WO2019022175A1 - インプリント用硬化性組成物、硬化物、パターン製造方法、リソグラフィ方法、パターン、および、インプリント用重合性組成物 - Google Patents
インプリント用硬化性組成物、硬化物、パターン製造方法、リソグラフィ方法、パターン、および、インプリント用重合性組成物 Download PDFInfo
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- WO2019022175A1 WO2019022175A1 PCT/JP2018/028019 JP2018028019W WO2019022175A1 WO 2019022175 A1 WO2019022175 A1 WO 2019022175A1 JP 2018028019 W JP2018028019 W JP 2018028019W WO 2019022175 A1 WO2019022175 A1 WO 2019022175A1
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- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000004897 thiazines Chemical class 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 229950003937 tolonium Drugs 0.000 description 1
- HNONEKILPDHFOL-UHFFFAOYSA-M tolonium chloride Chemical compound [Cl-].C1=C(C)C(N)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 HNONEKILPDHFOL-UHFFFAOYSA-M 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 150000005219 trimethyl ethers Chemical class 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 125000001834 xanthenyl group Chemical class C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- 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
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(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
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/16—Esters having free carboxylic acid groups, e.g. monoalkyl maleates or fumarates
-
- 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
- C08F222/26—Esters of unsaturated alcohols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- 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
-
- 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
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
-
- 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
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
-
- 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
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/3065—Plasma etching; Reactive-ion etching
Definitions
- the present invention relates to a curable composition for imprinting, a cured product, a pattern manufacturing method, a lithography method, a pattern, a mask for lithography, and a polymerizable composition for imprinting.
- the imprint method is a technology 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
- Application to various fields is expected in recent years because precise fine patterns can be easily produced by using an imprint method.
- a nanoimprint technique for forming a nano-order fine pattern has attracted attention.
- a method called a thermal imprint method or an optical imprint method has been proposed from the transfer method.
- a thermal imprint method a method is pressed on a thermoplastic resin heated to a temperature higher than the glass transition temperature (hereinafter sometimes referred to as "Tg"), and after cooling, the mold is released to form a fine pattern.
- Tg glass transition temperature
- the photo-curing is performed in a state where the mold is pressed against the curable composition for imprinting, and then the mold is released. There is no need for high pressure or high temperature heating for imprinting on an uncured material, and it is possible to easily form a fine pattern.
- a curable composition for imprinting is applied on a substrate (which is subjected to an adhesion treatment if necessary), and then a mold made of a light-transmissive material such as quartz is pressed. While the mold is pressed, the curable composition for imprints is cured by light irradiation, and then the mold is released to produce a cured product to which a target pattern is transferred.
- Examples of a method of applying the curable composition for imprints on a substrate include a spin coating method and an inkjet method.
- the inkjet method is an application method that has recently been attracting attention from the viewpoint of a small loss of the curable composition for imprints.
- NIL nanoimprint lithography
- EUV extreme ultraviolet
- the curable composition for imprints used for NIL is capable of resolving an ultrafine pattern of 30 nm or less, and is highly etched as a mask when microprocessing a processing object Resistance is required.
- throughput productivity
- nanoimprint suitability such as pattern filling property (filling time reduction) and mold releasability (mold release time reduction) is also required.
- Patent Documents 1 to 6 are known as disclosed as a curable composition for imprints excellent in etching resistance, filling property and releasability.
- Patent Documents 1 to 3 phenylethylene glycol diacrylate is used as an acrylate monomer having high etching resistance.
- the polyfunctional acrylate containing at least one of an alicyclic structure and an aromatic ring structure is used.
- Patent Documents 5 and 6 in order to improve etching resistance, an acrylate monomer containing silicon is used.
- the object of the present invention is to solve the above-mentioned problems, and is a curable composition for imprints which has high adhesion to a substrate when made into a cured product and is excellent in storage stability, It is an object of the present invention to provide a cured product, a pattern manufacturing method, a lithography method, a pattern, a mask for lithography, and a polymerizable composition for imprints.
- the above problems can be solved by blending a predetermined compound. Specifically, the above problems have been solved by the following means ⁇ 1>, preferably by ⁇ 2> to ⁇ 20>.
- a curable composition for imprints which comprises a compound represented by the following formula (1), a radically polymerizable compound other than the compound represented by the above formula (1), and a photoradical polymerization initiator;
- R 1 and R 2 each independently represent a hydrogen atom or an organic group having 1 to 8 carbon atoms, and may combine with each other to form a ring; and
- R 3 is monovalent
- R 4 and R 5 are each independently a hydrogen atom or a monovalent organic group.
- the content of the compound represented by ⁇ 2> said Formula (1) is 0.005-1 mass with respect to 100 mass parts of content of radically polymerizable compounds other than the compound represented by said Formula (1)
- the curable composition for imprints as described in ⁇ 1> which is a part.
- the curable composition for imprints as described in ⁇ 1> or ⁇ 2> in which radically polymerizable compounds other than the compound represented by ⁇ 3> said Formula (1) contain at least 1 sort (s) of a (meth) acryloyl group. . ⁇ 4>
- ⁇ 5> The curable composition for imprints according to any one of ⁇ 1> to ⁇ 4>, wherein the compound represented by the formula (1) has a radically polymerizable group.
- ⁇ 6> The curable composition for imprints according to any one of ⁇ 1> to ⁇ 5>, wherein R 4 or R 5 in the above formula (1) is represented by the following formula (1-3); In formula (1-3), R 6 represents a monovalent organic group; * represents a bonding position.
- ⁇ 9> The compound according to any one of ⁇ 1> to ⁇ 8>, wherein at least one of radically polymerizable compounds other than the compound represented by the above formula (1) is a monofunctional (meth) acrylic monomer Curable composition for imprints.
- ⁇ 10> The curable composition for imprints according to any one of ⁇ 1> to ⁇ 9>, wherein a content of a solvent in the curable composition for imprints is 5% by mass or less.
- ⁇ 11> The imprinting according to any one of ⁇ 1> to ⁇ 10>, wherein the content of the component having a weight average molecular weight of more than 2000 in the curable composition for imprints is 5% by mass or less Curable composition.
- ⁇ 12> The curable composition for imprints according to any one of ⁇ 1> to ⁇ 11>, wherein the viscosity at 25 ° C. of the curable composition for imprints is 3 to 15 mPa ⁇ s.
- ⁇ 13> A cured product formed from the curable composition for imprints according to any one of ⁇ 1> to ⁇ 12>.
- ⁇ 14> The cured product according to ⁇ 13>, wherein the cured product is provided on a silicon substrate.
- ⁇ 15> The curable composition for imprints according to any one of ⁇ 1> to ⁇ 12> is applied on a substrate or a mold, and the curable composition for imprints is the same as the mold and the above.
- the pattern manufacturing method as described in ⁇ 15> whose size of the ⁇ 16> above-mentioned pattern is 30 nm or less.
- ⁇ 18> A pattern formed from the curable composition according to any one of ⁇ 1> to ⁇ 12>, wherein the pattern size is 30 nm or less.
- a polymerizable composition for imprint comprising a compound represented by the following formula (1) and a compound represented by the following formula (2);
- R 1 and R 2 each independently represent a hydrogen atom or an organic group having 1 to 8 carbon atoms, and may combine with each other to form a ring; and
- R 3 is monovalent
- R 4 and R 5 are each independently a hydrogen atom or a monovalent organic group;
- R 21 is a q-valent organic group
- R 22 is a hydrogen atom or a methyl group
- q is an integer of 2 or more.
- a curable composition for imprints having high adhesion to a substrate when cured and excellent storage stability, a cured product, a pattern manufacturing method, a lithography method, a pattern, a mask for lithography, It has become possible to provide a polymerizable composition for imprinting.
- imprinting preferably refers to pattern transfer of a size of 1 nm to 10 mm, more preferably, pattern transfer of a size (nanoimprint) of about 10 nm to 100 ⁇ m.
- groups atomic groups
- the notations not describing substitution and non-substitution include those having no substituent and those having 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 light of wavelengths in the ultraviolet, near-ultraviolet, far-ultraviolet, visible, infrared and other regions, and radiation as well as electromagnetic waves. Radiation includes, for example, microwave, electron beam, extreme ultraviolet (EUV), and x-ray. Laser light such as 248 nm excimer laser, 193 nm excimer laser, 172 nm excimer laser can also be used. The light may be monochrome light (single wavelength light) passing through an optical filter, or may be light of different wavelengths (composite light). As used herein, total solids refers to the total mass of all components of the composition excluding the solvent.
- the atmospheric pressure at the time of boiling point measurement in the present invention is 101325 Pa (1 atm).
- the temperature in the present invention is 25 ° C. unless otherwise stated.
- the term "process” is included in the term if the intended function of the process is achieved, even if it can not be clearly distinguished from other processes, not only the independent process. .
- weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise stated.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corp.), guard column HZ-L as a column, TSKgel Super HZM-M, TSKgel It can be determined by using Super HZ4000, TSKgel Super HZ3000 or TSKgel Super HZ2000 (manufactured by Tosoh Corp.). Eluents are to be determined using THF (tetrahydrofuran) unless otherwise stated. Moreover, a detection shall use the wavelength 254 nm detector of a UV ray (ultraviolet light), unless it mentions specially.
- the curable composition for imprints of the present invention is a compound represented by the following formula (1) and a radically polymerizable compound other than the compound represented by the formula (1) (hereinafter simply referred to as “other radically polymerizable
- the compound includes a compound or a polymerizable compound having no aminomethyl group, and a photo radical polymerization initiator.
- R 1 and R 2 each independently represent a hydrogen atom or an organic group having 1 to 8 carbon atoms, and may combine with each other to form a ring; and R 3 is monovalent R 4 and R 5 are each independently a hydrogen atom or a monovalent organic group.
- the curable composition for imprints of the present invention contains the compound represented by the above formula (1). It is preferable that the compound represented by Formula (1) has a radically polymerizable group. By having a radically polymerizable group, it becomes a part of a cured product, and the adhesion to the resist tends to be further improved. Preferred examples of the radically polymerizable group are the same as those specified in R 3 below.
- the number of radically polymerizable groups in one molecule of the compound represented by the formula (1) is preferably 1 to 5, more preferably 2 to 5, and further preferably 2 or 3. Preferably, two are more preferable.
- R 1 and R 2 each independently represent a hydrogen atom or an organic group having 1 to 8 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a hydrogen atom A methyl group, an ethyl group, an n-propyl group, an isopropyl group or a benzyl group is more preferable, a hydrogen atom, a methyl group or an ethyl group is more preferable, a methyl group or an ethyl group is more preferable, and an ethyl group is more preferable.
- R 1 and R 2 may or may not have the following substituent T as long as the effects of the present invention are not impaired.
- R 1 and R 2 preferably have no substituent.
- an aryl group is preferred.
- R 1 and R 2 are the same group. With such a configuration, the effects of the present invention are more effectively exhibited.
- a linear or branched alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, still more preferably 1 to 6), and a cycloalkyl group (preferably having 3 to 24 carbon atoms) -12 is more preferable, 3 to 6 is more preferable, aralkyl group (preferably having 7 to 21 carbon atoms, more preferably 7 to 15 and still more preferably 7 to 11), linear or branched alkenyl group (having carbon atoms) 2 to 24 is preferable, 2 to 12 is more preferable, 2 to 6 is more preferable, cycloalkenyl group (having 3 to 24 carbon atoms is preferable, 3 to 12 is more preferable, 3 to 6 is more preferable), hydroxyl Group, hydroxyl alkyl group (preferably having a carbon number of 1 to 24, more preferably 1 to 12, still more preferably 1 to 6; the number of hydroxyl groups is preferably 1 to 6, preferably 1 to 6).
- the alkyl group may be linear or branched, and may be linear or cyclic, hydroxyl alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and still more preferably 2 to 6 carbon atoms; hydroxyl group
- the number of groups is preferably 1 to 6, and more preferably 1 to 3.
- the alkenyl group may be linear, branched, linear or cyclic), amino group (preferably having a carbon number of 0 to 24, more preferably 0 to 12)
- 0 to 6 is more preferable
- an aminoalkyl group having 1 to 24 carbon atoms is preferable, 1 to 12 is more preferable, and 1 to 6 is more preferable; the number of amino groups is preferably 1 to 6, 1 to 3
- the alkyl group is preferably linear, branched, linear or cyclic), amino alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and 2 to 6 carbon atoms.
- the number of amino groups is preferably 1 to 6, more preferably 1 to 3.
- the alkenyl group may be linear, branched, linear or cyclic), thiol group, thiol alkyl group (having 1 to 6 carbon atoms) 24 is preferable, 1 to 12 is more preferable, and 1 to 6 is more preferable; the number of thiol groups is preferably 1 to 6 and more preferably 1 to 3.
- the alkyl group may be linear or branched, linear or cyclic And a thiol alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 and still more preferably 2 to 6); the number of thiol groups is preferably 1 to 6 and more preferably 1 to 3; alkenyl group May be linear, branched, linear or cyclic), carboxyl group or carboxyalkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms The number of carboxyl groups is preferably 1 to 6, and more preferably 1 to 3.
- the alkyl group may be linear, branched, linear or cyclic, or carboxyalkenyl group (having 2 to 24 carbon atoms). 2 to 12 is more preferable, 2 to 6 is more preferable; the number of carboxyl groups is preferably 1 to 6 and more preferably 1 to 3.
- the alkenyl group may be linear or branched, and may be linear or cyclic) Aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), acyl groups (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 3 carbon atoms ), An acyloxy group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 and further preferably 2 to 3), an aryloyl group (preferably having 7 to 23 carbon atoms, and more preferably 7 to 19).
- Aryl groups preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms
- acyl groups preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 3 carbon atoms
- An acyloxy group preferably having 2 to 12 carbon atoms, more
- R 3 is a monovalent organic group, preferably an organic group having 1 to 40 carbon atoms, more preferably an organic group having 2 to 30 carbon atoms, and an organic group having 3 to 20 carbon atoms It is more preferable that the carbon number is 6 to 20.
- R 3 preferably contains one or two (preferably one) radically polymerizable groups, and preferably has the same radically polymerizable group as the radically polymerizable groups possessed by the other radically polymerizable compounds.
- R 3 is more preferably an organic group possessed by another radically polymerizable compound.
- Examples of the radically polymerizable group include groups having an ethylenically unsaturated bond such as vinylphenyl group, vinyl group, (meth) acryloyl group and allyl group, (meth) acryloyl group is preferable, and acryloyl group is more preferable.
- the use of the (meth) acryloyl group tends to further improve the adhesion between the substrate and the curable composition for imprints.
- R 3 is preferably represented by the following formula (1-1).
- R 7 represents a divalent organic group
- R C represents a hydrogen atom or a methyl group
- * represents a bonding position.
- R C is preferably a hydrogen atom.
- the organic group of R 7 is preferably a linking group represented by the following formula (1-2).
- each of Z 1 and Z 2 is preferably independently a single bond, -Alk- or -AlkO-.
- Alk represents an alkylene group (preferably having a carbon number of 1 to 12, more preferably 1 to 6, still more preferably 1 to 3), and may have a substituent T within the range not impairing the effects of the present invention .
- Preferred examples of this substituent include groups having the same meanings as R 101 to R 117 below.
- O (oxygen atom) of -AlkO- is linked so as to be on the R 9 side.
- R 9 is preferably a single bond or a linking group selected from the following formulas (9-1) to (9-10) or a combination thereof. Among them, a linking group selected from formulas (9-1) to (9-3), (9-7), and (9-8) is preferable.
- R 101 to R 117 are optional substituents, and a substituent T is preferable.
- a substituent T is preferable.
- an alkyl group preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and further preferably 1 to 3
- an aralkyl group preferably having 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms, and 7 to 11
- thienyl group preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms
- thienyl group furyl group
- the alkyl group preferably has 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 6 carbon atoms).
- Examples of the linking group L described later when the ring is formed include the examples of the linking group L described later, and among them, an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and more preferably 1 to 3) is preferable.
- the cyclohexane ring of formulas (9-6) and (9-7) may form a norbornane ring or an adamantane ring.
- R 101 to R 117 may further have a substituent T as long as the effects of the present invention are not impaired.
- R 9 has a ring structure, it is a structure containing an alicyclic or aromatic ring described later in “(3) Alicyclic or aromatic ring substituted by a linear or branched alkyl group having 5 or more carbon atoms”. Is also preferred.
- the linking group L is a linear or branched alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 and still more preferably 1 to 6), or a linear or branched alkenylene group (having 2 carbon atoms) preferably to 24, more preferably from 2 to 12, more preferably 2 ⁇ 6), - O - , - S -, - CO -, - NR N -, - NR N CO-, and connected according to a combination thereof Groups are mentioned.
- RN is as defined above.
- 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.
- p is an integer greater than or equal to 0 and less than or equal to the maximum number that can be substituted for each ring. In each case, the upper limit is preferably independently at most half of the substitutable maximum number, more preferably four or less, and still more preferably two or less.
- Ar is an arylene group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms). Specifically, phenylene group, naphthalenediyl group, anthracenediyl group, phenanthrenediyl group, It includes a fluorenediyl group. Examples of Z 3 include a single bond or a linking group L.
- Z 3 is preferably a single bond, —O—, or an alkylene group (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably a methylene group or 2,2-propylenediyl group).
- the substituent T may be substituted, and in particular, a halogen atom (particularly a fluorine atom) may be substituted.
- hCy is a heterocyclic group (preferably having a carbon number of 1 to 12, more preferably 1 to 6, still more preferably 2 to 5), and a 5- or 6-membered ring is more preferred.
- heterocyclic ring constituting hCy examples include thiophene ring, furan ring, dibenzofuran ring, carbazole ring, indole ring, tetrahydropyran ring, tetrahydrofuran ring, pyrrole ring, pyridine ring, pyrazole ring, pyrazole ring, imidazole ring, benzimidazole ring, A triazole ring, a thiazole ring, an oxazole ring, a pyrrolidone ring and a morpholine ring can be mentioned, and among them, a thiophene ring, a furan ring and a dibenzofuran ring are preferable.
- n and m are natural numbers of 100 or less, preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.
- R 4 and R 5 are each independently a hydrogen atom or a monovalent organic group.
- the monovalent organic group is preferably an organic group having 1 to 40 carbon atoms, more preferably an organic group having 3 to 35 carbon atoms, and further preferably an organic group having 5 to 30 carbon atoms. Preferably, it may have 8 to 20 carbon atoms.
- R 4 and R 5 preferably contain a radically polymerizable group, and have the same radically polymerizable group as a radically polymerizable group possessed by a radically polymerizable compound other than the compound represented by Formula (1) described later preferable. It is preferable that at least one of R 4 and R 5 contains the organic group of R 3 in Formula (1).
- At least one of R 4 and R 5 has the same organic group as the organic group possessed by the other radically polymerizable compound.
- the radically polymerizable group include groups having an ethylenically unsaturated bond such as a vinylphenyl group, a vinyl group, a (meth) acryloyl group and an allyl group.
- the radically polymerizable group is preferably a (meth) acryloyl group.
- R 4 or R 5 in the formula (1) is (i) an embodiment in which the both are hydrogen atoms, or (ii) an organic group in which one is a hydrogen atom and the other is a formula (1-3)
- An embodiment is preferable, and an embodiment in which one of them is a hydrogen atom and the other is an organic group represented by the following formula (1-3) is more preferable.
- R 6 represents a monovalent organic group, and is preferably a group as defined for R 3 above.
- the preferable range is also the same as R 3 .
- * Represents a bonding position.
- R 7 represents a divalent organic group
- R 8 represents an alkyl group.
- the preferred range of R 7 is the same as in Formula (1-1), and the preferred range is also the same.
- R 8 may have a substituent T as long as the effects of the present invention are not impaired. Examples of this substituent include an amino group (preferably having a carbon number of 0 to 12, more preferably 0 to 6, and still more preferably 0 to 3).
- the compound represented by the formula (1) is more preferably represented by the following formula (1-4).
- R 1 to R 3 each independently have the same meaning as R 1 to R 3 in the formula (1), and the preferred ranges are also the same.
- two R 3 s may be the same or different, but are preferably the same.
- the compound represented by the above formula (1) preferably has a molecular weight of 100 to 1,500, more preferably 150 to 1300, still more preferably 200 to 1000, and even 200 to 700. Good. By setting the amount in such a range, the effect of improving the adhesion by adding a small amount is more effectively exhibited.
- the compound represented by the above formula (1) may not have a radically polymerizable group, but preferably has a radically polymerizable group, and at least one of R 3 to R 5 is radically polymerizable. It is more preferable to have a group, and it is further preferable that R 3 and one of R 4 and R 5 have a radical polymerizable group. Two selected from R 3 to R 5 may be bonded to each other to form a ring.
- the compound represented by the formula (1) is preferably constituted only by an atom selected from a carbon atom, an oxygen atom, a hydrogen atom and a nitrogen atom.
- the content of the compound represented by the above formula (1) in the curable composition for imprints of the present invention is 100 parts by mass of the content of the radically polymerizable compound other than the compound represented by the formula (1)
- the amount is preferably 0.005 to 1 parts by mass, more preferably 0.01 to 0.75 parts by mass, and still more preferably 0.05 to 0.5 parts by mass. With such a range, the adhesiveness, the mold release force, and the temporal stability tend to be more excellent in a well-balanced manner.
- the compound represented by the above formula (1) and the compound represented by the formula (2) described later are combined with other components if necessary, and polymerization for imprints It may constitute a sex composition.
- Content of the compound represented by said Formula (1) in the curable composition for imprints of this invention is 0.005 with respect to 100 mass parts of content of the compound represented by Formula (2) mentioned later. It is preferably 1 part by mass, more preferably 0.01 to 0.75 parts by mass, and still more preferably 0.05 to 0.5 parts by mass. With such a range, the adhesiveness, the mold release force, and the temporal stability tend to be more excellent in a well-balanced manner.
- the compound represented by the formula (1) is preferably 0.005 to 1% by mass of the total solid content of the curable composition for imprints, The content is more preferably 0.01 to 0.75% by mass, and still more preferably 0.05 to 0.5% by mass.
- the compound represented by the above formula (1) may contain only one type, or two or more types. When it contains 2 or more types, it is preferable that a total amount becomes said range.
- the curable composition for imprints of the present invention contains a radically polymerizable compound (other radically polymerizable compound) other than the compound represented by the formula (1).
- Other radically polymerizable compounds preferably have no aminomethyl group.
- the other radically polymerizable compound may be a monofunctional radically polymerizable compound having one radically polymerizable group or a polyfunctional radically polymerizable compound having two or more radically polymerizable groups.
- the curable composition for imprints of the present invention preferably comprises a polyfunctional radically polymerizable compound, and more preferably comprises both a polyfunctional radically polymerizable compound and a monofunctional radically polymerizable compound.
- the polyfunctional radically polymerizable compound preferably includes at least one of a difunctional radically polymerizable compound and a trifunctional radically polymerizable compound, and more preferably includes at least one difunctional radically polymerizable compound.
- Examples of the radically polymerizable group possessed by other radically polymerizable compounds include groups having an ethylenically unsaturated bond such as a vinylphenyl group, a vinyl group, a (meth) acryloyl group and an allyl group.
- the radically polymerizable group is preferably a (meth) acryloyl group, more preferably an acryloyl group.
- the content of the other radically polymerizable compound in the curable composition for imprints of the present invention is preferably 40 to 99.9% by mass, more preferably 60 to 99% by mass, and 75 to 98 More preferably, it is mass%.
- Other radically polymerizable compounds may contain only 1 type, and may contain 2 or more types. When it contains 2 or more types, it is preferable that a total amount becomes said range.
- the radically polymerizable compound other than the compound represented by the above formula (1) preferably contains a compound represented by the following formula (2). With such a range, the adhesiveness, the mold release force, and the temporal stability tend to be more excellent in a well-balanced manner.
- R 21 is a q-valent organic group
- R 22 is a hydrogen atom or a methyl group
- q is an integer of 2 or more.
- q is preferably an integer of 2 or more, 7 or less, more preferably an integer of 2 or more, 4 or less, 2 or 3 more preferably, and 2 is more preferable.
- R 21 is preferably a divalent to heptavalent organic group, more preferably a divalent to tetravalent organic group, still more preferably a divalent or trivalent organic group, and a divalent organic group It is more preferable that R 21 is preferably a hydrocarbon group having at least one of linear, branched and cyclic structures.
- the carbon number of the hydrocarbon group is preferably 2 to 20, and more preferably 2 to 10.
- R 21 is a divalent organic group, it is preferably a linking group represented by the above formula (1-2), and the preferred range is also the same. It is mentioned as a preferred embodiment of the present invention that the structure of the formula (1-2) in the formula (1) and the structure of the formula (1-2) in the formula (2) coincide in the composition.
- R 21 has a ring structure, it is also a structure containing an alicyclic or aromatic ring described later in “(3) an alicyclic or aromatic ring substituted by a linear or branched alkyl group having 5 or more carbon atoms” Also preferred.
- the polyfunctional radically polymerizable compound is preferably represented by the following formula (2-1).
- R 7 and R C are as defined in the above formula (1-1).
- These polyfunctional radically polymerizable compounds may be contained alone or in combination of two or more.
- the Onishi parameter mentioned later is 4.5 or less.
- the lower limit value of the Onishi parameter is not particularly limited, but may be, for example, 2.0 or more.
- the molecular weight of the polyfunctional radically polymerizable compound used in the present invention is preferably 1000 or less, more preferably 800 or less, still more preferably 500 or less, still more preferably 350 or less, and still more preferably 230 or less. By setting the upper limit value of the molecular weight to the upper limit value or less, there is a tendency that the viscosity of the compound can be reduced.
- the lower limit value of the molecular weight is not particularly limited, but can be, for example, 170 or more.
- the number of polymerizable groups contained in the polyfunctional radically polymerizable compound used in the present invention is 2 or more, preferably 2 to 7, more preferably 2 to 4, still more preferably 2 or 3, and still more preferably 2.
- the type of atoms constituting the polyfunctional radically polymerizable compound used in the present invention is not particularly limited, it is preferably composed of only atoms selected from carbon atoms, oxygen atoms, hydrogen atoms and halogen atoms, and carbon More preferably, it is composed of only atoms selected from atoms, oxygen atoms and hydrogen atoms.
- the viscosity at 25 ° C. of the polyfunctional radically polymerizable compound used in the present invention is preferably 180 mPa ⁇ s or less, more preferably 10 mPa ⁇ s or less, still more preferably 7 mPa ⁇ s or less, further preferably 5 mPa ⁇ s or less preferable.
- the lower limit value of the viscosity is not particularly limited, but can be, for example, 2 mPa ⁇ s or more.
- Examples of the polyfunctional radically polymerizable compound preferably used in the present invention include polymerizable compounds described in JP-A-2014-170949, the contents of which are included in the present specification.
- the following compounds may be mentioned as specific examples of the compound represented by the formula (2).
- the amount of the polyfunctional radically polymerizable compound used in the present invention relative to the total radically polymerizable compound in the curable composition for imprints is preferably 30 to 99% by mass, and 50 to 95% by mass. Is more preferable, 75 to 90% by mass is further preferable, and 80 to 90% by mass may be sufficient.
- the polyfunctional radically polymerizable compound may contain only one type, or two or more types. When it contains 2 or more types, it is preferable that a total amount becomes said range.
- the method for producing the polyfunctional radically polymerizable compound may be a conventional method. Synthetic methods or sources are listed for some of the exemplified compounds.
- B-22 can be synthesized from ⁇ , ⁇ '-dichloro-m-xylene and acrylic acid.
- B-16 can be synthesized from 1,4-cyclohexanedimethanol and acryloyl chloride.
- A-DCP (trade name) manufactured by Shin-Nakamura Chemical Co., Ltd. can be used.
- B-32 Kyoeisha Chemical Co., Ltd. can use light acrylate BP-4PA (trade name).
- B-9 can use Shin-Nakamura Chemical Co., Ltd.
- A-NPG brand name
- B-3 can use A-HD-N (brand name) manufactured by the company.
- B-6 Kyoeisha Chemical Co., Ltd. Light Ester 2EG (trade name) can be used.
- B-2 can be synthesized from cis-2-butene-1,4-diol and acryloyl chloride.
- Sartmar SR341 (trade name) can be used.
- the type of the monofunctional radically polymerizable compound used in the present invention is not particularly limited unless it deviates from the scope of the present invention.
- the monofunctional radically polymerizable compound used in the present invention preferably has a linear or branched hydrocarbon chain having 4 or more carbon atoms. In the present invention, only one monofunctional radically polymerizable compound may be contained, or two or more monofunctional radical polymerizable compounds may be contained.
- the Onishi parameter of the monofunctional radically polymerizable compound used in the present invention is preferably 8.1 or less, more preferably 4.0 or less, and still more preferably 3.9 or less. It is more preferably 7 or less, still more preferably 3.5 or less.
- the lower limit value of the Onishi parameter is not particularly limited, but may be, for example, 2.0 or more, or even 2.5 or more.
- the Onishi parameter is 4.0 or less, the etching rate can be lowered, the etching selectivity to the object to be processed is improved, and the etching processing margin is expanded.
- the Onishi parameter is a value calculated by the following equation.
- Onishi parameter (sum of the number of atoms of C, H and O) / (number of C atoms-number of O atoms) 50 or more are preferable, as for the molecular weight of the monofunctional radically polymerizable compound used by this invention, 150 or more are more preferable, and 220 or more are more preferable.
- the upper limit value of 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. By setting the molecular weight to the above lower limit or more, volatility tends to be suppressed. By setting the molecular weight to the above upper limit or less, the viscosity tends to be able to be reduced.
- the boiling point at 1013 hPa of the monofunctional radically polymerizable compound used in the present invention is not particularly limited, and may be, for example, less than 60 ° C. or 60 ° C. or more. It is mentioned that it is 80 ° C or more as one embodiment of the above-mentioned boiling point. Volatility can be suppressed by setting the boiling point at 667 Pa to the above lower limit value or more.
- the upper limit value of the boiling point is not particularly limited, but for example, the boiling point at 667 Pa can be 170 ° C. or less.
- the monofunctional radically polymerizable compound used in the present invention is preferably liquid at 25 ° C.
- a liquid at 25 ° C. means a compound having fluidity at 25 ° C., for example, a compound having a viscosity of 1 to 100,000 mPa ⁇ s at 25 ° C.
- the viscosity at 25 ° C. of the monofunctional radically polymerizable compound is, for example, more preferably 10 to 20,000 mPa ⁇ s, and still more preferably 100 to 15,000 mPa ⁇ s.
- viscosity at 25 ° C. of the monofunctional radically polymerizable compound used in the present invention is preferably 100 mPa ⁇ s or less, more preferably 10 mPa ⁇ s or less, still more preferably 8 mPa ⁇ s or less, and still more preferably 6 mPa ⁇ s or less.
- the lower limit value is not particularly limited, but can be, for example, 1 mPa ⁇ s or more.
- the monofunctional radically polymerizable compound used in the present invention is preferably a monofunctional (meth) acrylic monomer, and more preferably a monofunctional acrylate.
- the type of atoms constituting the monofunctional radically polymerizable compound used in the present invention is not particularly limited, it is preferably composed of only atoms selected from carbon atoms, oxygen atoms, hydrogen atoms and halogen atoms, and carbon More preferably, it is composed of only atoms selected from atoms, oxygen atoms and hydrogen atoms.
- the monofunctional radically polymerizable compound used in the present invention preferably has a linear or branched hydrocarbon chain having 4 or more carbon atoms.
- the hydrocarbon chain in the present invention represents an alkyl chain, an alkenyl chain or an alkynyl chain, preferably an alkyl chain or an alkenyl chain, more preferably an alkyl chain.
- the alkyl chain represents an alkyl group and an alkylene group.
- the alkenyl chain represents an alkenyl group and an alkenylene group
- the alkynyl chain represents an alkynyl group and an alkynylene group.
- linear or branched alkyl groups and alkenyl groups are more preferable, linear or branched alkyl groups are more preferable, and linear alkyl groups are more preferable.
- the linear or branched hydrocarbon chain (preferably, an alkyl group) has 4 or more carbon atoms, preferably 6 or more carbon atoms, more preferably 8 or more carbon atoms, and still more preferably 10 or more carbon atoms, 12 or more is more preferable.
- the upper limit of the carbon number is not particularly limited, but may be, for example, 25 or less.
- the linear or branched hydrocarbon chain may contain an ether group (—O—), but it is preferable from the viewpoint of improving mold releasability that it does not contain an ether group.
- the elastic modulus of the cured film is reduced and the releasability is improved with a relatively small addition amount.
- a monofunctional radically polymerizable compound having a linear or branched alkyl group is used, the interfacial energy between the mold and the cured film can be reduced, and the releasability can be further improved.
- hydrocarbon groups possessed by the monofunctional radically polymerizable compound used in the present invention (1) to (3) can be mentioned.
- straight-chain alkyl group having 8 or more carbon atoms (2) branched alkyl group having 10 or more carbon atoms (3) an alicyclic or aromatic ring substituted with a linear or branched alkyl group having 5 or more carbon atoms
- Straight-chain alkyl group having 8 or more carbon atoms >>> 10 or more carbon atoms are more preferable, 11 or more carbon atoms are more preferable, and 12 or more carbon atoms are more preferable. Moreover, carbon number 20 or less is preferable, carbon number 18 or less is more preferable, carbon number 16 or less is more preferable, and carbon number 14 or less is more preferable.
- Branched alkyl group having 10 or more carbon atoms >>> The branched alkyl group having 10 or more carbon atoms preferably has 10 to 20 carbon atoms, more preferably 10 to 16 carbon atoms, still more preferably 10 to 14 carbon atoms, and still more preferably 10 to 12 carbon atoms.
- Alicyclic or aromatic ring substituted by a linear or branched alkyl group having 5 or more carbon atoms is more preferably a linear alkyl group.
- the carbon number of the alkyl group is more preferably 6 or more, still more preferably 7 or more, and still more preferably 8 or more.
- the carbon number of the alkyl group is preferably 14 or less, more preferably 12 or less, and still more preferably 10 or less.
- the ring structure of the alicyclic or aromatic ring may be a single ring or a condensed ring, but is preferably a single ring. When it is a condensed ring, the number of rings is preferably two or three.
- the ring structure is preferably a 3- to 8-membered ring, more preferably a 5- or 6-membered ring, and still more preferably a 6-membered ring.
- the ring structure is an alicyclic or aromatic ring, preferably an aromatic ring.
- ring structure examples include cyclohexane ring, norbornane ring, isobornane ring, tricyclodecane ring, tetracyclododecane ring, adamantane ring, benzene ring, naphthalene ring, anthracene ring and fluorene ring, and among these, cyclohexane ring A tricyclodecane ring, an adamantane ring and a benzene ring are more preferable, and a benzene ring is more preferable.
- the monofunctional radically polymerizable compound used in the present invention 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,
- the compound in which the polymerizable group is directly bonded to any one of the groups (3) to (3) is more preferable.
- 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 Particularly preferred.
- a monofunctional radically polymerizable compound preferably used by this invention the compound used by the following 1st group and 2nd group and the Example other than these can be illustrated. However, it goes without saying that the present invention is not limited to these. Also, the first group is more preferable than the second group.
- the amount of the monofunctional radically polymerizable compound used in the present invention to the total radically polymerizable compound in the curable composition for imprints is preferably 1% by mass or more, more preferably 3% by mass or more, as the lower limit. 5 mass% or more is further preferable, and 7 mass% or more is more preferable. Moreover, 29 mass% or less is more preferable, 27 mass% or less is more preferable, 25 mass% or less is especially more preferable, 20 mass% or less is more preferable, 15 mass% or less is still more preferable.
- the amount of the monofunctional radically polymerizable compound By setting the amount of the monofunctional radically polymerizable compound to the above-mentioned lower limit value or more with respect to all radically polymerizable compounds, releasability can be improved, and defects and mold breakage can be suppressed at the time of mold release. Further, by setting the upper limit value or less, the Tg of the cured film of the curable composition for imprints can be increased, and the etching processability, in particular, the undulation of the pattern at the time of etching can be suppressed.
- monofunctional radically polymerizable compounds other than the above monofunctional radically polymerizable compounds may be used without departing from the spirit of the present invention, and among the polymerizable compounds described in JP-A-2014-170949, Examples are monofunctional radically polymerizable compounds, the contents of which are included herein.
- 90% by mass or more of all the monofunctional radically polymerizable compounds contained in the curable composition for imprints is a monofunctional radically polymerizable compound having the above groups (1) to (3) Preferably, it is 95 mass% or more.
- the curable composition for imprints of the present invention contains a radical photopolymerization initiator.
- a radical photopolymerization initiator used by this invention if it is a compound which generate
- radical photopolymerization initiator for example, a commercially available initiator can be used.
- a commercially available initiator for example, those described in Paragraph No. 0091 of JP-A-2008-105414 can be preferably adopted.
- acetophenone compounds, acyl phosphine oxide compounds, and oxime ester compounds are preferable from the viewpoint of curing sensitivity and absorption characteristics.
- an oxime compound having a fluorine atom can also be used as a radical photopolymerization initiator.
- oxime compound having a fluorine atom examples include the compounds described in JP-A-2010-262028, the compounds 24 and 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. And the like (C-3) and the like. The contents of these are incorporated herein.
- the photo radical polymerization initiator may be used singly or in combination of two or more. Specifically, IRGACURE 1173 and IRGACURE 907, IRGACURE 1173 and LUCIRIN TPO, IRGACURE 1173 and IRGACURE 819, IRGACURE 1173 and IRGACURE OXE01, IRGACURE 907 and LUCIRIN TPO, IRGACURE 907 and IRGACURE 819 are exemplified. By such a combination, the exposure margin can be expanded.
- the content of the curable composition for imprints used in the present invention is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0. 5 to 3% by mass.
- the curable composition for imprints may contain only one type of photo radical polymerization initiator, or may contain two or more types. When 2 or more types are included, it is preferable that the total amount becomes the said range.
- a sensitizer may be added to the curable composition for imprints used in the present invention, in addition to the radical photopolymerization initiator.
- the curability can be improved by blending a sensitizer.
- preferred sensitizers include compounds belonging to the following compounds and having a maximum absorption wavelength in the range of 350 nm to 450 nm.
- Polynuclear aromatics eg, pyrene, perylene, triphenylene, anthracene, phenanthrene
- xanthenes eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
- xanthones eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone , 2-isopropylthioxanthone, 2-chlorothioxanthone
- cyanines eg, thiacarbocyanine, oxacarbocyanine
- merocyanines eg, merocyanine, carbomerocyanine
- rhodacyanines oxonols
- thiazines eg, thionine
- acridines eg, acridine orange, chlorofla
- Preferred specific examples of the sensitizer include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone And phenothiazines.
- the sensitizer is preferably added in a proportion of 30 to 200 parts by mass with respect to 100 parts by mass of the radical photopolymerization initiator.
- the sensitizer may be contained singly or in combination of two or more kinds in the curable composition for imprints of the present invention. When 2 or more types are contained, it is preferable that a total amount becomes said range.
- the type of the release agent used in the present invention is not particularly limited as long as it does not deviate from the spirit of the present invention, but preferably, it has a function of segregating at the interface with the mold and promoting release from the mold.
- a compound (Hereinafter, it may be mentioned "non-polymerizable compound which has mold release property") is mentioned.
- the release agent may contain only one type, or two or more types. When the release agent is contained, the total content is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, and still more preferably 2 to 5% by mass.
- nonionic surfactant is preferable.
- the nonionic surfactant is a compound having at least one hydrophobic portion and at least one nonionic hydrophilic portion.
- the hydrophobic part and the hydrophilic part may be at the end of the molecule or at the inside, respectively.
- the hydrophobic portion is composed of a hydrophobic group selected from a hydrocarbon group, a fluorine-containing group, and a Si-containing group, and the carbon number of the hydrophobic portion is preferably 1 to 25, more preferably 2 to 15, and still more preferably 4 to 10. Preferably, 5 to 8 are more preferred.
- the nonionic hydrophilic portion is an alcoholic hydroxyl group, a phenolic hydroxyl group, an ether group (preferably a polyoxyalkylene group, a cyclic ether group), an amide group, an imide group, a ureido group, a urethane group, a cyano group, a sulfonamide group, a lactone group It is preferable to have at least one group selected from the group consisting of lactam groups and cyclocarbonate groups.
- the nonionic surfactant may be any of hydrocarbon type, fluorine type, Si type, fluorine and Si type nonionic surfactant, but fluorine type or Si type is more preferable, and fluorine type is preferable. Is more preferred.
- a fluorine and Si type surfactant means what has the requirements of both a fluorine type surfactant and a Si type surfactant.
- fluoroionic nonionic surfactants include Florard FC-4430 and FC-4431 manufactured by Sumitomo 3M Co., Ltd., Surflon S-241 and S-242 and S-243 manufactured by Asahi Glass Co., Ltd., Mitsubishi Materials Electronic Chemicals Co., Ltd. (E.F.
- the content of the surfactant is preferably 0.1 to 10% by mass in the total composition excluding the solvent, and 0.2 to 5%. % By mass is more preferable, and 0.5 to 5% by mass is more preferable.
- the curable composition for imprints may contain only one type of surfactant, or may contain two or more types. When 2 or more types are included, it is preferable that the total amount becomes the said range.
- the curable composition for imprinting has a polyalkylene glycol structure having at least one hydroxyl group at the end or an etherified hydroxyl group, and is a non-polymerizable compound substantially free of fluorine atoms and silicon atoms May be included.
- the nonpolymerizable compound means a compound having no polymerizable group.
- having substantially no fluorine atom and silicon atom means, for example, that the total content of fluorine atom and silicon atom is 1% by mass or less, and having no fluorine atom and silicon atom at all. Is preferred.
- the compatibility with a polymerizable compound is improved, and in particular, in a curable composition for imprint substantially containing no solvent, coating uniformity, pattern formation at imprinting And good line edge roughness after dry etching.
- a polyalkylene glycol structure which a non-polymerizable compound having releasability has a polyalkylene glycol structure containing an alkylene group having 1 to 6 carbon atoms is preferable, and a polyethylene glycol structure, a polypropylene glycol structure, a polybutylene glycol structure, or these A mixed structure is more preferable, a polyethylene glycol structure, a polypropylene glycol structure, or a mixed structure of these is more preferable, and a polypropylene glycol structure is more preferable.
- the non-polymerizable compound may be constituted substantially only of the polyalkylene glycol structure except for the terminal substituent.
- substantially means that the component other than the polyalkylene glycol structure is 5% by mass or less of the whole, and preferably 1% by mass or less.
- the polyalkylene glycol structure preferably has 3 to 100 alkylene glycol structural units, more preferably 4 to 50, and still more preferably 5 to 30. It is more preferable to have ⁇ 20.
- the non-polymerizable compound having releasability preferably has at least one hydroxyl group at the end or the hydroxyl group is etherified.
- the remaining terminal may be a hydroxyl group, or the hydrogen atom of the terminal hydroxyl group may be substituted.
- an alkyl group namely, polyalkylene glycol alkyl ether
- an acyl group namely, polyalkylene glycol ester
- Compounds having a plurality of (preferably 2 or 3) polyalkylene glycol chains via a linking group can also be preferably used.
- nonpolymerizable compound having releasability examples include polyethylene glycol, polypropylene glycol (eg, manufactured by Wako Pure Chemical Industries, Ltd.), mono or dimethyl ether thereof, mono or dibutyl ether, mono or dioctyl ether, mono or dicetyl. Ethers, monostearic acid esters, monooleic acid esters, polyoxyethylene glyceryl ethers, polyoxypropylene glyceryl ethers, and trimethyl ethers thereof.
- the weight average molecular weight of the nonpolymerizable compound having releasability is preferably 150 to 6000, more preferably 200 to 3000, still more preferably 250 to 2000, and still more preferably 300 to 1200.
- a non-polymerizable compound having releasability which can be used in the present invention a non-polymerizable compound having releasability having an acetylene diol structure can also be exemplified.
- Olfin E1010 made by Nisshin Chemical Industry Co., Ltd.
- the content of the nonpolymerizable compound having releasability is 0.1% of the total composition excluding the solvent. % By mass or more is preferable, 0.5% by mass or more is more preferable, 1.0% by mass or more is more preferable, and 2% by mass or more is more preferable. Moreover, 20 mass% or less is preferable, 10 mass% or less is more preferable, and 5 mass% or less is more preferable as said content.
- the curable composition for imprints may contain only one type of non-polymerizable compound having releasability, or may contain two or more types. When 2 or more types are included, it is preferable that the total amount becomes the said range.
- the curable composition for imprints of the present invention may contain an antioxidant.
- the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
- phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl ) Propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 4 , 4'-Butylidene-bis (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9- Bis ⁇ 2- [3- (3-t-butyl-4-
- phenolic antioxidants include Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 245, Irganox 259, Irganox 295, and Irganox 3114 (all from BASF Corporation).
- phosphorus-based antioxidants include trisnonylphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-t) -Butylphenyl) pentaerythritol phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphos Phyto, tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylene-di-phosphanite and the like can be mentioned.
- Adekastab 1178 manufactured by ADEKA Co., Ltd.
- Sumilyzer TNP manufactured by Sumitomo Chemical Co., Ltd.
- JP-135 manufactured by Johoku Chemical Co., Ltd.
- Adekastab 2112 manufactured by Co., Ltd.
- Adeka, JPP-2000 made by Johoku Chemical Co., Ltd.
- Weston 618 made by GE
- Adekastab PEP-24G made by ADEKA
- Adekastab PEP-36 made by Adeka
- Adekastab HP -10 manufactured by ADEKA Co., Ltd.
- Sandstab P-EPQ manufactured by Sand Co., Ltd.
- Phosphite 168 manufactured by BASF
- sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythritol Tetrakis (3-lauryl thiopropionate) and the like can be mentioned.
- sulfur-based antioxidants include Sumilizer TPL (manufactured by Sumitomo Chemical Co., Ltd.), Yoshinox DLTP (manufactured by Yoshitomi Seiyaku Co., Ltd.), Anthiox L (manufactured by NOF Corporation), Sumilizer TPM (Sumitomo Chemical Co., Ltd.) Co., Ltd., Yoshinox DMTP (Yoshitomi Pharmaceutical Co., Ltd.), Anthiox M (Nippon Oil Co., Ltd.), Sumilyzer TPS (Sumitomo Chemical Co., Ltd.), Yoshinox DSTP (Yoshitomi Pharmaceutical Co., Ltd.) , Anthiox S (manufactured by NOF Corporation), Adekastab AO-412S (manufactured by ADEKA), SEENOX 412S (manufactured by Shipro Kasei Co., Ltd.), Sumilyzer TDP (manufactured by Sumitoto Chemical
- the antioxidant used by the Example mentioned later can be used preferably.
- the content of the antioxidant is preferably 0.001 to 5% by mass in the curable composition for imprints, when blended.
- the antioxidant may be contained singly or in combination of two or more kinds in the curable composition for imprints. When 2 or more types are contained, it is preferable that a total amount becomes said range.
- the curable composition for imprints used in the present invention is a polymerization inhibitor (for example, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1) in addition to the above, without departing from the scope of the present invention.
- a polymerization inhibitor for example, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1
- -Oxyl free radical etc., UV absorber, solvent etc. may be included.
- Each of these compounds may contain only one kind, or two or more kinds. The details of these can be referred to the description of paragraphs 0061 to 0064 of JP-A-2014-170949, the contents of which are incorporated herein.
- the content of the component having a weight average molecular weight of more than 2000 can be 5% by mass or less, preferably 3% by mass or less, and 1% by mass. It is further more preferable that it is% or less, and it is still more preferable that it is 0.1 mass% or less.
- the curable composition for imprints of the present invention preferably has a viscosity of 15 mPa ⁇ s or less at 25 ° C., more preferably 13 mPa ⁇ s or less, still more preferably 11 mPa ⁇ s or less, and even more preferably 9 mPa ⁇ s or less.
- 8 mPa ⁇ s or less is more preferable.
- the lower limit value of the viscosity is not particularly limited, but can be, for example, 3 mPa ⁇ s or more, and further 5 mPa ⁇ s or more. With such a range, the curable composition for imprints of the present invention can easily enter the mold, and the mold filling time can be shortened. Furthermore, it also becomes possible to improve pattern formability and throughput.
- the Onishi parameter of the curable composition for imprints of this invention is 3.4 or less. Is even more preferred.
- the lower limit value of the Onishi parameter is not particularly limited, but can be, for example, equal to or higher than the above-mentioned lower limit value. By setting the Onishi parameter to the upper limit value or less, it is possible to more effectively suppress etching processing characteristics, in particular, pattern disconnection after etching.
- the glass transition temperature after hardening of the curable composition for imprints of this invention is 100 degreeC or more, It is more preferable that it is 120 degreeC or more, It is more preferable that it is 150 degreeC or more.
- the upper limit of the glass transition temperature is not particularly limited, but may be, for example, 350 ° C. or less.
- the curable composition for imprints of the present invention may be filtered before use.
- a polytetrafluoroethylene (PTFE) filter can be used.
- the pore size of the filter is preferably 0.003 ⁇ m to 5.0 ⁇ m.
- the details of the filtration can be referred to the description in paragraph 0070 of JP-A-2014-170949, the contents of which are incorporated herein.
- a conventionally known storage container can be used as a storage container for the curable composition for imprints of the present invention.
- the inner wall of the container is made of a multilayer bottle consisting of 6 kinds of resin and 6 layers of resin, and 6 kinds of resin with 7 layers structure It is also preferred to use a bottle which has been As such a container, for example, the container described in JP-A-2015-123351 can be mentioned.
- the curable composition for imprints of the present invention is used as a photocured cured product. More specifically, a pattern is formed and used by the optical imprint method.
- the pattern manufacturing method of the present invention is to apply the curable composition for imprints of the present invention on a substrate or a mold, and irradiate light in a state in which the curable composition for imprints is sandwiched between the mold and the substrate. including.
- a pattern is applied on a substrate or a mold.
- the method of application is not particularly limited, and the description of paragraph 0102 of JP-A-2010-109092 (corresponding US application, US Patent Application Publication No. 2011/199592) can be referred to and the contents thereof are incorporated herein.
- a spin coating method or an inkjet method is preferred.
- the substrate is not particularly limited, and the contents thereof are incorporated herein by reference to the description in paragraph 0103 of JP-A-2010-109092 (corresponding US application is US Patent Application Publication 2011/199592).
- an aluminosilicate glass, an alumino borosilicate glass, barium borosilicate glass is mentioned as a specific example of a material of a glass substrate.
- a silicon substrate is preferred.
- the mold is not particularly defined, and the description of paragraphs 0105 to 0109 of JP 2010-109092 A (corresponding US application is US Patent Application Publication 2011/199592) can be referred to and the contents thereof are incorporated herein.
- a quartz mold is preferred.
- the pattern (line width) of the mold used in the present invention preferably has a size of 50 nm or less.
- the curable composition for imprints is irradiated with light in a state of being sandwiched between the mold and the substrate.
- the step of pressing against the substrate or the mold can be preferably performed in a rare gas atmosphere, a reduced pressure atmosphere, or a reduced rare gas atmosphere.
- the reduced pressure atmosphere means a state in a space viewed at a pressure lower than atmospheric pressure (101325 Pa), preferably 1000 Pa or less, more preferably 100 Pa or less, and still more preferably 1 Pa or less. If a noble gas is used, helium is preferred.
- the exposure dose is preferably in the range of 5 mJ / cm 2 to 1000 mJ / cm 2 .
- the curable composition for imprints of the present invention is preferably further heated and cured after light irradiation.
- an underlayer film composition may be provided between the substrate and the curable composition layer for imprints. That is, the curable composition for imprinting (and the cured product of the present invention) may be provided directly on the surface of the substrate or mold, or provided on the substrate or mold via one or more layers. It is also good.
- the details of the pattern manufacturing method can be referred to the description of paragraph Nos. 0103 to 0115 of JP-A-2010-109092 (corresponding US application: US Patent Application Publication No. 2011/199592), and the contents thereof are described in this specification. Incorporated into the book.
- the pattern manufacturing method of the present invention can form a fine pattern at low cost and with high accuracy by a photo imprinting method (more preferably, a photo nanoimprinting method). For this reason, it is possible to form the one formed using the conventional photolithography technology with higher accuracy and lower cost.
- the pattern in the present invention may be applied as a permanent film such as an overcoat layer or an insulating film, or an etching resist such as a semiconductor integrated circuit, a recording material, or a flat panel display, which is used for liquid crystal display (LCD) or the like. It is possible.
- the pattern obtained by the pattern manufacturing method of the present invention is excellent in etching resistance, and can be preferably used as an etching resist for dry etching using fluorocarbon or the like.
- the concentration of ionic impurities of metal or organic substance in the curable composition for imprints used in the present invention is preferably 1 mass ppm (parts per million) or less, and 100 mass ppb (parts per billion) or less More preferably, 10 mass ppb or less is more preferable, and 100 mass ppt or less is more preferable.
- Examples of the method for removing metal or organic ionic impurities from the curable composition for imprints include filtration using a filter.
- the pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less.
- filters made of polytetrafluoroethylene, polyethylene, or nylon are preferable.
- the filter may be one previously washed with an organic solvent.
- plural types of filters may be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes and / or different materials may be used in combination.
- the various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulation filtration step.
- filter filtration is performed on the materials constituting the various materials, in which the material having a small metal content is selected as the materials constituting the various materials. It is possible to cite a method such as distilling under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark) or the like.
- Teflon registered trademark
- the preferable conditions in the filter filtration performed with respect to the raw material which comprises various materials are the same as the conditions mentioned above.
- filter filtration and adsorbent may be used in combination.
- adsorbent known adsorbents can be used.
- inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
- the pattern formed by the pattern manufacturing method of the present invention can be used as a permanent film used for LCD or the like, or as an etching resist for semiconductor processing.
- a polarizing plate described in JP-A-2015-132825 or WO 2011/132649 can be manufactured.
- 1 inch is 25.4 mm.
- permanent membranes are bottled in containers such as gallon bottles and coated bottles after manufacture, and transported and stored.
- the inside of the container is replaced with inert nitrogen or argon or the like for the purpose of preventing deterioration. You may leave it.
- the temperature may be normal temperature, the temperature may be controlled in the range of ⁇ 20 ° C. to 0 ° C. to further prevent deterioration of the permanent film. Of course, it is preferable to shield the light at a level at which the reaction does not proceed.
- the pattern of the present invention is a recording medium such as a magnetic disk, a light receiving element such as a solid-state image sensor, a light emitting element such as an LED or an organic EL, an optical device such as an LCD, a diffraction grating, a relief hologram, an optical waveguide, Optical components such as optical filters and microlens arrays, thin film transistors, organic transistors, color filters, antireflection films, polarizing plates, polarizing elements, members for flat panel displays such as optical films and columns, nanobiodevices, immunoassay chips, deoxyribo It can be preferably used for producing a nucleic acid (DNA) separation chip, a microreactor, a photonic liquid crystal, a guide pattern for directed self-assembly (DSA) using self-assembly of a block copolymer, and the like.
- DNA nucleic acid
- DSA directed self-assembly
- the pattern formed by the pattern manufacturing method of the present invention is also useful as an etching resist (a mask for lithography).
- a silicon substrate (silicon wafer or the like) or the like on which a thin film such as SiO 2 is formed is used as a substrate, and the pattern manufacturing method of the present invention Or form a fine pattern of micro order.
- the present invention is particularly advantageous in that fine patterns of nano order can be formed, and also patterns of 50 nm or less in size, particularly 30 nm or less can be formed.
- the lower limit value of the size of the pattern formed by the pattern manufacturing method of the present invention is not particularly limited, but can be, for example, 1 nm or more.
- the pattern obtained by the manufacturing method of the present invention is preferably used as a mask for etching.
- the present invention also discloses a method for producing a substrate to be processed, in which etching is performed using the pattern obtained by the production method of the present invention as a mask.
- the resultant was filtered with a polytetrafluoroethylene (PTFE) filter with a pore size of 0.1 ⁇ m to prepare a curable composition for imprinting.
- PTFE polytetrafluoroethylene
- Tables 2 to 4 are mass ratios.
- the following evaluation was performed about the obtained curable composition for imprints. The results are shown in Table 5.
- ⁇ Viscosity> The viscosity of the curable composition for imprint (before curing) and the viscosity of the polyfunctional radically polymerizable compound were measured at 25 ° C. using a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd. The rotational speed at the time of measurement was as shown in Table 1 below according to the viscosity.
- the adhesion between the substrate and the cured product for imprinting was evaluated as follows.
- the quartz mold used was a quartz mold having a line / space (Space) with a line width of 30 nm and a depth of 60 nm.
- the curable composition for imprints was applied on a silicon wafer by an ink jet method using an ink jet printer DMP-2831 manufactured by FUJIFILM Dimatix as an ink jet apparatus, and then sandwiched by the mold in a helium atmosphere.
- the quartz mold was exposed to light at 100 mJ / cm 2 using a high pressure mercury lamp from the quartz mold surface, and the quartz mold was released to obtain a pattern with a pattern size (line width) of 30 nm (hereinafter referred to as a sample).
- the thickness (pattern height) of the residual film of the sample was 60 nm.
- the force required for mold release was measured. Evaluation was made according to the following evaluation categories. A: F ⁇ 12 N B: 12N ⁇ F ⁇ 18N C: F> 18 N
- the compounds used in Tables 2 to 4 are as follows.
- the compounds represented by the formula (1) are the compounds exemplified above by the numbers of GX (X is an ordinal number, hereinafter the same) except G-1-13 and G-1-14.
- the compounds represented by the formula (2) are the compounds exemplified above by the BX number except B-1-13 and B-1-14.
- the monofunctional radically polymerizable compound is a compound shown in the following Table 6 as a number of AX.
- the photo radical polymerization initiator is a compound shown in the following Table 7 as the number of C—X.
- the releasing agent is a compound shown in Table 8 below as the number of D-X.
- Onishi parameter (sum of the number of atoms of C, H and O) / (number of C atoms-number of O atoms)
- the curable composition for imprints of the present invention As apparent from Table 5 and the like, in the curable composition for imprints of the present invention, the cured product was excellent in the adhesion to the substrate, and the storage stability of the curable composition for imprints itself was excellent. Furthermore, the curable composition for imprints of the present invention was also excellent in mold releasability. Moreover, from this result, the curable composition for imprints of the present invention can be used as a material for cured products and patterns used in various applications, and the cured products and patterns are particularly suitable as a mask for lithography. It is understood that it can be used.
- the curable composition for imprints of a comparative example which does not contain the compound represented by Formula (1) is inferior to the adhesiveness with the board
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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。
本発明の課題は、上記問題点を解決することを目的とするものであって、硬化物としたときの基板との密着性が高く、保存安定性に優れたインプリント用硬化性組成物、硬化物、パターン製造方法、リソグラフィ方法、パターン、リソグラフィ用マスク、および、インプリント用重合性組成物を提供することを目的とする。
<1> 下記式(1)で表される化合物と、上記式(1)で表される化合物以外のラジカル重合性化合物と、光ラジカル重合開始剤を含む、インプリント用硬化性組成物;
<2> 上記式(1)で表される化合物の含有量が、上記式(1)で表される化合物以外のラジカル重合性化合物の含有量100質量部に対して、0.005~1質量部である、<1>に記載のインプリント用硬化性組成物。
<3> 上記式(1)で表される化合物以外のラジカル重合性化合物は、(メタ)アクリロイル基の少なくとも1種を含む、<1>または<2>に記載のインプリント用硬化性組成物。
<4> 上記式(1)で表される化合物の分子量が100~1500である、<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> 上記式(1)で表される化合物が、ラジカル重合性基を有する、<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> 上記式(1)のR4またはR5が下記式(1-3)で表される、<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> 上記式(1)のR3および上記式(1-3)のR6がそれぞれ独立に下記式(1-1)で表される、<6>に記載のインプリント用硬化性組成物;
<8> 上記式(1)で表される化合物以外のラジカル重合性化合物の少なくとも1種が、下記式(2)で表される化合物を含む、<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> 上記式(1)で表される化合物以外のラジカル重合性化合物の少なくとも1種が、単官能(メタ)アクリルモノマーである、<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おける溶剤の含有量が、5質量%以下である、<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おける重量平均分子量が2000を超える成分の含有量が、5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25℃における粘度が3~15mPa・s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> <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から形成される硬化物。
<14> 上記硬化物が、シリコン基板の上に設けられている、<13>に記載の硬化物。
<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、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製造方法。
<16> 上記パターンのサイズが30nm以下である、<15>に記載のパターン製造方法。
<17> <15>または<16>に記載のパターン製造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、被加工基板の製造方法。
<18> <1>~<12>のいずれか1つに記載の硬化性組成物から形成されるパターンであって、パターンサイズが30nm以下であるパターン。
<19> <18>に記載のパターンの少なくとも1種を含む、エッチング用マスク。
<20> 下記式(1)で表される化合物と下記式(2)で表される化合物とを含む、インプリント用重合性組成物;
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、光学フィルター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。
本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。
本発明における沸点測定時の気圧は、特に述べない限り、101325Pa(1気圧)とする。本発明における温度は、特に述べない限り、25℃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。
本明細書において、重量平均分子量(Mw)および数平均分子量(Mn)は、特に述べない限り、ゲル浸透クロマトグラフィ(GPC測定)に従い、ポリスチレン換算値として定義される。本明細書において、重量平均分子量(Mw)および数平均分子量(Mn)は、例えば、HLC-8220(東ソー(株)製)を用い、カラムとしてガードカラムHZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000またはTSKgel Super HZ2000(東ソー(株)製)を用いることによって求めることができる。溶離液は特に述べない限り、THF(テトラヒドロフラン)を用いて測定したものとする。また、検出は特に述べない限り、UV線(紫外線)の波長254nm検出器を使用したものとする。
このメカニズムは、アミノ基(R1R2N-)(下記式の<ii>の部分)が基板との密着性を高める作用を奏し、メチレン基(-CH2-)(下記式の<i>の部分)に発生したラジカルが組成物を不安定にする系内の活性酸素種をトラップする作用を奏するものと推定される(下記式1a参照)。
本発明のインプリント用硬化性組成物は、上記式(1)で表される化合物を含有する。式(1)で表される化合物はラジカル重合性基を有することが好ましい。ラジカル重合性基を有することにより、硬化物の一部となり、レジストとの密着力がより向上する傾向にある。ラジカル重合性基の好ましいものは、後記R3で規定するものと同義である。ラジカル重合性基は、式(1)で表される化合物一分子中、1~5個であることが好ましく、2~5個であることがより好ましく、2個または3個であることがさらに好ましく、2個であることが一層好ましい。
本発明の一実施形態として、R1およびR2が同じ基であることが挙げられる。このような構成とすることにより、本発明の効果がより効果的に発揮される。
このような構成とすることにより、基板とインプリント用硬化性組成物の密着性がより向上する傾向にある。
R7の有機基は下記式(1-2)で表される連結基であることが好ましい。
また、R9が環構造を有するとき、後記「(3)炭素数5以上の直鎖または分岐のアルキル基が置換した脂環または芳香環」で述べる脂環または芳香環を含有する構造であることもまた好ましい。
連結基Lとしては、直鎖または分岐のアルキレン基(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)、直鎖または分岐のアルケ二レン基(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)、-O-、-S-、-CO-、-NRN-、-NRNCO-、およびそれらの組み合わせに係る連結基が挙げられる。RNは上記と同義である。連結基Lに含まれる原子数は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。
pは0以上で、各環に置換可能な最大数以下の整数である。上限値は、それぞれの場合で独立に、置換可能最大数の半分以下であることが好ましく、4以下であることがより好ましく、2以下であることがさらに好ましい。
*は結合位置を表す。
Arはアリーレン基(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)であり、具体的には、フェニレン基、ナフタレンジイル基、アントラセンジイル基、フェナントレンジイル基、フルオレンジイル基が挙げられる。
Z3は、単結合または連結基Lの例が挙げられる。Z3は、中でも、単結合、-O-、またはアルキレン基(炭素数1~6が好ましく、1~3がより好ましい、特に、メチレン基、2,2-プロピレンジイル基が好ましい)が好ましい。Z3がアルキレン基であるときは置換基Tが置換していてもよく、特にはハロゲン原子(特にフッ素原子)が置換していてもよい。
hCyはヘテロ環基(炭素数1~12が好ましく、1~6がより好ましく、2~5がさらに好ましい)であり、5員環または6員環がより好ましい。hCyを構成するヘテロ環の具体例としては、チオフェン環、フラン環、ジベンゾフラン環、カルバゾール環、インドール環、テトラヒドロピラン環、テトラヒドロフラン環、ピロール環、ピリジン環、ピラゾール管、イミダゾール環、ベンゾイミダゾール環、トリアゾール環、チアゾール環、オキサゾール環、ピロリドン環、モルホリン環が挙げられ、中でも、チオフェン環、フラン環、ジベンゾフラン環が好ましい。
nおよびmは100以下の自然数であり、1~12が好ましく、1~6がより好ましく、1~3がさらに好ましい。
R7の好ましい範囲は、式(1-1)におけると同義であり、好ましい範囲も同様である。
R8は本発明の効果を損ねない範囲で、置換基Tを有していてもよい。この置換基としては、例えば、アミノ基(炭素数0~12が好ましく、0~6がより好ましく、0~3がさらに好ましい)が挙げられる。
また、上記式(1)で表される化合物は、ラジカル重合性基を有していなくてもよいが、ラジカル重合性基を有することが好ましく、R3~R5の少なくとも一つがラジカル重合性基を有することがより好ましく、R3とR4およびR5のいずれか一方とがラジカル重合性基を有することがさらに好ましい。
R3~R5から選ばれる2つはそれぞれ互いに結合して環を形成していてもよい。形成される環には任意の連結基が介在してもよく、例えば連結基Lの例が挙げられる。
式(1)で表される化合物は、炭素原子、酸素原子、水素原子および窒素原子から選択される原子のみによって構成されていることが好ましい。
本発明のインプリント用硬化性組成物において、上記式(1)で表される化合物と後述する式(2)で表される化合物とは、必要により他の成分と組み合わせて、インプリント用重合性組成物を構成していてもよい。本発明のインプリント用硬化性組成物における上記式(1)で表される化合物の含有量は、後述する式(2)で表される化合物の含有量100質量部に対して、0.005~1質量部であることが好ましく、0.01~0.75質量部であることがより好ましく、0.05~0.5質量部であることがさらに好ましい。このような範囲とすることにより、密着性、離型力、経時安定性について、バランスよく、より優れる傾向にある。
また、本発明のインプリント用硬化性組成物における、式(1)で表される化合物は、インプリント用硬化性組成物の全固形分の0.005~1質量%であることが好ましく、0.01~0.75質量%であることがより好ましく、0.05~0.5質量%であることがさらに好ましい。
上記の含有量(式(1)の化合物の配合量)を上記上限値以下とすることで、良好な離型性を維持することができ好ましい。一方、この含有量を上記下限値以上とすることで、上記密着性と安定性とが一層効果的に発揮され好ましい。
本発明のインプリント用硬化性組成物において、上記式(1)で表される化合物は、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、式(1)で表される化合物以外のラジカル重合性化合物(他のラジカル重合性化合物)を含む。他のラジカル重合性化合物は、アミノメチル基を有さないことが好ましい。
他のラジカル重合性化合物は、ラジカル重合性基が1つである単官能ラジカル重合性化合物でも、ラジカル重合性基が2つ以上である多官能ラジカル重合性化合物でもよい。本発明のインプリント用硬化性組成物は、多官能ラジカル重合性化合物を含むことが好ましく、多官能ラジカル重合性化合物と単官能ラジカル重合性化合物の両方を含むことがより好ましい。
多官能ラジカル重合性化合物は、二官能ラジカル重合性化合物および三官能ラジカル重合性化合物の少なくとも1種を含むことが好ましく、二官能ラジカル重合性化合物の少なくとも1種を含むことがより好ましい。
他のラジカル重合性化合物は、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種以上含む場合は、合計量が上記範囲となることが好ましい。
本発明では、上記式(1)で表される化合物以外のラジカル重合性化合物が、下記式(2)で表される化合物を含むことが好ましい。このような範囲とすることにより、密着性、離型力、経時安定性について、バランスよく、より優れる傾向にある。
R21は、2~7価の有機基であることが好ましく、2~4価の有機基であることがより好ましく、2または3価の有機基であることがさらに好ましく、2価の有機基であることが一層好ましい。R21は直鎖、分岐および環状の少なくとも1つの構造を有する炭化水素基であることが好ましい。炭化水素基の炭素数は、2~20が好ましく、2~10がより好ましい。
R21が2価の有機基であるとき、上記式(1-2)で表される連結基であることが好ましく、その好ましい範囲も同じである。式(1)における式(1-2)の構造と、式(2)における式(1-2)の構造が組成物内で一致していることが、本発明の好ましい態様として挙げられる。
R21が環構造を有するとき、後記「(3)炭素数5以上の直鎖または分岐のアルキル基が置換した脂環または芳香環」で述べる脂環または芳香環を含有する構造であることもまた好ましい。
本発明で用いる多官能ラジカル重合性化合物は、後述する大西パラメータが、4.5以下であることが好ましい。大西パラメータの下限値については、特に定めるものでは無いが、例えば、2.0以上とすることもできる。
本発明で用いる多官能ラジカル重合性化合物の分子量は、1000以下であることが好ましく、800以下であることがより好ましく、500以下がさらに好ましく、350以下が一層好ましく、230以下がより一層好ましい。分子量の上限値を上記上限値以下とすることで、化合物の粘度を低減できる傾向がある。
分子量の下限値については、特に定めるものでは無いが、例えば、170以上とすることができる。
式(2)で表される化合物の具体例としては下記化合物が挙げられる。
多官能ラジカル重合性化合物は、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種以上含む場合は、合計量が上記範囲となることが好ましい。
多官能ラジカル重合性化合物の製造方法は定法によればよい。いくつかの例示化合物について合成法または入手元を挙げる。B-22はα,α’-ジクロロ-m-キシレンとアクリル酸より合成できる。B-16は1,4-シクロヘキサンジメタノールとアクリロイルクロリドより合成できる。B-14は新中村化学工業(株)製 A-DCP(商品名)を使用できる。B-32は共栄社化学株式会社 ライトアクリレートBP-4PA(商品名)を使用できる。B-9は新中村化学工業(株)製 A-NPG(商品名)、B-3は同社製 A-HD-N(商品名)を使用できる。B-6は共栄社化学株式会社 ライトエステル2EG(商品名)を使用できる。B-2はcis-2-ブテン-1,4-ジオールとアクリロイルクロリドより合成できる。B-10はサートマー社製のSR341(商品名)を使用できる。
本発明で用いる単官能ラジカル重合性化合物は、その種類は本発明の趣旨を逸脱しない限り特に定めるものではない。本発明で用いる単官能ラジカル重合性化合物は、炭素数4以上の直鎖または分岐の炭化水素鎖を有することが好ましい。本発明では単官能ラジカル重合性化合物を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。
ここで、大西パラメータは、以下の式で算出される値である。
大西パラメータ=(C、H、およびOの原子数の和)/(C原子数-O原子数)
本発明で用いる単官能ラジカル重合性化合物の分子量は、50以上が好ましく、150以上がより好ましく、220以上がさらに好ましい。分子量の上限値は、1000以下が好ましく、800以下がより好ましく、300以下がさらに好ましく、270以下が一層好ましい。分子量を上記下限値以上とすることで、揮発性を抑制できる傾向がある。分子量を上記上限値以下とすることで、粘度を低減できる傾向がある。
本発明で用いる単官能ラジカル重合性化合物の1013hPaにおける沸点は、特に定めるものではなく、例えば、60℃未満であってもよいし、60℃以上であってもよい。上記沸点の一実施形態として、80℃以上であることが挙げられる。667Paにおける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、667Paにおける沸点を170℃以下とすることができる。
本発明において、25℃で液体とは、25℃で流動性を有する化合物であって、例えば、25℃での粘度が、1~100,000mPa・sである化合物を意味する。単官能ラジカル重合性化合物の25℃での粘度は、例えば、10~20,000mPa・sがより好ましく、100~15,000mPa・sが一層好ましい。
25℃で液体の化合物を用いることにより、溶剤を実質的に含まない構成とすることができる。ここで、溶剤を実質的に含まないとは、例えば、本発明のインプリント用硬化性組成物に対する溶剤の含有量が5質量%以下であることをいい、さらには3質量%以下であることをいい、特には1質量%以下であることをいう。
本発明で用いる単官能ラジカル重合性化合物の25℃での粘度は、100mPa・s以下が好ましく、10mPa・s以下がより好ましく、8mPa・s以下がさらに好ましく、6mPa・s以下が一層好ましい。単官能ラジカル重合性化合物の25℃での粘度を上記上限値以下とすることで、インプリント用硬化性組成物の粘度を低減でき、充填性が向上する傾向がある。下限値については、特に定めるものではないが、例えば、1mPa・s以上とすることができる。
本発明において、アルキル鎖とは、アルキル基およびアルキレン基を表す。同様に、アルケニル鎖とは、アルケニル基およびアルケニレン基を表し、アルキニル鎖とはアルキニル基およびアルキニレン基を表す。これらの中でも、直鎖または分岐のアルキル基、アルケニル基がより好ましく、直鎖または分岐のアルキル基がさらに好ましく、直鎖のアルキル基が一層好ましい。
上記直鎖または分岐の炭化水素鎖(好ましくは、アルキル基)は、炭素数4以上であり、炭素数6以上が好ましく、炭素数8以上がより好ましく、炭素数10以上がさらに好ましく、炭素数12以上が一層好ましい。炭素数の上限値については、特に定めるものではないが、例えば、炭素数25以下とすることができる。
上記直鎖または分岐の炭化水素鎖は、エーテル基(-O-)を含んでいてもよいが、エーテル基を含んでいない方が離型性向上の観点から好ましい。
このような炭化水素鎖を有する単官能ラジカル重合性化合物を用いることで、比較的少ない添加量で、硬化膜の弾性率を低減し、離型性が向上する。また、直鎖または分岐のアルキル基を有する単官能ラジカル重合性化合物を用いると、モールドと硬化膜の界面エネルギーを低減して、さらに離型性を向上することができる。
本発明で用いる単官能ラジカル重合性化合物が有する好ましい炭化水素基として、(1)~(3)を挙げることができる。
(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5以上の直鎖または分岐のアルキル基が置換した脂環または芳香環
炭素数8以上の直鎖アルキル基は、炭素数10以上がより好ましく、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5以上の直鎖または分岐のアルキル基が置換した脂環または芳香環>>>
炭素数5以上の直鎖または分岐のアルキル基は、直鎖のアルキル基がより好ましい。上記アルキル基の炭素数は、6以上がより好ましく、7以上がさらに好ましく、8以上が一層好ましい。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。
脂環または芳香環の環構造は、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。環構造は、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。また、環構造は、脂環または芳香環であるが、芳香環であることが好ましい。環構造の具体例としては、シクロヘキサン環、ノルボルナン環、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、ベンゼン環、ナフタレン環、アントラセン環、フルオレン環が挙げられ、これらの中でもシクロヘキサン環、トリシクロデカン環、アダマンタン環、ベンゼン環がより好ましく、ベンゼン環がさらに好ましい。
本発明で好ましく用いられる単官能ラジカル重合性化合物としては、下記第1群および第2群並びにこれら以外の実施例で用いている化合物を例示することができる。しかしながら、本発明がこれらに限定されるものでは無いことは言うまでもない。また、第1群の方が第2群よりもより好ましい。
第1群
本発明では、インプリント用硬化性組成物に含まれる全単官能ラジカル重合性化合物の90質量%以上が、上記(1)~(3)の基を有する単官能ラジカル重合性化合物であることが好ましく、95質量%以上であることがより好ましい。
本発明のインプリント用硬化性組成物は、光ラジカル重合開始剤を含む。
本発明で用いられる光ラジカル重合開始剤としては、光照射により上述のラジカル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。
本発明は、光ラジカル重合開始剤として、フッ素原子を有するオキシム化合物を用いることもできる。フッ素原子を有するオキシム化合物の具体例としては、特開2010-262028号公報に記載の化合物、特表2014-500852号公報に記載の化合物24、36~40、特開2013-164471号公報に記載の化合物(C-3)などが挙げられる。これらの内容は本明細書に組み込まれる。
本発明で用いるインプリント用硬化性組成物には、光ラジカル重合開始剤の他に、増感剤を加えることもできる。本発明のインプリント用硬化性組成物が、酸素雰囲気下で硬化しにくい場合、増感剤を配合することにより、硬化性を改善することができる。
好ましい増感剤の例としては、以下の化合物類に属しており、かつ350nmから450nm領域に極大吸収波長を有する化合物を挙げることができる。多核芳香族類(例えば、ピレン、ペリレン、トリフェニレン、アントラセン、フェナントレン)、キサンテン類(例えば、フルオレセイン、エオシン、エリスロシン、ローダミンB、ローズベンガル)、キサントン類(例えば、キサントン、チオキサントン、ジメチルチオキサントン、ジエチルチオキサントン、2-イソプロピルチオキサントン、2-クロロチオキサントン)、シアニン類(例えば、チアカルボシアニン、オキサカルボシアニン)、メロシアニン類(例えば、メロシアニン、カルボメロシアニン)、ローダシアニン類、オキソノール類、チアジン類(例えば、チオニン、メチレンブルー、トルイジンブルー)、アクリジン類(例えば、アクリジンオレンジ、クロロフラビン、アクリフラビン、ベンゾフラビン)、アクリドン類(例えば、アクリドン、10-ブチル-2-クロロアクリドン)、アントラキノン類(例えば、アントラキノン、9,10-ジブトキシアントラセン)、スクアリリウム類(例えば、スクアリリウム)、スチリル類、ベーススチリル類、クマリン類(例えば、7-ジエチルアミノ-4-メチルクマリン、ケトクマリン)、カルバゾール類(例えば、N-ビニルカルバゾール)、カンファーキノン類、フェノチアジン類。
この他、本発明において用いることができる典型的な増感剤としては、クリベロ〔J. V. Crivello, Adv. in Polymer Sci., 62, 1 (1984)〕に開示しているものが挙げられる。
増感剤の好ましい具体例としては、ピレン、ペリレン、アクリジンオレンジ、チオキサントン、2-クロロチオキサントン、ベンゾフラビン、N-ビニルカルバゾール、9,10-ジブトキシアントラセン、アントラキノン、クマリン、ケトクマリン、フェナントレン、カンファーキノン、フェノチアジン類などを挙げることができる。
また、本発明では、増感剤として、特許第4937806号公報の段落0043~0046、特開2011-3916号公報の段落0036に記載の化合物も好ましく用いることができる。
増感剤は、本発明のインプリント用硬化性組成物に含まれる場合、光ラジカル重合開始剤100質量部に対し、30~200質量部の割合で添加することが好ましい。
増感剤は、本発明のインプリント用硬化性組成物に1種のみ含まれていても、2種以上含まれていてもよい。2種以上含まれている場合は、合計量が上記範囲となることが好ましい。
本発明に用いる離型剤は、その種類は本発明の趣旨を逸脱しない限り特に定めるものではないが、好ましくは、モールドとの界面に偏析し、モールドとの離型を促進する機能を有する添加剤を意味する。具体的には、界面活性剤および、末端に少なくとも1つの水酸基を有するか、または、水酸基がエーテル化されたポリアルキレングリコール構造を有し、フッ素原子およびシリコン原子を実質的に含有しない非重合性化合物(以下、「離型性を有する非重合性化合物」ということがある)が挙げられる。
離型剤は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。また、離型剤を含む場合、含有量は、合計で0.1~20質量%が好ましく、1~10質量%がより好ましく、2~5質量%がさらに好ましい。
界面活性剤としては、ノニオン性界面活性剤が好ましい。
ノニオン性界面活性剤とは、少なくとも一つの疎水部と少なくとも一つのノニオン性親水部を有する化合物である。疎水部と親水部は、それぞれ、分子の末端にあっても、内部にあってもよい。疎水部は、炭化水素基、含フッ素基、含Si基から選択される疎水基で構成され、疎水部の炭素数は、1~25が好ましく、2~15がより好ましく、4~10がさらに好ましく、5~8が一層好ましい。ノニオン性親水部は、アルコール性水酸基、フェノール性水酸基、エーテル基(好ましくはポリオキシアルキレン基、環状エーテル基)、アミド基、イミド基、ウレイド基、ウレタン基、シアノ基、スルホンアミド基、ラクトン基、ラクタム基、シクロカーボネート基からなる群より選ばれる少なくとも1つの基を有することが好ましい。ノニオン性界面活性剤としては、炭化水素系、フッ素系、Si系、またはフッ素およびSi系のいずれかのノニオン性界面活性剤であってもよいが、フッ素系またはSi系がより好ましく、フッ素系がさらに好ましい。ここで、「フッ素およびSi系界面活性剤」とは、フッ素系界面活性剤およびSi系界面活性剤の両方の要件を併せ持つものをいう。
フッ素系ノニオン性界面活性剤の市販品としては、住友スリーエム(株)製フロラードFC-4430、FC-4431、旭硝子(株)製サーフロンS-241、S-242、S-243、三菱マテリアル電子化成(株)製エフトップEF-PN31M-03、EF-PN31M-04、EF-PN31M-05、EF-PN31M-06、MF-100、OMNOVA社製Polyfox PF-636、PF-6320、PF-656、PF-6520、(株)ネオス製フタージェント250、251、222F、212M DFX-18、ダイキン工業(株)製ユニダインDS-401、DS-403、DS-406、DS-451、DSN-403N、DIC(株)製メガファックF-430、F-444、F-477、F-553、F-556、F-557、F-559、F-562、F-565、F-567、F-569、R-40、DuPont社製Capstone FS-3100、Zonyl FSO-100が挙げられる。
本発明のインプリント用硬化性組成物が界面活性剤を含有する場合、界面活性剤の含有量は、溶剤を除く全組成物中、0.1~10質量%が好ましく、0.2~5質量%がより好ましく、0.5~5質量%がさらに好ましい。インプリント用硬化性組成物は、界面活性剤を1種のみ含んでいてもよく、2種以上含んでいてもよい。2種以上含む場合は、その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は、末端に少なくとも1つの水酸基を有するか、または、水酸基がエーテル化されたポリアルキレングリコール構造を有し、フッ素原子およびシリコン原子を実質的に含有しない非重合性化合物を含んでいてもよい。ここで、非重合性化合物とは、重合性基を持たない化合物をいう。また、フッ素原子およびシリコン原子を実質的に含有しないとは、例えば、フッ素原子およびシリコン原子の合計含有率が1質量%以下であることを表し、フッ素原子およびシリコン原子を全く有していないことが好ましい。フッ素原子およびシリコン原子を有さないことにより、重合性化合物との相溶性が向上し、特に溶剤を実質的に含有しないインプリント用硬化性組成物において、塗布均一性、インプリント時のパターン形成性、ドライエッチング後のラインエッジラフネスが良好となる。
離型性を有する非重合性化合物が有するポリアルキレン構造としては、炭素数1~6のアルキレン基を含むポリアルキレングリコール構造が好ましく、ポリエチレングリコール構造、ポリプロピレングリコール構造、ポリブチレングリコール構造、またはこれらの混合構造がより好ましく、ポリエチレングリコール構造、ポリプロピレングリコール構造、またはこれらの混合構造がさらに好ましく、ポリプロピレングリコール構造が一層好ましい。
さらに、非重合性化合物は、末端の置換基を除き実質的にポリアルキレングリコール構造のみで構成されていてもよい。ここで実質的にとは、ポリアルキレングリコール構造以外の構成要素が全体の5質量%以下であることをいい、好ましくは1質量%以下であることをいう。特に、離型性を有する非重合性化合物として、実質的にポリプロピレングリコール構造のみからなる化合物を含むことが特に好ましい。
ポリアルキレングリコール構造としてはアルキレングリコール構成単位を3~100個有していることが好ましく、4~50個有していることがより好ましく、5~30個有していることがさらに好ましく、6~20個有していることが一層好ましい。
離型性を有する非重合性化合物は、末端に少なくとも1つの水酸基を有するかまたは水酸基がエーテル化されていることが好ましい。末端に少なくとも1つの水酸基を有するかまたは水酸基がエーテル化されていれば、残りの末端は水酸基であってもよく、末端水酸基の水素原子が置換されているものであってもよい。末端水酸基の水素原子が置換されていてもよい基としてはアルキル基(すなわちポリアルキレングリコールアルキルエーテル)、アシル基(すなわちポリアルキレングリコールエステル)が好ましい。連結基を介して複数(好ましくは2または3本)のポリアルキレングリコール鎖を有している化合物も好ましく用いることができる。
離型性を有する非重合性化合物の好ましい具体例としては、ポリエチレングリコール、ポリプロピレングリコール(例えば、和光純薬製)、これらのモノまたはジメチルエーテル、モノまたはジブチルエーテル、モノまたはジオクチルエーテル、モノまたはジセチルエーテル、モノステアリン酸エステル、モノオレイン酸エステル、ポリオキシエチレングリセリルエーテル、ポリオキシプロピレングリセリルエーテル、これらのトリメチルエーテルである。
離型性を有する非重合性化合物の重量平均分子量としては150~6000が好ましく、200~3000がより好ましく、250~2000がさらに好ましく、300~1200が一層好ましい。
また、本発明で用いることができる離型性を有する非重合性化合物として、アセチレンジオール構造を有する離型性を有する非重合性化合物も例示できる。このような離型性を有する非重合性化合物の市販品としては、オルフィンE1010(日信化学工業社製)等が例示される。
本発明のインプリント用硬化性組成物が離型性を有する非重合性化合物を含有する場合、離型性を有する非重合性化合物の含有量は、溶剤を除く全組成物中、0.1質量%以上が好ましく、0.5質量%以上がより好ましく、1.0質量%以上がさらに好ましく、2質量%以上が一層好ましい。上記含有量は、また、20質量%以下が好ましく、10質量%以下がより好ましく、5質量%以下がさらに好ましい。
インプリント用硬化性組成物は、離型性を有する非重合性化合物を1種のみ含んでいてもよく、2種以上含んでいてもよい。2種以上含む場合は、その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、酸化防止剤を含んでいてもよい。酸化防止剤としては、フェノール系酸化防止剤、リン系酸化防止剤、およびイオウ系酸化防止剤等が挙げられる。
フェノール系酸化防止剤の具体例としては、2,6-ジ-t-ブチル-4-メチルフェノール、n-オクタデシル-3-(3’,5’-ジ-t-ブチル-4’-ヒドロキシフェニル)プロピオネート、テトラキス〔メチレン-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート〕メタン、トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)イソシアヌレート、4,4’-ブチリデン-ビス(3-メチル-6-t-ブチルフェノール)、トリエチレングリコール-ビス〔3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオネート〕、3,9-ビス{2-〔3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ〕-1,1-ジメチルエチル}-2,4,8,10-テトラオキサスピロ〔5,5〕ウンデカン等が挙げられる。
フェノール系酸化防止剤の市販品としては、イルガノックス1010、イルガノックス1035、イルガノックス1076、イルガノックス1135、イルガノックス245、イルガノックス259、イルガノックス295、およびイルガノックス3114(以上、いずれもBASF社製)、アデカスタブ AO-20、アデカスタブ AO-30、アデカスタブ AO-40、アデカスタブ AO-50、アデカスタブ AO-60、アデカスタブ AO-70、アデカスタブ AO-80、アデカスタブ AO-90、およびアデカスタブ AO-330(以上、いずれもADEKA社製)、スミライザー BHT、スミライザー BP-101、スミライザー GA-80、スミライザー MDP-S、スミライザー BBM-S、スミライザー GM、スミライザー GS(F)、およびスミライザー GP(以上、いずれも住友化学工業社製)、HOSTANOX O10、HOSTANOX O16、HOSTANOX O14、およびHOSTANOX O3(以上、いずれもクラリアント社製)、アンテージ BHT、アンテージ W-300、アンテージ W-400、およびアンテージ W500(以上、いずれも川口化学工業社製)、並びにSEENOX 224M、およびSEENOX 326M(以上、いずれもシプロ化成社製)、ヨシノックスBHT、ヨシノックスBB、トミノックスTT、トミノックス917(以上、いずれも吉富製薬(株)製)、TTHP(東レ(株)製)等が挙げられる。
リン系酸化防止剤の具体例としては、トリスノニルフェニルホスファイト、トリス(2,4-ジ-t-ブチルフェニル)ホスファイト、ジステアリルペンタエリスリトールジホスファイト、ビス(2,4-ジ-t-ブチルフェニル)ペンタエリスリトールホスファイト、ビス(2,6-ジ-t-ブチル-4-メチルフェニル)ペンタエリスリトールホスファイト、2,2-メチレンビス(4,6-ジ-t-ブチルフェニル)オクチルホスファイト、テトラキス(2,4-ジ-t-ブチルフェニル)-4,4-ビフェニレン-ジ-ホスファナイト等が挙げられる。リン系酸化防止剤の市販品としては、アデカスタブ1178((株)ADEKA製)、スミライザーTNP(住友化学(株)製)、JP-135(城北化学(株)製)、アデカスタブ2112((株)ADEKA製)、JPP-2000(城北化学(株)製)、Weston 618(GE社製)、アデカスタブPEP-24G((株)ADEKA製)、アデカスタブPEP-36((株)ADEKA製)、アデカスタブHP-10((株)ADEKA製)、SandstabP-EPQ(サンド(株)製)、ホスファイト168(BASF社製)等が挙げられる。
イオウ系酸化防止剤の具体例としては、ジラウリル-3,3’-チオジプロピオネート、ジミリスチル-3,3’-チオジプロピオネート、ジステアリル-3,3’-チオジプロピオネート、ペンタエリスリトールテトラキス(3-ラウリルチオプロピオネート)等が挙げられる。イオウ系酸化防止剤の市販品としては、スミライザーTPL(住友化学(株)製)、ヨシノックスDLTP(吉富製薬(株)製)、アンチオックスL(日油(株)製)、スミライザーTPM(住友化学(株)製)、ヨシノックスDMTP(吉富製薬(株)製)、アンチオックスM(日油(株)製)、スミライザーTPS(住友化学(株)製)、ヨシノックスDSTP(吉富製薬(株)製)、アンチオックスS(日油(株)製)、アデカスタブAO-412S((株)ADEKA製)、SEENOX 412S(シプロ化成(株)製)、スミライザーTDP(住友化学(株)製)等が挙げられる。
また、後述する実施例で用いる酸化防止剤を好ましく用いることができる。
酸化防止剤の含有量は、配合する場合、インプリント用硬化性組成物中、0.001~5質量%であることが好ましい。酸化防止剤は、インプリント用硬化性組成物に1種のみ含まれていても、2種以上含まれていてもよい。2種以上含まれている場合は、合計量が上記範囲となることが好ましい。
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、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など)、紫外線吸収剤、溶剤等を含んでいてもよい。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、これらの内容は本明細書に組み込まれる。
本発明のインプリント用硬化性組成物は、25℃における粘度が、15mPa・s以下であることが好ましく、13mPa・s以下がより好ましく、11mPa・s以下がさらに好ましく、9mPa・s以下が一層好ましく、8mPa・s以下がより一層好ましい。粘度の下限値としては、特に定めるものでは無いが、例えば、3mPa・s以上、さらには、5mPa・s以上とすることができる。このような範囲とすることにより、本発明のインプリント用硬化性組成物がモールド内に入り込みやすくなり、モールド充填時間を短くできる。また、さらに、パターン形成性およびスループットを向上させることも可能になる。
本発明のインプリント用硬化性組成物の硬化後のガラス転移温度は、100℃以上であることが好ましく、120℃以上であることがより好ましく、150℃以上であることがさらに好ましい。ガラス転移温度の上限値は、特に定めるものでは無いが例えば、350℃以下とすることができる。
本発明のパターン製造方法は、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、インプリント用硬化性組成物を、モールドと基板で挟んだ状態で光照射することを含む。
本発明のパターン製造方法では、基板上またはモールド上にパターンを適用する。適用方法としては、特に定めるものでは無く、特開2010-109092号公報(対応米国出願は、米国特許出願公開2011/199592)の段落0102の記載を参酌できこれらの内容は本明細書に組み込まれる。本発明では、スピンコート法やインクジェット法が好ましい。
基板としては、特に定めるものでは無く、特開2010-109092号公報(対応米国出願は、米国特許出願公開2011/199592)の段落0103の記載を参酌できこれらの内容は本明細書に組み込まれる。具体的には、シリコン基板、ガラス基板、サファイア基板、シリコンカーバイド(炭化ケイ素)基板、窒化ガリウム基板、金属アルミニウム基板、アモルファス酸化アルミニウム基板、多結晶酸化アルミニウム基板、GaAsP、GaP、AlGaAs、InGaN、GaN、AlGaN、ZnSe、AlGaInP、または、ZnOから構成される基板が挙げられる。なお、ガラス基板の具体的な材料例としては、アルミノシリケートガラス、アルミノホウケイ酸ガラス、バリウムホウケイ酸ガラスが挙げられる。
本発明では、シリコン基板が好ましい。
モールドとしては、特に定めるものでは無く、特開2010-109092号公報(対応米国出願は、米国特許出願公開2011/199592)の段落0105~0109の記載を参酌できこれらの内容は本明細書に組み込まれる。本発明では、石英モールドが好ましい。本発明で用いるモールドのパターン(線幅)は、サイズが50nm以下であることが好ましい。
ここで、本発明のインプリント用硬化性組成物は、光照射後にさらに加熱して硬化させることが好ましい。また、基板とインプリント用硬化性組成物層の間に下層膜組成物を設けてもよい。すなわち、インプリント用硬化性組成物(ひいては、本発明の硬化物)は、基板またはモールドの表面に直接に設けてもよいし、基板またはモールドの上に、一層以上の層を介して設けてもよい。
上記の他、パターン製造方法の詳細は、特開2010-109092号公報(対応米国出願は、米国特許出願公開2011/199592)の段落番号0103~0115の記載を参酌でき、これらの内容は本明細書に組み込まれる。
インプリント用硬化性組成物から金属あるいは有機物のイオン性不純物を除去する方法としては、例えば、フィルターを用いた濾過を挙げることができる。フィルター孔径としては、孔径10nm以下が好ましく、5nm以下がより好ましく、3nm以下がさらに好ましい。フィルターの材質としては、ポリテトラフロロエチレン製、ポリエチレン製、ナイロン製のフィルターが好ましい。フィルターは、有機溶剤であらかじめ洗浄したものを用いてもよい。フィルター濾過工程では、複数種類のフィルターを直列または並列に接続して用いてもよい。複数種類のフィルターを使用する場合は、孔径および/または材質が異なるフィルターを組み合わせて使用してもよい。また、各種材料を複数回濾過してもよく、複数回濾過する工程が循環濾過工程であってもよい。
また、上記各種材料に含まれる金属等の不純物を低減する方法としては、各種材料を構成する原料として金属含有量が少ない原料を選択する、各種材料を構成する原料に対してフィルター濾過を行う、装置内をテフロン(登録商標)でライニングする等してコンタミネーションを可能な限り抑制した条件下で蒸留を行う等の方法を挙げることができる。各種材料を構成する原料に対して行うフィルター濾過における好ましい条件は、上記した条件と同様である。
フィルター濾過の他、吸着材による不純物の除去を行っても良く、フィルター濾過と吸着材を組み合わせて使用してもよい。吸着材としては、公知の吸着材を用いることができ、例えば、シリカゲル、ゼオライトなどの無機系吸着材、活性炭などの有機系吸着材を使用することができる。
上述のように本発明のパターン製造方法によって形成されたパターンは、LCDなどに用いられる永久膜や、半導体加工用のエッチングレジストとして使用することができる。また、本発明のパターンを利用してLCDのガラス基板にグリッドパターンを形成し、反射や吸収が少なく、大画面サイズ(例えば55インチ、60インチ超)の偏光板を安価に製造することが可能である。例えば、特開2015-132825号公報やWO2011/132649号に記載の偏光板が製造できる。なお、1インチは25.4mmである。
また、永久膜は、製造後にガロン瓶やコート瓶などの容器にボトリングし、輸送、保管されるが、この場合に、劣化を防ぐ目的で、容器内を不活性な窒素、またはアルゴンなどで置換しておいてもよい。また、輸送、保管に際しては、常温でもよいが、より永久膜の変質を防ぐため、-20℃から0℃の範囲に温度制御してもよい。勿論、反応が進行しないレベルで遮光することが好ましい。
本発明のパターンは、具体的には、磁気ディスク等の記録媒体、固体撮像素子等の受光素子、LEDや有機EL等の発光素子、LCD等の光デバイス、回折格子、レリーフホログラム、光導波路、光学フィルター、マイクロレンズアレイ等の光学部品、薄膜トランジスタ、有機トランジスタ、カラーフィルター、反射防止膜、偏光板、偏光素子、光学フィルム、柱材等のフラットパネルディスプレイ用部材、ナノバイオデバイス、免疫分析チップ、デオキシリボ核酸(DNA)分離チップ、マイクロリアクター、フォトニック液晶、ブロックコポリマーの自己組織化を用いた微細パターン形成(directed self-assembly、DSA)のためのガイドパターン等の作製に好ましく用いることができる。
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、エッチング用マスクとして好ましく用いられる。また、本発明では、本発明の製造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被加工基板の製造方法についても開示する。
<<中間体G-9A>>
N2フローしている2Lの三口フラスコにG-9Aを50g(0.18mol)、共栄社化学株式会社製ライトアクリレートNP-Aを38g(0.18mol)、アセトニトリル0.2L加え、-10℃に冷却した。ジエチルアミン 13g(0.18mol)を上記フラスコの内温が0℃を超えない温度で2時間かけて滴下し、さらに0℃で5時間熟成を行った。その後、-10℃まで冷却し、蒸留水0.5Lを上記フラスコの内温が0℃を超えない温度で0.5時間かけて滴下した。さらに、酢酸エチル2.0Lを加え、激しく30分間撹拌した。その後、静止して水層を除去し、蒸留水1.0Lを加え、激しく30分間撹拌した。その後、静止して水層を除去した。得られた有機層を減圧濃縮し、シリカゲルクロマトグラフィで精製することで化合物(G-9)を得た。
上記G-9にならい、G-1~G-7およびG-9~G-40についても合成した。
<インプリント用硬化性組成物の調製>
下記表2~4に記載のとおり、各化合物(表中、A,B,C,D,Gの番号を付して示した化合物)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(表中のA,B,Gの化合物の総量)100質量%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0.1μmのポリテトラフルオロエチレン(PTFE)製フィルターで濾過し、インプリント用硬化性組成物を調製した。尚、表2~4における各成分の配合量は質量比である。
得られたインプリント用硬化性組成物について以下の評価を行った。結果は表5に示した。
インプリント用硬化性組成物(硬化前)および多官能ラジカル重合性化合物の粘度の測定は、東機産業(株)製のRE-80L型回転粘度計を用い、25℃で行った。
測定時の回転速度は、粘度に応じて以下の表1の通りとした。
基板とインプリント用硬化物との密着力は以下の通り評価した。
シリコンウェハ上に製膜したSOC(Spun On Carbon)表面に、25℃に温度調整した実施例および比較例のインプリント用硬化性組成物を、富士フイルムダイマティックス製インクジェットプリンターDMP-2831を用いて、ノズルあたり1plの液滴量で吐出して、上記密着膜上に液滴が約100μm間隔の正方配列となるように塗布した。
上から線幅30nm、深さ60nmのライン(Line)/スペース(Space)を有する石英モールドをインプリント用硬化性組成物層と接するように載せ、石英ウェハ側から高圧水銀ランプを用い300mJ/cm2の条件で露光した。露光後、石英モールドを離し、そのときの剥がれ面積%を測定した。
この剥がれ面積%が密着力F(単位:N)に相当する。
A:剥がれ面積≦1%
B:5%>剥がれ面積>1%
C:剥がれ面積≧5%
<離型力>
石英モールドは、線幅30nm、深さ60nmのライン(Line)/スペース(Space)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エ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。石英モールド面から高圧水銀ランプを用いて、100mJ/cm2の条件で露光し、石英モールドを離型することで、パターンサイズ(線幅)が30nmのパターン(以下、サンプルという)を得た。サンプルの残膜の厚み(パターンの高さ)は、60nmであった。また、その際の離型に必要な力(離型力F)を測定した。
以下の評価区分に従って評価した。
A:F≦12N
B:12N<F≦18N
C:F>18N
実施例および比較例のインプリント用硬化性組成物を40℃1週間の雰囲気下に置いたのち、組成物中の単体の純度の低下率を測定し、それらの合計低下率を安定性とした。
以下の評価区分に従って評価した。
A:合計低下率≦1%
B:5%>合計低下率>1%
C:合計低下率≧5%
さらに、本発明のインプリント用硬化性組成物は、モールド離型性にも優れていた。
また、この結果から、本発明のインプリント用硬化性組成物は、各種用途に用いられる硬化物およびパターンの材料として利用することができ、その硬化物およびパターンは特にリソグラフィ用のマスクとして好適に利用できることが分かる。
これに対し、式(1)で表される化合物を含まない比較例のインプリント用硬化性組成物は、硬化物の基板との密着性およびインプリント用硬化性組成物の保存安定性に劣っていた。
Claims (20)
- 前記式(1)で表される化合物の含有量が、前記式(1)で表される化合物以外のラジカル重合性化合物の含有量100質量部に対して、0.005~1質量部である、請求項1に記載のインプリント用硬化性組成物。
- 前記式(1)で表される化合物以外のラジカル重合性化合物は、(メタ)アクリロイル基の少なくとも1種を含む、請求項1または2に記載のインプリント用硬化性組成物。
- 前記式(1)で表される化合物の分子量が100~1500である、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。
- 前記式(1)で表される化合物が、ラジカル重合性基を有する、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。
- 前記式(1)で表される化合物以外のラジカル重合性化合物の少なくとも1種が、単官能(メタ)アクリルモノマーである、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おける溶剤の含有量が、5質量%以下である、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おける重量平均分子量が2000を超える成分の含有量が、5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25℃における粘度が3~15mPa・s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。
- 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から形成される硬化物。
- 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13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製造方法。
- 前記パターンのサイズが30nm以下である、請求項15に記載のパターン製造方法。
- 請求項15または16に記載のパターン製造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、被加工基板の製造方法。
- 請求項1~12のいずれか1項に記載の硬化性組成物から形成されるパターンであって、パターンサイズが30nm以下であるパターン。
- 請求項18に記載のパターンの少なくとも1種を含む、エッチング用マスク。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009244402A (ja) * | 2008-03-28 | 2009-10-22 | Fujifilm Corp | ナノインプリント用硬化性組成物、微細パターンとその製造方法、カラーフィルタ、表示装置、および処理基板の製造方法 |
JP2011066370A (ja) * | 2009-03-25 | 2011-03-31 | Fujifilm Corp | 光インプリント用硬化性組成物およびそれを用いた硬化物の製造方法 |
WO2016152600A1 (ja) * | 2015-03-24 | 2016-09-29 | 富士フイルム株式会社 | 下層膜形成用樹脂組成物、積層体、パターン形成方法、インプリント形成用キットおよびデバイスの製造方法 |
Family Cites Families (13)
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US5134175A (en) * | 1987-12-16 | 1992-07-28 | Michael Lucey | Curable composition for electrical and electronic components |
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JP4859004B2 (ja) * | 1999-06-23 | 2012-01-18 | 東レ株式会社 | コンタクトレンズ、眼内レンズまたは人工角膜用のポリマーおよびコンタクトレンズ |
JP2001322361A (ja) | 2000-05-17 | 2001-11-20 | Oji Paper Co Ltd | 熱転写記録用被記録体 |
JP5665329B2 (ja) * | 2009-03-09 | 2015-02-04 | 富士フイルム株式会社 | インプリント用硬化性組成物、パターン形成方法およびパターン |
JP5760332B2 (ja) | 2010-06-04 | 2015-08-05 | 大日本印刷株式会社 | インプリント用基板およびインプリント方法 |
JP5838160B2 (ja) * | 2010-08-06 | 2015-12-24 | 綜研化学株式会社 | ナノインプリント用樹脂製モールドおよびその製造方法 |
JP5846974B2 (ja) | 2012-03-13 | 2016-01-20 | 富士フイルム株式会社 | 光インプリント用硬化性組成物、パターン形成方法およびパターン |
JP6080813B2 (ja) | 2013-08-30 | 2017-02-15 | キヤノン株式会社 | 光インプリント用組成物、これを用いた、膜の製造方法、光学部品の製造方法、回路基板の製造方法、電子部品の製造方法 |
JP6643802B2 (ja) | 2014-05-09 | 2020-02-12 | キヤノン株式会社 | 硬化性組成物、その硬化物、硬化物の製造方法、光学部品の製造方法、回路基板の製造方法、および電子部品の製造方法 |
JP6624808B2 (ja) | 2014-07-25 | 2019-12-25 | キヤノン株式会社 | 光硬化性組成物、これを用いた硬化物パターンの製造方法、光学部品の製造方法、回路基板の製造方法 |
US10392339B2 (en) | 2015-02-09 | 2019-08-27 | Jnc Corporation | Polymerizable polar compound, liquid crystal composition, and liquid crystal display element |
JP6011671B2 (ja) | 2015-04-02 | 2016-10-19 | 大日本印刷株式会社 | インプリント用基板およびインプリント方法 |
-
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009244402A (ja) * | 2008-03-28 | 2009-10-22 | Fujifilm Corp | ナノインプリント用硬化性組成物、微細パターンとその製造方法、カラーフィルタ、表示装置、および処理基板の製造方法 |
JP2011066370A (ja) * | 2009-03-25 | 2011-03-31 | Fujifilm Corp | 光インプリント用硬化性組成物およびそれを用いた硬化物の製造方法 |
WO2016152600A1 (ja) * | 2015-03-24 | 2016-09-29 | 富士フイルム株式会社 | 下層膜形成用樹脂組成物、積層体、パターン形成方法、インプリント形成用キットおよびデバイスの製造方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020175301A1 (ja) * | 2019-02-27 | 2020-09-03 | 富士フイルム株式会社 | インプリント用の硬化性組成物、キット、パターン製造方法、および半導体素子の製造方法 |
JPWO2020175301A1 (ja) * | 2019-02-27 | 2021-11-25 | 富士フイルム株式会社 | インプリント用の硬化性組成物、キット、パターン製造方法、および半導体素子の製造方法 |
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KR102383361B1 (ko) | 2022-04-08 |
US11401361B2 (en) | 2022-08-02 |
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