WO2014112295A1 - Photocurable composition for nanoimprint and method for producing finely patterned substrate using same - Google Patents

Abstract

Provided is a photocurable composition for nanoimprint, which is able to be quickly cured and form a thin film by being thinly applied over a substrate and irradiated with light, and which is small in curing shrinkage, thereby capable of transferring a fine pattern of a mold with high accuracy. A photocurable composition for nanoimprint according to the present invention contains the following component (A) and component (B). Component (A): a compound represented by formula (a-1) (wherein each of R¹-R¹⁸ represents a hydrogen atom, a halogen atom, a hydrocarbon group which may contain an oxygen atom or a halogen atom, or an optionally substituted alkoxy group; and X represents a single bond or a linking group) Component (B): a cationic photopolymerization initiator having a fluorinated alkylfluorophosphate anion

Description

Photocurable composition for nanoimprint, and method for producing fine pattern substrate using the same

The present invention relates to a photocurable composition for nanoimprint and a method for producing a fine pattern substrate using the same. This application claims the priority of Japanese Patent Application No. 2013-004758 filed in Japan on January 15, 2013, the contents of which are incorporated herein by reference.

A light emitting diode (LED) is excellent in energy conversion efficiency and has a long life, so that it is often used in electronic devices and the like. The LED has a structure in which a light emitting layer made of a GaN-based semiconductor is laminated on an inorganic material substrate. However, since there is a large refractive index difference between the inorganic material substrate, the GaN-based semiconductor, and the atmosphere, most of the total amount of light generated in the light emitting layer disappears due to repeated internal reflection, resulting in poor light extraction efficiency. That was the problem.

As a method for solving the above problem, a method is known in which a fine pattern of about several μm is formed on the surface of an inorganic material substrate, and a light emitting layer made of a GaN-based semiconductor is laminated thereon.

As a method for forming a fine pattern, conventionally, a mask is formed on an inorganic material substrate by photolithography, and the pattern is formed by etching using the obtained mask. However, the increase in size and nanopatterning of inorganic material substrates has been a problem, and the associated increase in cost and processing time has become a problem. Therefore, a method of forming a mask by nanoimprinting instead of the photolithography has attracted attention.

As a photocurable composition used for nanoimprint, it is known to use, for example, a radical polymerizable compound such as vinyl ether having an alicyclic structure or vinyl ether having an alicyclic structure and an aromatic ring structure ( Patent Documents 1 and 2). However, the radical polymerizable compound has a large shrinkage due to curing, and it has been difficult to accurately produce a fine pattern. In addition, the photocurable composition is required to quickly cure and form a thin film after coating on the substrate, but the radically polymerizable compound is subjected to polymerization inhibition by oxygen, and the curing rate decreases. In particular, it has been a problem that curability is lowered in a thin film. A method of curing in an atmosphere of inert gas such as nitrogen is also conceivable for inhibiting polymerization by oxygen, but the cost is increased due to the large equipment, and work efficiency is required because it takes time to replace air. There was a problem that decreased.

JP 2003-327628 A JP 2011-84527 A JP 2011-157482 A

Accordingly, an object of the present invention is to form a thin film by quickly applying a light to a substrate and irradiating with light, thereby forming a thin film, curing shrinkage is small, and a fine pattern of a mold can be accurately transferred. The object is to provide a photocurable composition for nanoimprinting.
Another object of the present invention is to provide a method for producing a fine pattern substrate using the photocurable composition for nanoimprint.
Still another object of the present invention is to provide a fine pattern substrate obtained by the method for producing a fine pattern substrate, and a semiconductor device including the same.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a curable composition containing a specific cationic polymerizable compound having an alicyclic epoxy group and a photo cationic polymerization initiator having a fluorinated alkylfluorophosphate anion. Since the composition is not hindered by oxygen, the composition can be applied to a substrate thinly even in an oxygen atmosphere and lightly irradiated to cure quickly to form a thin film (that is, excellent thin film curability), curing It was found that the shrinkage is small and a fine pattern of the mold can be transferred with high accuracy. And when nanoimprinting was performed using the said curable composition, it discovered that the mask by which the fine pattern of the mold was transcribe | transferred accurately can be formed. In the present specification, the “alicyclic epoxy group” means a group in which two adjacent carbon atoms constituting an alicyclic ring form a ring together with one oxygen atom (particularly, adjacent cyclohexane ring constituting a cyclohexane ring). An epoxy group composed of two carbon atoms and an oxygen atom). The present invention has been completed based on these findings.

That is, this invention provides the photocurable composition for nanoimprint containing the following component (A) and component (B).
Component (A): Compound represented by the following formula (a-1)

[Wherein, R ¹ to R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group that may contain a halogen atom, or an alkoxy group that may have a substituent. . X represents a single bond or a linking group]
Component (B): Photocationic polymerization initiator having a fluorinated alkylfluorophosphate anion

The present invention further provides the above-mentioned photocurable composition for nanoimprint, which comprises the following component (C).
Component (C): Cationic polymerizable compound having a number average molecular weight of 500 or more (excluding compounds contained in component (A))

The present invention also provides the photocurable composition for nanoimprint, wherein the component (C) is a cationically polymerizable compound having a polycarbonate skeleton, a polyester skeleton, a polydiene skeleton, a novolac skeleton, or an alicyclic skeleton.

The present invention also provides a method for producing a fine pattern substrate in which an inorganic material substrate is etched using a mask obtained by imprinting the photocurable composition for nanoimprint described above.

The present invention also provides a fine pattern substrate obtained by the method for producing a fine pattern substrate described above.

The present invention also provides a semiconductor device including the fine pattern substrate described above.

That is, the present invention relates to the following.
(1) A photocurable composition for nanoimprints comprising the following component (A) and component (B).
Component (A): Formula (a-1) [wherein R ¹ to R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom, or a hydrocarbon group that may contain a halogen atom, or a substituent The alkoxy group which may have is shown. X represents a single bond or a linking group] Component (B): Photocationic polymerization initiator having a fluorinated alkylfluorophosphate anion (2) and further comprising the following component (C) (1) The photocurable composition for nanoimprints described in 1.
Component (C): Cationic polymerizable compound having a number average molecular weight of 500 or more (excluding compounds contained in component (A))
(3) The photocurable composition for nanoimprints according to (2), wherein the component (C) is a cationically polymerizable compound having a polycarbonate skeleton, a polyester skeleton, a polydiene skeleton, a novolac skeleton, or an alicyclic skeleton.
(4) The content of component (A) in the total amount (100% by weight) of the cationically polymerizable compound contained in the photocurable composition for nanoimprinting is 10 to 70% by weight, and any one of (1) to (3) The photocurable composition for nanoimprints described in 1.
(5) The photocurable property for nanoimprints according to any one of (1) to (4), wherein the volume expansion coefficient when the compound represented by the formula (a-1) is cured is 0 to 30%. Composition.
(6) Among the compounds represented by the formula (a-1), the content of the compound in which X is a group containing an ester bond is represented by the formula (a-1) contained in the photocurable composition for nanoimprints. The photocurable composition for nanoimprints according to any one of (1) to (5), which is 40% by weight or less of the total amount of the compound to be formed (100% by weight).
(7) The nanoimprinting light according to any one of (1) to (6), wherein the cation part of the photocationic polymerization initiator having a fluorinated alkylfluorophosphate anion in component (B) is a triarylsulfonium ion Curable composition.
(8) The photocurable composition for nanoimprints according to any one of (1) to (7), further comprising the following component (D).
Component (D): The photocurable composition for nanoimprints according to any one of compounds (9) (1) to (8) having at least one oxetanyl group in the molecule and having a number average molecular weight of less than 500 A method for manufacturing a fine pattern substrate, in which an inorganic material substrate is etched using a mask obtained by imprinting.
(10) A fine pattern substrate obtained by the method for producing a fine pattern substrate according to (9).
(11) A semiconductor device comprising the fine pattern substrate according to (10).

Since the photocurable composition for nanoimprints of the present invention has the above-described structure, it is a thin film excellent in curability that is cured rapidly and while suppressing curing shrinkage when applied thinly to a substrate and irradiated with light even in an oxygen atmosphere. Can be formed. Therefore, a fine pattern can be transferred quickly and accurately. When nanoimprinting is performed using the photocurable composition for nanoimprinting of the present invention, it is possible to form a mask on which a fine pattern of the mold is accurately transferred, and etching the inorganic material substrate using the mask. By doing so, a fine pattern having excellent dimensional reproducibility according to the design drawing can be formed on the surface of the inorganic material substrate.

[Photocurable composition for nanoimprint]
The photocurable composition for nanoimprinting of the present invention comprises the following component (A) and component (B).
Component (A): Compound represented by formula (a-1) Component (B): Photocationic polymerization initiator having a fluoroalkylfluorophosphate anion

(Ingredient (A))
Component (A) of the present invention is a compound represented by the following formula (a-1). The compound represented by the following formula (a-1) has cationic polymerizability (that is, the compound represented by the following formula (a-1) is a cationic polymerizable compound) and is excellent in thin film curability.

R ¹ to R ¹⁸ in the above formula (a-1) are the same or different and may have a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group which may contain a halogen atom, or a substituent. An alkoxy group is shown. X represents a single bond or a linking group.

Examples of the halogen atom in R ¹ to R ¹⁸ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the hydrocarbon group in R ¹ to R ¹⁸ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded.

Examples of the aliphatic hydrocarbon group include a C _1-20 alkyl group (preferably a C _1-10 alkyl group, particularly a methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, isooctyl, decyl, dodecyl group). Preferably a C _1-4 alkyl group); vinyl, allyl, methallyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl C _2-20 alkenyl group such as 5-hexenyl group (preferably C _2-10 alkenyl group, particularly preferably C _2-4 alkenyl group); C _2-20 alkynyl group such as ethynyl, propynyl group (preferably C _2-10 alkynyl group, particularly preferably C _2-4 alkynyl group).

Examples of the alicyclic hydrocarbon group include C _3-12 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclododecyl groups; C _3-12 cycloalkenyl groups such as cyclohexenyl groups; and bicycloheptanyl. And a C _4-15 bridged cyclic hydrocarbon group such as a bicycloheptenyl group.

Examples of the aromatic hydrocarbon group include C _6-14 aryl groups (preferably C _6-10 aryl groups) such as phenyl and naphthyl groups.

In addition, the aliphatic hydrocarbon group and the alicyclic hydrocarbon group in a group in which two or more groups selected from the above-described aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group are bonded to each other. Examples of the bonded group include a C _3-12 cycloalkyl-C _1-20 alkyl group such as a cyclohexylmethyl group; a C _1-20 alkyl-C _3-12 cycloalkyl group such as a methylcyclohexyl group. Can do. Examples of the group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded include, for example, a C _7-18 aralkyl group such as a benzyl group or a phenethyl group (particularly a C _7-10 aralkyl group); _6-14 aryl-C _2-20 alkenyl group; C _1-20 alkyl substituted C _6-14 aryl group such as tolyl group; C _2-20 alkenyl substituted C _6-14 aryl group such as styryl group, etc. it can.

As the hydrocarbon group optionally containing an oxygen atom or a halogen atom in R ¹ to R ^18, at least one hydrogen atom in the above hydrocarbon group is substituted with a group having an oxygen atom or a group having a halogen atom. The group etc. can be mentioned. Examples of the group having an oxygen atom include hydroxyl group; hydroperoxy group; C _1-10 alkoxy group such as methoxy, ethoxy, propoxy, isopropyloxy, butoxy, isobutyloxy group; C _2-10 such as allyloxy group. An alkenyloxy group; a C _6-14 aryloxy group optionally having a substituent selected from a C _1-10 alkyl group, a C _2-10 alkenyl group, a halogen atom, and a C _1-10 alkoxy group (for example, C _7-18 aralkyloxy groups such as benzyloxy and phenethyloxy groups; C _1-10 acyloxy groups such as acetyloxy, propionyloxy, (meth) acryloyloxy and benzoyloxy groups; methoxy carbonyl, ethoxycarbonyl, propoxycarbonyl, C _1-10 aralkyl such as a butoxycarbonyl group Alkoxycarbonyl group; C _1-10 alkyl group, C _2-10 alkenyl group, a halogen atom, and C _1-10 may have a substituent group selected from an alkoxy group C _6-14 aryloxycarbonyl group ( For example, phenoxycarbonyl, tolyloxycarbonyl, naphthyloxycarbonyl group, etc.); C _7-18 aralkyloxycarbonyl group such as benzyloxycarbonyl group; epoxy group-containing group such as glycidyloxy group; oxetanyl group such as ethyloxetanyloxy group A C _1-10 acyl group such as an acetyl, propionyl, or benzoyl group; an isocyanate group; a sulfo group; a carbamoyl group; an oxo group; and two or more of these via a C _1-10 alkylene group or the like The group etc. which were couple | bonded without mentioning can be mentioned. Examples of the group having a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkoxy group in R ¹ to R ¹⁸ include C _1-10 alkoxy groups such as methoxy, ethoxy, propoxy, isopropyloxy, butoxy, isobutyloxy groups and the like.

Examples of the substituent that the alkoxy group may have include, for example, a halogen atom, a hydroxyl group, a C _1-10 alkoxy group, a C _2-10 alkenyloxy group, a C _6-14 aryloxy group, a C _1-10 Acyloxy group, mercapto group, C _1-10 alkylthio group, C _2-10 alkenylthio group, C _6-14 arylthio group, C _7-18 aralkylthio group, carboxyl group, C _1-10 alkoxycarbonyl group, C _{6- 14} aryloxycarbonyl group, C _7-18 aralkyloxycarbonyl group, amino group, mono or di C _1-10 alkylamino group, C _1-10 acylamino group, epoxy group-containing group, oxetanyl group-containing group, C _1-10 Examples include an acyl group, an oxo group, and a group in which two or more of these are bonded through or without a C _1-10 alkylene group.

R ¹ to R ¹⁸ are preferably hydrogen atoms.

X in the formula (a-1) represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, an amide group, and a group in which a plurality of these are linked. Examples of the divalent hydrocarbon group include linear or branched C _1-18 alkylene groups such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene groups (preferably linear or branched chain). C _1-3 alkylene group); 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, A divalent C _3-12 cycloalkylene group such as a cyclohexylidene group, and a divalent C _3-12 cycloalkylidene group (preferably a divalent C _3-6 cycloalkylene group and a divalent C _3-6 Cycloalkylidene group) and the like.

The volume expansion coefficient when the compound represented by the above formula (a-1) is cured is preferably about 0 to 30%, particularly preferably 0 to 10 based on the volume of the uncured product. %, Most preferably 0.5 to 5.0%. If the volume expansion rate is below the above range (a negative value), it tends to be difficult to accurately transfer a fine pattern of the mold due to curing shrinkage.

The volume expansion coefficient when the compound represented by the formula (a-1) is cured can be calculated by the following method.
That is, a composition containing the compound represented by formula (a-1) and a cationic polymerization initiator is cured by UV irradiation to form a cured product, and the specific gravity x of the composition before curing and the specific gravity of the cured product y can be obtained and calculated by the following formula.
Volume expansion coefficient = [(y−x) / x] × 100

The compounds represented by the formula (a-1) can be used singly or in combination of two or more. In the present invention, (3,4,3 ′, 4′-diepoxy) bicyclo is particularly advantageous in that it has a small steric hindrance, can rapidly proceed with a curing reaction upon irradiation with light, and has a curing expansion property. It is preferable to use xylil [volume expansion coefficient: 2.4%].

In addition, among the compounds represented by the formula (a-1), the amount of the compound in which X is a group containing an ester bond is 40% of the total amount (100% by weight) of the compound represented by the formula (a-1). It is preferred that it is not more than wt% (preferably not more than 30 wt%, particularly preferably less than 10 wt%, most preferably less than 5 wt%). Among the compounds represented by the formula (a-1), when the content of the compound in which X is a group containing an ester bond exceeds the above range, the thin film curability tends to decrease.

The compound represented by the above formula (a-1) can be produced, for example, by epoxidizing an olefin represented by the formula (a-1 ′). The epoxidation reaction can be carried out by a known or conventional method. Incidentally, R ¹ ~ R ¹⁸ in the formula (a-1 '), X is the same as R ¹ ~ R ^18, X in formula (a-1).

As the epoxidizing agent used in the epoxidation reaction, a known or conventional oxidizing agent (for example, organic percarboxylic acids, hydroperoxides, etc.) can be used. Examples of the organic percarboxylic acids include performic acid, peracetic acid, perpropionic acid, perbenzoic acid, trifluoroperacetic acid, and perphthalic acid. Examples of the hydroperoxides include hydrogen peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, and the like.

In addition, the content of the component (A) in the total amount (100% by weight) of the cationically polymerizable compound contained in the photocurable composition for nanoimprinting (the total amount when containing two or more types) is, for example, about 10 to 70% by weight. It is preferably 20 to 60% by weight. When content of a component (A) is less than the said range, there exists a tendency for thin film sclerosis | hardenability and transferability to fall. On the other hand, when the content of the component (A) exceeds the above range, the etching resistance tends to decrease.

(Ingredient (B))
The photocationic polymerization initiator in the component (B) of the present invention is a compound (= photoacid) that generates an acid upon irradiation with light and initiates a curing reaction of the cationically polymerizable compound contained in the photocurable composition for nanoimprinting. A cation moiety that absorbs light and an anion moiety that is a source of acid generation.

In the present invention, a compound having a fluoroalkylfluorophosphate anion is used as a cationic photopolymerization initiator. The compound is excellent in safety, can accelerate curing of the cationic polymerizable compound containing the component (A) only by light irradiation, and imparts excellent thin film curability to the photocurable composition for nanoimprinting. be able to. The photocationic polymerization initiator of the present invention can be used alone or in combination of two or more.

The fluorinated alkyl fluorophosphate anion is represented, for example, by the following formula (b).
[(Rf) _n PF _6-n ] ^- (b)
(In the formula (b), Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, and n represents an integer of 1 to 5)

In the formula (b), Rf is an alkyl group (preferably a C _1-4 alkyl group) in which 80% or more of hydrogen atoms are substituted with fluorine atoms, and among them, CF ₃ , C ₂ F ₅ , (CF _{3) 2 CF, C 3 F} 7, C 4 F 9, (CF 3) 2 CFCF 2, CF 3 CF 2 (CF 3) CF, (CF 3) the ₃ C, etc., 100% fluorine atom hydrogen atom A linear or branched C _1-4 alkyl group substituted with is preferred.

Therefore, the anionic part of the photocationic polymerization initiator is particularly [(C ₂ F ₅ ) ₃ PF ₃ ] ⁻ , [(C ₃ F ₇ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF). ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , and [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF _4] ^-, and the like are preferable.

Further, examples of the cation part of the photocationic polymerization initiator include iodonium ions, sulfonium ions, and selenium ions. In the present invention, among them, donium ions and sulfonium ions are preferable.

Examples of the iodonium ion include diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4- Aryl iodonium ions such as decyloxy) phenyliodonium, 4- (2-hydroxytetradecyloxyphenyl) phenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium and 4-isobutylphenyl (p-tolyl) iodonium (especially bisaryl) Iodonium ion).

Examples of the sulfonium ions include arylsulfonium ions (particularly, triarylsulfonium ions) such as triphenylsulfonium, diphenyl [4- (phenylthio) phenyl] sulfonium, and tri-p-tolylsulfonium.

Examples of the photocationic polymerization initiator of the present invention include 4-isopropylphenyl (p-tolyl) iodonium tris (pentafluoroethyl) trifluorophosphate, [1,1′-biphenyl] -4-yl [4- (1 , 1′-biphenyl) -4-ylthiophenyl] phenyl tris (pentafluoroethyl) trifluorophosphate, diphenyl [4- (phenylsulfonyl) phenyl] tris (pentafluoroethyl) trifluorophosphate, triphenylsulfonium tris (penta Fluoroethyl) trifluorophosphate, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium, tris (pentafluoroethyl) trifluorophosphate, and the like can be preferably used.

The content of the component (B) is, for example, 0.1 to 20 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound (the total amount when containing two or more kinds) contained in the photocurable composition for nanoimprints. Degree, preferably 0.5 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight. When content of a component (B) is less than the said range, there exists a tendency for thin film sclerosis | hardenability to fall. On the other hand, when content of a component (B) exceeds the said range, there exists a tendency for the storage stability of the photocurable composition for nanoimprints to fall.

(Ingredient (C))
The photocurable composition for nanoimprinting of the present invention may contain a compound other than the compound (component (A)) represented by the above formula (a-1) as a cationic polymerizable compound. In particular, the photocurable composition for nanoimprinting of the present invention preferably contains a cationic polymerizable compound having a number average molecular weight of 500 or more (hereinafter sometimes referred to as “high molecular weight cationic polymerizable compound”). By using a high molecular weight cationic polymerizable compound in combination, the thin film curability can be further improved. Moreover, since the high molecular weight cationically polymerizable compound is excellent in shape stability, when used in combination, curing shrinkage can be suppressed and transferability can be further improved.

The number average molecular weight of the high molecular weight cationic polymerizable compound is 500 or more, preferably 500 to 100,000, particularly preferably 500 to 80,000, and most preferably 500 to 50,000. When the number average molecular weight of the high molecular weight cationic polymerizable compound is below the above range, the effect of imparting shape stability tends to be difficult to obtain. On the other hand, when the number average molecular weight of the high molecular weight cationic polymerizable compound exceeds the above range, the viscosity of the curable composition tends to increase and the workability tends to decrease. Moreover, there exists a tendency for the surface smoothness of the hardened | cured material obtained by hardening | curing the photocurable composition for nanoimprints to fall.

The high molecular weight cationic polymerizable compound contains a cationic curable functional group. The number of cationic curable functional groups contained in one molecule of the high molecular weight cationic polymerizable compound is preferably 2 or more.

Examples of the cationically curable functional group include electron donating groups such as a hydroxyl group, an epoxy group, and an oxetanyl group. The high molecular weight cationically polymerizable compound of the present invention may contain one kind of the electron donating group alone or in combination of two or more kinds.

Examples of the high molecular weight cationic polymerizable compound include a compound having a skeleton selected from a polycarbonate skeleton, a polyester skeleton, a polydiene skeleton, a novolak skeleton, an alicyclic skeleton, and the like, and the above cation-curable functional group. These can be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a high molecular weight cationic polymerizable compound containing an epoxy group as a cationically curable functional group.

The high molecular weight cationically polymerizable compound having a polycarbonate skeleton is a phosgene method or a dialkyl carbonate (for example, dimethyl carbonate, diethyl carbonate, etc.) or a transesterification reaction between diphenyl carbonate and a polyol (Japanese Patent Laid-Open Nos. 62-187725 and 62 No. 2-175721, JP-A-2-49025, JP-A-3-220233, JP-A-3-252420).

Examples of the polyol used in the transesterification reaction include 1,6-hexanediol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3- Butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,12-dodecanediol, polybutadienediol, neopentyl glycol, tetramethylene glycol, propylene glycol, Dipropylene glycol, glycerin, trimethylolpropane, 1,3-dihydroxyacetone, hexylene glycol, 1,2,6-hexanetriol, ditrimethylolpropane, trimethylolethane, trimethyloloctane Mention may be made of pentaerythritol. Also, ester glycol (manufactured by Mitsubishi Gas Chemical Co., Inc.), polyester polyol, and polyether polyol can be used.

Examples of the high molecular weight cationically polymerizable compound having a polycarbonate skeleton include trade names “Placcel CD205”, “Plaxel CD205PL”, “Plaxel CD205HL”, “Plaxel D210”, “Plaxel CD210PL”, “Plaxel CD210HL”, “Plaxel” CD220 "," Placcel CD220PL "," Placcel CD220HL "," Placcel CD220EC "," Placcel CD221T "(manufactured by Daicel Corporation), trade names" UM-CARB90 (1/3) "," UM-CARB90 ( 1/1) ”,“ UC-CARB100 ”(manufactured by Ube Industries, Ltd.) and the like are commercially available.

The high molecular weight cationic polymerizable compound having a polyester skeleton can be synthesized through a reaction between a polyol and a carboxylic acid. In addition, it can be synthesized through ring-opening polymerization of lactones.

Examples of the polyol used as a raw material for the high molecular weight cationically polymerizable compound having the polyester skeleton include the same examples as the polyol used in the transesterification reaction.

Examples of the carboxylic acid used as a raw material for the high molecular weight cationic polymerizable compound having a polyester skeleton include oxalic acid, adipic acid, sebacic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, azelaic acid, citric acid, and 2 , 6-Naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, citraconic acid, 1,10-decanedicarboxylic acid, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride Products, pyromellitic anhydride, trimellitic anhydride, lactic acid, malic acid, glycolic acid, dimethylolpropionic acid, dimethylolbutanoic acid and the like.

Examples of lactones used as a raw material for the high molecular weight cationic polymerizable compound having a polyester skeleton include ε-caprolactone, δ-valerolactone, and γ-butyrolactone.

Examples of the high molecular weight cationic polymerizable compound having a polyester skeleton include “Placcel 205U”, “Placcel L205AL”, “Placcel L208AL”, “Placcel L212AL”, “Placcel L220AL”, “Placcel L230AL”, “Placcel 220ED”. , “Plaxel 220EC”, “Plaxel 220EB”, “Plaxel 303”, “Plaxel 305”, “Plaxel 308”, “Plaxel 312”, “Plaxel L312AL”, “Plaxel 320”, “Plaxel L320AL”, “Plaxel 320ML” , “Placcel 410”, “Placcel 410D”, “Placcel P3403”, “Placcel E227”, “Placcel DC2009”, “Placcel DC2016”, “Placcel” Kuseru DC2209 "(or, Ltd. Daicel) or," Kuraray Polyol P-510 "(manufactured by Kuraray Co., Ltd.) and the like are available as commercial products.

Examples of the high molecular weight cationic polymerizable compound having a polydiene skeleton include a compound having a cationic curable functional group at both ends of a molecular chain having a polybutadiene skeleton or a polyisoprene skeleton, and a molecule having the polybutadiene skeleton or a polyisoprene skeleton. Examples include compounds in which a part of the double bond of the chain is epoxidized. For example, trade names “Epolide PB3600” (manufactured by Daicel Corporation), “Poly ip” (manufactured by Idemitsu Kosan Co., Ltd.), and the like are commercially available.

Examples of the high molecular weight cationic polymerizable compound having a novolak skeleton include trade names “EPICLON N-740”, “EPICLON N-770”, “EPICLON N-775”, “EPICLON N-865”, “EPICLON N-”. 890 ”,“ EPICLON N-660 ”,“ EPICLON N-670 ”,“ EPICLON N-673 ”,“ EPICLON N-680 ”,“ EPICLON N-690 ”,“ EPICLON N-695 ”,“ EPICLON N-665 ” -EXP, EPICLON N-672-EXP, EPICLON N-655-EXP-S, EPICLON N-662-EXP-S, EPICLON N-665-EXP-S, EPICLON N- 70-EXP-S "," EPICLON N-685-EXP-S "(manufactured by DIC Corporation)," YDPN-638 "," YDCN-700-2 "," YDCN-700-3 "," YDCN " -700-5 "," YDCN-700-7 "," YDCN-700-10 "," YDCN-704 "," YDCN-704A "(the above, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) are available as commercial products. Is possible.

Examples of the high molecular weight cationic polymerizable compound having an alicyclic skeleton include a trade name “EHPE3150” (manufactured by Daicel Corporation), trade names “EPICLON HP-7200L”, “EPICLON HP-7200”, “EPICLON HP-”. 7200H ”,“ EPICLON HP-7200HH ”,“ EPICLON HP-7200HHH ”(hereinafter, manufactured by DIC Corporation), and the like.

The compounding amount of component (C) in the total amount (100% by weight) of the cationically polymerizable compound contained in the photocurable composition for nanoimprinting of the present invention (the total amount when two or more are used) is, for example, 10 to 50% by weight. Degree, preferably 20 to 40% by weight, particularly preferably 25 to 40% by weight.

(Component (D))
The photocurable composition for nanoimprinting of the present invention is a cation having a number average molecular weight of less than 500 (for example, about 100 to 450, preferably 300 to 450) in addition to the components (A) and (C) as the cationic polymerizable compound. A polymerizable compound (excluding the compound represented by the above formula (a-1) (component (A)), hereinafter may be referred to as “low molecular weight cationic polymerizable compound”) may be contained.

The low molecular weight cationic polymerizable compound contains one or more cationically curable functional groups in one molecule.

Examples of the cationically curable functional group include electron donating groups such as an epoxy group, an oxetanyl group, and a vinyl ether group. These can be used alone or in combination of two or more.

Accordingly, examples of the low molecular weight cationic polymerizable compound include epoxy compounds other than the compound represented by the formula (a-1), compounds having one or more oxetanyl groups in the molecule, and one or more compounds in the molecule. Examples thereof include compounds having a vinyl ether group. These can be used alone or in combination of two or more.

Examples of the epoxy compound other than the compound represented by the formula (a-1) include aromatic glycidyl ether type epoxy compounds such as bisphenol A type epoxy compounds and bisphenol F type epoxy compounds; and the above aromatic glycidyl ether type epoxy compounds. Alicyclic glycidyl ether epoxy compounds obtained by hydrogenating glycidyl ether epoxy compounds such as aliphatic polyhydric alcohol mono- or polyglycidyl ethers; glycidyl ester epoxy compounds; glycidyl amine epoxy compounds be able to.

Examples of the compound having one or more oxetanyl groups in the molecule include 3,3-bis (vinyloxymethyl) oxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyl). Oxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (Chloromethyl) oxetane, 3,3-bis (chloromethyl) oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis ([1-ethyl (3-oxetanyl)] methyl ) Ether, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] bicyclohexyl 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] cyclohexane, 1,4-bis ([(3-ethyl-3-oxetanyl) methoxy] methyl) benzene, 3-ethyl-3 ([( And 3-ethyloxetane-3-yl) methoxy] methyl) oxetane, xylylenebisoxetane, and the like. In the present invention, for example, commercial products such as trade names “OXT221”, “OXT121” (manufactured by Toagosei Co., Ltd.), and trade names “OXBP” (manufactured by Ube Industries) can be used. .

Examples of the compound having one or more vinyl ether groups in the molecule include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3- Hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4 -Hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1,4-cyclohexa Dimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, p-xylene glycol monovinyl ether, m-xylene glycol monovinyl ether, o-xylene glycol monovinyl ether, diethylene glycol monovinyl ether, Triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, oligoethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, tetrapropylene glycol monovinyl ether, pentapro Glycol monovinyl ether, oligo propylene glycol monomethyl ether, polypropylene glycol monovinyl ether, and may be derivatives thereof.

The photocurable composition for nanoimprinting of the present invention includes a component (D) (particularly one in the molecule) as the cationic polymerizable compound, together with the component (A) (preferably components (A) and (C)). The compound having the above oxetanyl group and having a number average molecular weight of less than 500 is preferable from the viewpoint that the initial curing rate can be improved and the thin film curability can be further improved.

The content of component (D) in the total amount (100% by weight) of the photocurable composition for nanoimprinting of the present invention is, for example, about 5 to 40% by weight, preferably 10 to 30% by weight. By containing the component (D) in the above range, the initial curing rate can be improved, and the thin film curability can be further improved.

The photocurable composition for nanoimprinting of the present invention may contain other components in addition to the cationic polymerizable compound and the cationic photopolymerization initiator as long as the effects of the present invention are not impaired. Examples of other components include a hydroxyl group-containing compound (eg, diethylene glycol), a photosensitizer (eg, a thioxanthone compound), an antifoaming agent, a leveling agent, a coupling agent (eg, a silane coupling agent), Conventional additives such as a surfactant, an inorganic filler, a flame retardant, an ultraviolet absorber, an ion adsorbent, a phosphor, a release agent, a pigment dispersant, and a dispersion aid can be exemplified.

The content of other components (the total amount when two or more types are contained) is about 10% by weight or less of the total amount (100% by weight) of the photocurable composition for nanoimprint.

As the photocurable composition for nanoimprinting of the present invention, it is particularly preferable that a leveling agent is contained because the surface smoothness of the resulting cured product can be improved.

Examples of the leveling agent include an acrylic leveling agent and a silicon leveling agent. In the present invention, for example, commercially available products such as trade names “BYK-350” and “BYK-UV3510” (manufactured by Big Chemie Japan Co., Ltd.) can be preferably used.

The amount of the leveling agent used is about 0.1 to 5% by weight of the total amount (100% by weight) of the photocurable composition for nanoimprint.

The photocurable composition for nanoimprinting of the present invention can be prepared, for example, by stirring and mixing the above components at a predetermined ratio and defoaming under vacuum as necessary.

The viscosity of the photocurable composition for nanoimprinting of the present invention is, for example, about 20 Pa · s or less, preferably 10 Pa · s or less. When the viscosity exceeds the above range, workability tends to be lowered. Moreover, there exists a tendency for the surface smoothness of the hardened | cured material obtained to fall. The viscosity of the present invention is a value obtained by measuring at a temperature of 25 ° C. and a rotation speed of 20 / sec using a rheometer (trade name “PHYSICA MCR301”, manufactured by Anton Paar).

[Production method of fine pattern substrate]
The manufacturing method of the fine pattern board | substrate of this invention etches an inorganic material board | substrate using the mask obtained by imprinting to the said photocurable composition for nanoimprints, It is characterized by the above-mentioned.

The fine pattern substrate of the present invention can be manufactured through the following steps, for example.
Step 1: A photocurable composition for nanoimprint is thinly applied to the surface of an inorganic material substrate to form a coating film.
Step 2: A mold on which a pattern is formed is brought into contact with the obtained coating film to transfer the pattern (imprint process).
Step 3: The photocurable composition for nanoimprint is cured by light irradiation, and then released to obtain a thin film to which the pattern shape of the mold is transferred.
Process 4: A fine pattern is obtained by etching an inorganic material board | substrate using the thin film to which the pattern shape of the mold was transferred as a mask.

As the inorganic material substrate used in Step 1, for example, a silicon substrate, a sapphire substrate, a ceramic substrate, an alumina substrate, a gallium phosphide substrate, a gallium arsenide substrate, an indium phosphide substrate, a gallium nitride substrate, or the like may be used. it can.

Examples of the method for applying the photocurable composition for nanoimprinting to the surface of the inorganic material substrate include a screen printing method, a curtain coating method, and a spray method. At that time, if necessary, a diluent solvent (eg, glycol derivatives such as ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate; acetone, methyl ethyl ketone) The concentration can be adjusted by diluting with ketones such as methyl butyl ketone and cyclohexanone; esters such as methyl lactate, ethyl lactate, ethyl acetate and butyl acetate). The thickness of the coating film is, for example, about 0.1 to 10 μm, preferably 0.3 to 3 μm. In this invention, since the said photocurable composition for nanoimprints is used, it is excellent in thin film sclerosis | hardenability.

Examples of the mold used in step 2 include a silicone mold, a thermoplastic resin mold, a curable resin mold, and a metal mold. The pressing force for bringing the mold into contact with the coating film is, for example, about 100 to 1000 Pa. The time for contacting the mold with the coating film is, for example, about 1 to 100 seconds. Further, the pattern shape of the mold is not particularly limited as long as it is a shape that can improve the extraction efficiency of light generated in the light emitting layer, and examples thereof include a trapezoidal shape, a conical shape, and a round shape. Can do.

The light (active energy ray) used for light irradiation in the step 3 may be light that causes the polymerization reaction of the photocurable composition for nanoimprinting to proceed, and may be infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α Any of a line, a beta ray, a gamma ray, etc. can be used. Of these, ultraviolet rays are preferable in terms of excellent handleability. For irradiation with ultraviolet rays, for example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, an LED lamp, a laser, or the like can be used.

Since the photocurable composition for nanoimprinting of the present invention has the above-described configuration, the curing rate is very high and the thin film curability is excellent. As for the light irradiation condition, when a 1 μm-thick film is formed by irradiating with ultraviolet rays, it is preferable to adjust the ultraviolet ray integrated light amount to, for example, about 100 to 3000 mJ / cm ² .

A post cure step may be provided between step 3 and step 4. By providing the post-cure process, the stability of the shape and the reproducibility of etching can be improved. Post-cure can be performed by heating and / or light irradiation. When post-cure is performed by heating, it is preferable to heat at 50 to 180 ° C. for about 0.5 to 3 hours, for example. When post-cure is performed by light irradiation, it is preferable to irradiate for about 10 to 100 seconds with an irradiation intensity of about 10 to 100 mW / cm ² , for example.

Examples of the etching method in step 4 include a dry etching method and a wet etching method. In the present invention, it is particularly preferable to employ a dry etching method, and in particular, it is preferable to employ reactive ion etching (RIE) in terms of enabling highly accurate fine processing.

In the method for producing a fine pattern substrate of the present invention, a thin film having a very low curing shrinkage can be rapidly formed on the surface of an inorganic material substrate by irradiation with light because the above-described photocurable composition for nanoimprinting is used. In addition, since the thin film onto which the shape of the mold thus obtained is accurately transferred is used as a mask, a fine pattern substrate on which a fine pattern of the mold is accurately transferred can be obtained.

[Semiconductor device]
The semiconductor device (for example, LED) of this invention is equipped with the said fine pattern board | substrate, It is characterized by the above-mentioned.

For example, the LED is composed of a light emitter obtained by growing a light emitting layer (GaN layer) on the surface of the fine pattern substrate by metal organic vapor phase epitaxy (MOVPE), a lens, a wiring, and the like.

The semiconductor device (especially LED) of the present invention has a fine pattern substrate formed using the photocurable composition for nanoimprinting of the present invention, and thus has excellent light extraction efficiency, high luminance, long life, and low power consumption. And low heat-generating properties.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Preparation Example 1 (Preparation of compound represented by formula (a-1))
A dehydration catalyst was prepared by stirring and mixing 70 g (0.68 mol) of 95 wt% sulfuric acid and 55 g (0.36 mol) of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU).
Into a 3 liter flask equipped with a stirrer, a thermometer, and a dehydration pipe and equipped with a heated distillation pipe, 1000 g (5.05 mol) of hydrogenated biphenol (= 4,4′-dihydroxybicyclohexyl), the above 125 g of dehydration catalyst (0.68 mol as sulfuric acid) and pseudocumene 1500 g prepared in (1) were added, and the flask was heated. The generation of water was confirmed when the internal temperature exceeded 115 ° C. The temperature was further raised to raise the temperature to the boiling point of pseudocumene (internal temperature 162 to 170 ° C.), and dehydration reaction was carried out at normal pressure. By-product water was distilled off and discharged out of the system through a dehydration tube. The dehydration catalyst was liquid under the reaction conditions and was finely dispersed in the reaction solution. After about 3 hours, almost theoretical amount of water (180 g) was distilled, and the reaction was terminated.
After completion of the reaction, the pseudocumene was distilled off from the liquid in the reactor using a 10-stage Oldershaw type distillation column, and then distilled at an internal pressure of 10 Torr (1.33 kPa) and an internal temperature of 137 to 140 ° C. , 731 g of bicyclohexyl-3,3′-diene was obtained.

The obtained bicyclohexyl-3,3′-diene (243 g) and ethyl acetate (730 g) were charged into a reactor, and nitrogen was blown into the gas phase portion, and the temperature in the reaction system was controlled to 37.5 ° C. Then, 274 g of a 30 wt% peracetic acid ethyl acetate solution (water content 0.41 wt%) was added dropwise over about 3 hours. After the peracetic acid solution was dropped, the reaction was terminated by aging at 40 ° C. for 1 hour. Further, the crude liquid at the end of the reaction was washed with water at 30 ° C., and the low boiling point compound was removed at 70 ° C./20 mmHg to obtain 270 g of an alicyclic epoxy compound. The oxirane oxygen concentration of the obtained alicyclic epoxy compound was 15.0% by weight. In ¹ H-NMR measurement, a peak derived from an internal double bond in the vicinity of δ4.5 to 5 ppm disappeared, and a proton peak derived from an epoxy group was confirmed in the vicinity of δ3.1 ppm. , 3 ′, 4′-diepoxybicyclohexyl was confirmed.

Examples 1-9, Comparative Examples 1-6
Each component was blended according to the blending composition (unit: parts by weight) shown in the table, and stirred and mixed in a flask at room temperature to obtain a uniform photocurable composition for nanoimprinting.
About the obtained photocurable composition for nanoimprint and the cured product obtained by curing the photocurable composition for nanoimprint, the following methods were used: (1) Viscosity, (2) Curability, (3) Shape Transferability and (4) surface uniformity were evaluated. The evaluation results are summarized in Table 1 below.

(1) Measurement of viscosity The viscosity (Pa · s) of the photocurable compositions for nanoimprints obtained in Examples and Comparative Examples is measured using a rheometer (trade name “PHYSICA MCR301”, manufactured by Anton Paar). It was measured at 25 ° C. and a rotation speed of 20 rotations / second.

(2) Evaluation of Curability Propylene glycol monomethyl ether acetate (trade name “MMPGAC”, manufactured by Daicel Corporation, hereinafter referred to as “MMPGAC”) was added to 103 parts by weight of the photocurable composition for nanoimprint obtained in Examples and Comparative Examples. The diluted solution obtained by adding 60 parts by weight is applied onto a silicon wafer at a spin coat rotational speed described in the table using a spin coater to form a coating film (film thickness: 1 μm). did.
In a state where a polydimethylsiloxane mold (pattern height to width ratio (= aspect ratio) of 2: 1) is pressed at 200 Pa and brought into contact with the obtained coating film for 60 seconds, an ultraviolet irradiation device (UV or UV-LED A thin film having a polydimethylsiloxane mold pattern imprinted on the surface was obtained by irradiating with ultraviolet rays having the light amount shown in the table using an irradiation apparatus and then releasing the mold.
The obtained thin film was immersed in acetone for 5 seconds at 25 ° C., and the subsequent thin film was visually observed, and the curability was evaluated according to the following criteria.
Evaluation criteria ○ (good): retained without disturbing the pattern shape Δ (somewhat good): part of the pattern was dissolved in acetone, the remaining resin remained white on the substrate, and the pattern was defective × (defect): The pattern is completely lost

(3) Evaluation of shape transferability About the thin film by which the pattern of the silicone mold was imprinted on the surface obtained in said (2) sclerosis | hardenability evaluation, the height-width ratio (= aspect ratio) of a pattern was measured, The shape transferability was evaluated according to the following criteria.
Evaluation criteria ○ (Good): When the aspect ratio is 2: 1 to 1.9: 1 Δ (Slightly good): When the aspect ratio is 1.5: 1 or more and less than 1.9: 1 × (Bad): When the aspect ratio is less than 1.5: 1 or there is a part where the pattern is broken

(4) Evaluation of surface uniformity The dilution obtained by adding 60 parts by weight of MMPMAC to 103 parts by weight of the photocurable composition for nanoimprints obtained in Examples and Comparative Examples was expressed using a spin coater. A coating film (film thickness: 1 μm) was formed by coating on a silicon wafer at the spin coat rotational speed described in 1). A thin film was obtained by irradiating the obtained coating film with ultraviolet rays having a light amount shown in the table using an ultraviolet irradiation device (UV or UV-LED irradiation device).
The thickness of the obtained thin film was measured using a step gauge (trade name “T-4000”, manufactured by Kosaka Laboratory Ltd.), and the thickness of the thinnest part (T ₁ ) and the thinnest part of the thin film were measured. The difference in thickness (T ₂ ) (T ₁ -T ₂ ) was taken as a step, and the surface uniformity was evaluated according to the following criteria.
Evaluation criteria ○ (Good): When the step (T ₁ -T ₂ ) is 0.02 μm or less Δ (Slightly good): When the step (T ₁ -T ₂ ) exceeds 0.02 μm and 0.050 μm or less × ( Defect): When the step (T ₁ -T ₂ ) exceeds 0.050 μm

In addition, the component used by the Example and the comparative example is as follows.
<Cationically polymerizable compound>
Bicyclodiepoxy compound (a-1): 3,4,3 ′, 4′-diepoxybicyclohexyl (the compound obtained in Preparation Example 1 was used), number average molecular weight: 194
OXT-221: 3-ethyl-3 ([(3-ethyloxetane-3-yl) methoxy] methyl) oxetane, trade name “OXT-221”, manufactured by Toagosei Co., Ltd., number average molecular weight: 214
OXBP: Oxetane compound having a biphenyl skeleton, trade name “OXBP”, manufactured by Ube Industries, Ltd., number average molecular weight: 383
N-890: Modified novolak type epoxy resin, trade name “EPICLON N-890”, manufactured by DIC Corporation, number average molecular weight: 500 or more HP-7200: dicyclopentadiene type epoxy resin, trade name “EPICLON HP-7200” DIC Corporation, number average molecular weight: 550
PB3600: Liquid epoxidized polybutadiene, trade name “Epolide PB3600”, manufactured by Daicel Corporation, number average molecular weight: 5900
EHPE3150: Transparent solid epoxy compound, trade name “EHPE3150”, manufactured by Daicel Corporation, number average molecular weight: 500 or more

<Photocationic polymerization initiator>
b-1: initiator containing fluorinated alkylfluorophosphate anion, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate with propylene carbonate in 50% B-2: initiator containing a fluoroalkylfluorophosphate anion, diphenyl [4- (phenylsulfonyl) phenyl] tris (pentafluoroethyl) trifluorophosphate 654027: allylsulfonium hexafluoroantimonate and diallylsulfonium A compound obtained by diluting a 50% mixture of hexafluoroantimonate with propylene carbonate to 50%, Sigma Aldrich Japan 407216: Allylsulfonium hexafluorophosphate and di Compound diluted to 50% 50% mixture of Lil hexafluorophosphate in propylene carbonate, manufactured by Sigma-Aldrich Japan Irgacure 250: iodonium salt photo cationic initiator, trade name "Irgacure 250", produced by BASF

<Additives>
BYK-350: Leveling agent, acrylic copolymer, trade name “BYK-350”, manufactured by BYK Japan Japan Co., Ltd. BYK-UV3510: Leveling agent, a mixture of polyether-modified polydimethylylsiloxane and polyether, trade name “ BYK-UV3510 ", manufactured by Big Chemie Japan

When the photocurable composition for nanoimprint of the present invention is thinly applied to a substrate even in an oxygen atmosphere and irradiated with light, it can be cured quickly and while suppressing curing shrinkage to form a thin film having excellent curability. it can. Therefore, a fine pattern can be transferred quickly and accurately. When nanoimprinting is performed using the photocurable composition for nanoimprinting of the present invention, it is possible to form a mask on which a fine pattern of the mold is accurately transferred, and etching the inorganic material substrate using the mask. By doing so, a fine pattern having excellent dimensional reproducibility according to the design drawing can be formed on the surface of the inorganic material substrate.

Claims (6)

1. The photocurable composition for nanoimprint containing the following component (A) and a component (B).
   Component (A): Compound represented by the following formula (a-1)
   

   

   [Wherein, R ¹ to R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group that may contain a halogen atom, or an alkoxy group that may have a substituent. . X represents a single bond or a linking group]
   Component (B): Photocationic polymerization initiator having a fluorinated alkylfluorophosphate anion
2. Furthermore, the photocurable composition for nanoimprints of Claim 1 containing the following component (C).
   Component (C): Cationic polymerizable compound having a number average molecular weight of 500 or more (excluding compounds contained in component (A))
3. The photocurable composition for nanoimprints according to claim 2, wherein the component (C) is a cationically polymerizable compound having a polycarbonate skeleton, a polyester skeleton, a polydiene skeleton, a novolac skeleton, or an alicyclic skeleton.
4. A method for producing a fine pattern substrate, wherein an inorganic material substrate is etched using a mask obtained by imprinting the photocurable composition for nanoimprints according to any one of claims 1 to 3.
5. A fine pattern substrate obtained by the method for producing a fine pattern substrate according to claim 4.
6. A semiconductor device comprising the fine pattern substrate according to claim 5.