はF2との結合部位が脂肪族炭化水素基でない2価の連結基であり、F2は水素原子、炭素数4~11の直鎖の脂肪族炭化水素基、炭素数5~18の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基であり、F2がフッ素原子を有することはなく、y2は0~30の整数であり、z2は0または1である;但し、y2が0のときは、B2またはE2が極性官能基を含む。 - A1が炭素数4~9の直鎖の脂肪族炭化水素基である離型剤を含む、請求項1に記載のインプリント用硬化性組成物。
- A2は炭素数4~9の直鎖の脂肪族炭化水素基、かつF2が炭素数4~9の直鎖の脂肪族炭化水素基である離型剤を含む、請求項1に記載のインプリント用硬化性組成物。
- 前記極性官能基がヒドロキシル基、アミノ基、スルホニル基含有基、スルフィノ基、スルホンイミドイル基含有基およびカルボキシル基からなる群から選ばれる、請求項1~3のいずれか1項に記載のインプリント用硬化性組成物。
- 前記y1およびy2がそれぞれ独立に5~20の整数である、請求項1~4のいずれか1項に記載のインプリント用硬化性組成物。
- 前記x1およびx2が0である、請求項1~5のいずれか1項に記載のインプリント用硬化性組成物。
- 式(I)において、A1は炭素数4~9の直鎖の脂肪族炭化水素基、炭素数5~18の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基を表し、y1は5~20の整数であるか、
式(II)において、A2は炭素数4~9の直鎖の脂肪族炭化水素基、炭素数5~18の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基を表し、F2は水素原子、炭素数4~9の直鎖の脂肪族炭化水素基、炭素数5~18の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基であり、y2は5~20の整数である、請求項1~6のいずれか1項に記載のインプリント用硬化性組成物。 - 前記離型剤の重量平均分子量が300~1000である、請求項1~7のいずれか1項に記載のインプリント用硬化性組成物。
- 前記離型剤の含有量が不揮発性成分中0.5質量%以上7.0質量%以下である、請求項1~8のいずれか1項に記載のインプリント用硬化性組成物。
- 前記インプリント用硬化性組成物に含まれる重合性化合物が、23℃において33mN/m以上の表面張力を示す、請求項1~9のいずれか1項に記載のインプリント用硬化性組成物。
- 前記インプリント用硬化性組成物に含まれる重合性化合物の粘度が20mPa・s以下であり、かつ、組成物中の溶剤含有量がインプリント用硬化性組成物の3質量%以下である、請求項1~10のいずれか1項に記載のインプリント用硬化性組成物。
- 前記インプリント用硬化性組成物の23℃における表面張力が28mN/m以上38mN/mである、請求項1~11のいずれか1項に記載のインプリント用硬化性組成物。
- 下記式(I)または式(II)で表される離型剤;
A1-(B1)x1-(D1)y1-(E1)z1-F1 :式(I)
式(I)において、A1は炭素数4~9の直鎖の脂肪族炭化水素基、炭素数5~18の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基を表し、A1がフッ素原子を有することはなく、B1はA1との結合部位が脂肪族炭化水素基でない2価の連結基であり、x1は0または1であり、D1はアルキレンオキシド構造であり、E1はF1との結合部位が脂肪族炭化水素基でない2価の連結基であり、F1は極性官能基であり、y1は5~20の整数であり、z1は0または1である;
A2-(B2)x2-(D2)y2-(E2)z2-F2 :式(II)
式(II)において、A2は炭素数4~9の直鎖の脂肪族炭化水素基、炭素数5~18の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基を表し、A2がフッ素原子を有することはなく、B2はA2との結合部位が脂肪族炭化水素基でない2価の連結基であり、x2は0または1であり、D2はアルキレンオキシド構造であり、E2はF2との結合部位が脂肪族炭化水素基でない2価の連結基であり、F2は水素原子、炭素数4~9の直鎖の脂肪族炭化水素基、炭素数5~18の分岐の脂肪族炭化水素基、または炭素数5または6の環状構造を含む炭素数5~11の脂肪族炭化水素基であり、F2がフッ素原子を有することはなく、y2は5~20の整数であり、z2は0または1である;但し、y2が0のときは、B2またはE2が極性官能基を含む。 - インプリント用硬化性組成物用である、請求項13に記載の離型剤。
- 請求項1~12のいずれか1項に記載のインプリント用硬化性組成物を硬化してなる硬化物。
- 前記硬化物が、シリコン基板の上に設けられている、請求項15に記載の硬化物。
- 請求項1~12のいずれか1項に記載のインプリント用硬化性組成物を、基板上またはモールド上に適用し、前記インプリント用硬化性組成物を、前記モールドと前記基板で挟んだ状態で光照射することを含むパターン形成方法。
- 前記パターンのサイズが20nm以下のライン、ホール、ピラーのいずれかの形状を含む請求項17に記載のパターン形成方法。
- 請求項17または18に記載のパターン形成方法で得られたパターンをマスクとしてエッチングを行う、リソグラフィー方法。
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