TWI593679B - Photocurable composition for nanoimprint, and method for producing fine pattern substrate using the same - Google Patents

Description

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

The present invention relates to a photocurable composition for nanoimprinting and a method for producing a fine pattern substrate using the same. The present application claims priority to Japanese Patent Application No. 2013-004758, filed on Jan.

Light-emitting diodes (LEDs) have superior energy conversion efficiency and are used in most electronic devices due to their long life. The LED has a structure in which a light-emitting layer containing a GaN-based semiconductor is laminated on an inorganic material substrate. However, since the refractive index difference existing between the inorganic material substrate and the GaN-based semiconductor and the air is large, most of the total amount of light generated by the light-emitting layer is repeatedly reflected and eliminated inside, and the light extraction efficiency is inferior.

As a method for solving the above problems, a method of forming a fine pattern of about several μm on the surface of an inorganic material substrate and laminating a light-emitting layer containing a GaN-based semiconductor thereon is conventionally known.

As a method of forming a fine pattern, it is conventional to form a mask on an inorganic material substrate by photolithography, and to form a pattern by etching using the obtained mask. However, the enlargement of the inorganic material substrate or the nano patterning has progressed, with the cost and An increase in processing time will be a problem. Here, a method of forming a mask by replacing the photolithography by nanoimprinting has attracted attention.

As a photocurable composition for nanoimprinting, For example, a radically polymerizable compound such as a vinyl ether having an alicyclic structure or a vinyl ether having an alicyclic structure and an aromatic ring structure is used (Patent Documents 1 and 2). However, this radically polymerizable compound has a large hardening shrinkage and is difficult to form a fine pattern with high precision. Further, the photocurable composition is formed by rapidly curing the film after coating on the substrate, but the radical polymerizable compound is inhibited by polymerization due to oxygen, and the curing rate is lowered, especially in the film. The problem that sex will be reduced. For the polymerization inhibition caused by oxygen, a method of hardening it in a gas atmosphere of an inert gas such as nitrogen is also considered. However, since the equipment is bulky, the cost is increased, and it takes time to replace the air, so work efficiency Will reduce problems like this.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2003-327628

Patent Document 2 Japanese Patent Laid-Open Publication No. 2011-84527

Patent Document 3 Japanese Patent Laid-Open Publication No. 2011-157482

Accordingly, an object of the present invention is to provide a photocurable composition for nanoimprinting which is applied to a substrate by thin layer and irradiated with light to form a film which is rapidly hardened and has a small hardening shrinkage and can be accurately Finely transfer the fine pattern of the mold.

Another object of the present invention is to provide a method for producing a fine pattern substrate using the photocurable composition for nanoimprinting.

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 problems, the present inventors have found that a hardened composition containing a specific cationically polymerizable compound having an alicyclic epoxy group and a photocationic polymerization initiator having a fluoroalkylfluorophosphate anion Since the polymerization is not inhibited by oxygen, even in an oxygen atmosphere, a thin film can be formed by applying a thin layer on a substrate and irradiating light to form a film (that is, having excellent film hardenability). The hardening shrinkage is small, and the fine pattern of the mold can be accurately transferred. Further, it has been found that when the imprinting composition is used to perform nanoimprinting, the fine pattern of the mold can be accurately transferred. Further, in the patent specification, the "alicyclic epoxy group" is a group in which two adjacent carbon atoms constituting an alicyclic ring form a ring together with one oxygen atom (in particular, by using cyclohexane). An epoxy group composed of two carbon atoms adjacent to the ring and an oxygen atom). The present invention has been accomplished in accordance with such findings.

That is, the present invention provides a photocurable composition for nanoimprinting comprising the following components (A) and (B); and component (A): 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, a hydrocarbon group which may contain an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent, and X represents a single bond or a linking group. Component (B): a photocationic polymerization initiator having a fluoroalkylfluorophosphate anion.

The present invention further provides a photocurable composition for nanoimprinting comprising the following component (C); component (C): a cationically polymerizable compound having a number average molecular weight of 500 or more (except for the compound contained in the component (A) other than).

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

Further, the present invention provides a method for producing a fine pattern substrate, which is obtained by etching a mask obtained by performing imprint processing on the photocurable composition for nanoimprint described above.

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

The present invention further provides a semiconductor device comprising the fine pattern substrate described above.

That is, the present invention relates to the following.

(1) A photocurable composition for nanoimprinting comprising the following components (A) and (B); and component (A): by the formula (a-1) [wherein, R ¹ to R ¹⁸ The same or different, meaning a hydrogen atom, a halogen atom, a hydrocarbon group which may contain an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent, and X represents a compound represented by a single bond or a linking group; ): Photocationic polymerization initiator having a fluoroalkyl fluorophosphate anion.

(2) The photocurable composition for nanoimprint described in (1), further comprising the following component (C); component (C): a cationically polymerizable compound having a number average molecular weight of 500 or more (except for the component ( A) in addition to the compounds contained in).

(3) The photocurable composition for nanoimprint described in (2), wherein the component (C) is a cation having a polycarbonate skeleton, a polyester skeleton, a polydiene skeleton, a phenolic skeleton, or an alicyclic skeleton. Polymeric compound.

(4) The photocurable composition for nanoimprint according to any one of (1) to (3), wherein the total amount of the cationically polymerizable compound contained in the photocurable composition for nanoimprinting is The content of the component (A) (100% by weight) is from 10 to 70% by weight.

(5) The photocurable composition for nanoimprint described in any one of (1) to (4), wherein a volume expansion coefficient when the compound represented by the formula (a-1) is cured is 0 to 30%.

(6) The photocurable composition for nanoimprint according to any one of (1) to (5) wherein, in the compound represented by the formula (a-1), X is a group containing an ester bond. Compound content, which is a photocurable composition for nanoimprinting It is contained in an amount of 40% by weight or less based on the total amount (100% by weight) of the compound represented by the formula (a-1).

The photocurable composition for nanoimprint according to any one of (1) to (6), wherein the photocationic polymerization initiator having a fluoroalkylfluorophosphate anion in the component (B) is The cationic moiety is a triarylphosphonium ion.

(8) The photocurable composition for nanoimprint according to any one of (1) to (7) further comprising the following component (D); and component (D): one or more in the molecule. A compound having a number average molecular weight of less than 500.

(9) A method of producing a fine pattern substrate, wherein the inorganic material is etched by using a mask obtained by performing imprint processing on the photocurable composition for nanoimprint described in any one of (1) to (8) Substrate.

(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 described in (10).

Since the photocurable composition for nanoimprinting of the present invention has the above-described structure, even if it is applied thinly on a substrate and irradiated with light in an oxygen gas atmosphere, it can be hardened while suppressing hardening and shrinking. On the other hand, a film excellent in hardenability is formed. Therefore, the fine pattern can be transferred quickly and accurately. Further, when the nano-imprinting photocurable composition of the present invention is used for nanoimprinting, a mask which can accurately transfer a fine pattern of a mold can be formed, and the inorganic material is etched by using the mask. The substrate can form a fine pattern having a dimensional reproducibility excellent in design surface on the surface of the inorganic material substrate.

[Formation of the Invention] [Photocurable composition for nanoimprinting]

The photocurable composition for nanoimprint of the present invention contains the following components (A) and (B).

Ingredient (A): a compound represented by formula (a-1)

Ingredient (B): Photocationic polymerization initiator with fluoroalkyl fluorophosphate anion

(ingredient (A))

The component (A) is a compound represented by the following formula (a-1). The compound represented by the following formula (a-1) has cationic polymerizability (that is, a compound-based cationically polymerizable compound represented by the following formula (a-1)), and has excellent film curability.

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

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

Examples of the hydroxyl group of R ¹ to R ¹⁸ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group obtained by bonding these two or more.

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

Examples of the alicyclic hydrocarbon group include a C _3-12 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a cyclododecyl group; and a C ₃ such as a cyclohexenyl group; _a C _4-15 cross-linked cyclic hydrocarbon group such as a _-12 cycloalkenyl group; a bicycloheptyl group or a bicycloheptenyl group; and the like.

The aromatic hydrocarbon group may, for example, be a C _6-14 aryl group (preferably a C _6-10 aryl group) such as a phenyl group or a naphthyl group.

In addition, in the group in which two or more groups selected from the group consisting of the above-mentioned aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group are bonded, a group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded is used. For example, 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; and the like can be given. Examples of the group in which the aliphatic hydrocarbon group and the aromatic hydrocarbon group are bonded to each other include a C _7-18 aralkyl group such as a benzyl group or a phenethyl group (especially, a C _7-10 aralkyl group); and a cinnamyl group. etc. -C _2-20 aryl-C _6-14 alkenyl group; tolyl, etc. C _1-20 alkyl-substituted C _6-14 aryl group; a styryl group, etc. C _2-20 alkenyl group substituted with C _6-14 Aryl and the like.

Examples of the hydrocarbon group which may contain an oxygen atom or a halogen atom in R ¹ to R ¹⁸ include a group in which at least one hydrogen atom of the above hydrocarbon group is substituted with a group having an oxygen atom or a group having a halogen atom. Examples of the group having an oxygen atom include a hydroxyl group; a hydroperoxy group; a C _1- group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group or an isobutoxy group. ₁₀ alkoxy; allyloxy, etc. C _2-10 alkenyloxy group; selected may have a C _1-10 alkyl, substituted C _2-10 alkenyl group, a halogen atom, a C _1-10 alkoxy groups and a C _6-14 aryloxy group (for example, a tolyloxy group, a naphthyloxy group, etc.); a C _7-18 aralkyloxy group such as a benzyloxy group or a phenethyloxy group; an ethoxy group or a propyloxy group; , (meth) Bing Xixi, benzyloxy, acyl group, the C _1-10 acyl group and the like; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, etc. the C _1-10 alkoxycarbonyl group; a a C _6-14 aryloxycarbonyl group 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, phenoxycarbonyl, tolylcarbonyl, a naphthoxycarbonyl group or the like; a C _7-18 aralkyloxycarbonyl group such as a benzyloxycarbonyl group; an epoxy group-containing group such as a glycidoxy group; and an oxycyclobutyl group such as an ethyloxycyclobutoxy group. ; acetyl group, propionyl, acyl, phenyl acyl, etc. C _1-10 acyl; isocyanate group; sulfone group; acyl urethane Oxo; and so to make two or more of such C _1-10 alkylene group and the like interposed therebetween, or do not interposed therebetween formed by the junction of the mode key group. 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 represented by R ¹ to R ¹⁸ include a C _1-10 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group or an isobutoxy group. base.

As the substituent which the alkoxy group may have, 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 decyloxy group, Sulfhydryl, C _1-10 alkylthio, C _2-10 alkenylthio, C _6-14 arylthio, C _7-18 aralkylthio, carboxyl, C _1-10 alkoxycarbonyl, C _{6-14 Oxycarbonyl} , C _7-18 aralkyloxycarbonyl, amine, mono or di C _1-10 alkylamino, C _1-10 fluorenyl, epoxy group-containing, oxocyclobutyl group, C _1-10 fluorenyl group, a pendant oxy group, and a group obtained by bonding these two or more so that a C _1-10 alkyl group or the like is interposed therebetween or not interposed therebetween.

As R ¹ to R ¹⁸ , a hydrogen atom is preferred.

X in the above 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, a guanamine group, and a group in which a plurality of these are bonded together. Examples of the divalent hydrocarbon group include a linear or branched chain such as a methylene group, a methylmethylene group, a dimethylmethylene group, an exoethyl group, a propyl group or a trimethylene group. C _1-18 alkylene (preferably a linear or branched chain C _1-3 alkyl); 1,2-cyclopentyl, 1,3-cyclopentyl, cyclopentylene a divalent C _3-12 cycloalkylene group having a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a cyclohexylene group, or the like, and a C _{3-12 having a} valence A cycloalkylene group (preferably a divalent C _3-6 cycloalkylene group and a divalent C _3-6 cycloalkylene group).

Based on the volume of the uncured material, the above formula (a-1) The volume expansion coefficient of the compound represented by curing is preferably, for example, about 0 to 30%, particularly preferably from 0 to 10%, most preferably from 0.5 to 5.0%. When the volume expansion coefficient is less than the above range (if it is a negative value), there is a tendency that the fine pattern of the mold is transferred with high precision due to hardening shrinkage.

Also, the body when the compound represented by the formula (a-1) is hardened The coefficient of expansion can be calculated by the following method.

That is, the composition containing the compound represented by the formula (a-1) and the cationic polymerization initiator can be hardened to form a cured product by UV irradiation, and the specific gravity x of the composition before hardening and the cured product can be obtained. The specific gravity y is calculated according to the following formula.

Volume expansion coefficient = [(y-x) / x] × 100

The compound 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'-dihydroxyoxy)dicyclohexyl is preferably used from the viewpoint of having a small steric hindrance, a rapid hardening reaction by light irradiation, and hardening expansibility. [Volume expansion coefficient: 2.4%].

Further, in the compound represented by the formula (a-1), the compound in which X is an ester bond-containing group is preferably used in an amount of 40% by weight based on the total amount (100% by weight) of the compound represented by the formula (a-1). The following (more preferably 30% by weight or less, particularly preferably less than 10% by weight, most preferably less than 5% by weight). In the compound represented by the formula (a-1), when the content of the compound in which X is an ester bond-containing group exceeds the above range, the film curability tends to be lowered.

The compound represented by the 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 according to conventional or customary methods. There, R in the formula (a-1 ') of ¹ to R ^18, X based on the same formula (a-1) of R ¹ to R ^18, X.

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

Moreover, it is contained in the photocurable composition for nanoimprinting The content of the component (A) in the total amount (100% by weight) of the cationically polymerizable compound (the total amount thereof is two or more) is, for example, about 10 to 70% by weight, preferably 20 to 60% by weight. When the content of the component (A) is less than the above range, the film curability and transferability tend to be lowered. On the other hand, when the content of the component (A) exceeds the above range, the etching endurance tends to be lowered.

(ingredient (B))

The photocationic polymerization initiator of the component (B) of the present invention is a compound which is caused by the irradiation of light to generate an acid, and the cationically polymerizable compound contained in the photocurable composition for nanoimprinting is hardened. (= Photoacid generator), which comprises an ionic portion that absorbs light and an anion portion that serves as an acid generating source.

In the present invention, it is characterized in that it has a fluoroalkyl fluoride The acid anion compound acts as a photocationic polymerization initiator. This compound has excellent safety and can accelerate the curing of the cationically polymerizable compound containing the component (A) by irradiation of light, so that excellent film hardenability can be imparted to the photocurable composition for nanoimprinting. . The photocationic polymerization initiator of the present invention can be used singly or in combination of two or more.

For example, the fluoroalkyl fluorophosphate anion is represented 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 a hydrogen atom is substituted by a fluorine atom, and n represents an integer of 1 to 5)

In the formula (b), an alkyl group (preferably a C _1-4 alkyl group) in which Rf is a hydrogen atom substituted with 80% or more of a hydrogen atom, preferably CF ₃ , C ₂ F ₅ , (CF _{3 ) 2} % of a hydrogen atom such as CF, C ₃ F ₇ , C ₄ F ₉ , (CF ₃ ) ₂ CFCF ₂ , CF ₃ CF ₂ (CF ₃ )CF, or (CF ₃ ) ₃ C is replaced by a fluorine atom Chain or branched chain C _1-4 alkyl.

Therefore, as the anion portion of the photocationic polymerization initiator, it is particularly preferably [(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.

Further, examples of the cationic portion of the photocationic polymerization initiator include cerium ions, cerium ions, and selenium ions. In the present invention, among them, cerium ions and cerium ions are preferred.

Examples of the phosphonium ion include diphenylphosphonium, di-p-tolylhydrazine, bis(4-dodecylphenyl)fluorene, and bis(4-methoxyphenyl). 錪, (4-octyloxyphenyl)phenyl hydrazine, bis(4-dodecyloxy)phenyl fluorene, 4-(2-hydroxytetradecyloxyphenyl)phenyl fluorene, 4-iso An aryl sulfonium ion (particularly, a bisaryl sulfonium ion) such as propylphenyl (p-tolyl) fluorene or 4-isobutylphenyl (p-tolyl) fluorene.

Examples of the cerium ion include triphenyl sulfonium and bis. An aryl sulfonium ion (particularly, a triaryl sulfonium ion) such as phenyl[4-(phenylthio)phenyl]anthracene or tri-p-tolylhydrazine.

As the photocationic polymerization initiator of the present invention, for example, It is suitable to use 4-isopropylphenyl (p-tolyl) ruthenium tris(pentafluoroethyl)trifluorophosphate, [1,1'-biphenyl]-4-yl [4-(1,1'- Biphenyl)-4-ylthiophenyl]phenyltris(pentafluoroethyl)trifluorophosphate, diphenyl[4-(phenylthioindolyl)phenyl]tris(pentafluoroethyl)trifluoro Phosphate, triphenylsulfanyl (pentafluoroethyl)trifluorophosphate, [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonyltris(pentafluoro) Base) trifluorophosphate and the like.

As the content of the component (B), it is hard relative to the nanoimprinting 100 parts by weight of the cationically polymerizable compound (in total of two or more kinds thereof) contained in the chemical composition is, for example, about 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, particularly preferably 0.5. Up to 5 parts by weight. When the content of the component (B) is less than the above range, the film hardenability tends to be lowered. On the other hand, when the content of the component (B) exceeds the above range, the storage stability of the photocurable composition for nanoimprinting tends to be lowered.

(ingredient (C))

The photocurable composition for nanoimprinting of the present invention may contain a compound other than the compound represented by the above formula (a-1) (ingredient (A)). It is a cationically polymerizable compound. The photocurable composition for nanoimprinting of the present invention preferably contains a cationically polymerizable compound having a number average molecular weight of 500 or more (hereinafter referred to as "high molecular weight cationically polymerizable compound"). The film hardenability can be further improved by using a high molecular weight cationically polymerizable compound in combination. Further, since the high molecular weight cationically polymerizable compound has excellent shape stability, the curing shrinkage can be suppressed by using it in combination, and the transfer property can be further improved.

Average number of high molecular weight cationically polymerizable compounds The amount 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 cationically polymerizable compound is less than the above range, it tends to be difficult to obtain an effect of imparting shape stability. On the other hand, when the number average molecular weight of the high molecular weight cationically polymerizable compound exceeds the above range, the viscosity of the curable composition tends to increase, and the workability tends to decrease. Further, the surface smoothness of the cured product obtained by curing the photocurable composition for nanoimprinting tends to be lowered.

High molecular weight cationically polymerizable compound contains cation Hardenable functional group. The number of cationically curable functional groups contained in the molecule of the high molecular weight cationically polymerizable compound 1 is preferably two or more.

As the cation hardening functional group, for example, An electron supply group such as a hydroxyl group, an epoxy group, or an oxocyclobutyl group. The high molecular weight cationically polymerizable compound of the present invention may be contained alone or in combination of two or more kinds and may contain the electron-donating group.

As a high molecular weight cationically polymerizable compound, for example, It may be selected from a polycarbonate skeleton, a polyester skeleton, a polydiene skeleton, A skeleton of a phenolic skeleton or an alicyclic skeleton, a compound of the above cationically curable functional group, or the like. These can be used alone or in combination of two or more. In the present invention, as the cation-curable functional group, a high molecular weight cationically polymerizable compound containing an epoxy group is preferably used.

High molecular weight cationic polymerization with the polycarbonate backbone The compound is transesterified by a phosgene method, or a dialkyl carbonate (for example, dimethyl carbonate, diethyl carbonate, etc.) or a diphenyl carbonate, and a polyhydric alcohol (see Japanese Patent Laid-Open No. 62). -187725, special Kaikai 2-157517, special Kaikai 2-49025, special Kaiping 3-220233, special Kaiping 3-252420).

As the polyol used in the transesterification reaction, for example, Examples thereof include 1,6-hexanediol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, and 2,3-butanediol. 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,12-dodecanediol, polybutadienediol, neopenta Glycol, tetramethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, 1,3-dihydroxyacetone, hexanediol, 1,2,6-hexanetriol, di(trishydroxyl) Base) propane, trimethylolethane, trimethylol octane, pentaerythritol, and the like. Further, an ester diol (manufactured by Mitsubishi Gas Chemical Co., Ltd.), a polyester polyol, or a polyether polyol can also be used.

As a high molecular weight cation having the polycarbonate skeleton For example, as a commercial product, the product name "PLACCEL CD205", "PLACCEL CD205PL", "PLACCEL CD205HL", "PLACCEL D210", "PLACCEL CD210PL", "PLACCEL CD210HL", "PLACCEL CD220", "" can be obtained as a commercial product. PLACCEL CD220PL", "PLACCEL CD220HL", "PLACCEL CD220EC", "PLACCEL CD221T" (above, manufactured by Daicel Co., Ltd.) or trade name "UM-CARB90 (1/3)", "UM-CARB90 (1/1)" "UM-CARB100" (above, manufactured by Ube Industries Co., Ltd.).

High molecular weight cationic polymerizable compound having a polyester skeleton The substance can be synthesized by the reaction of a polyol with a carboxylic acid. Others can be synthesized by ring-opening polymerization of lactones.

As a high molecular weight cation having a polyester skeleton Examples of the polyol of the polymerizable compound raw material include the same polyols used in the above transesterification reaction.

As a high molecular weight cation having a polyester skeleton Examples of the carboxylic acid of the polymerizable compound raw material include oxalic acid, adipic acid, sebacic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, sebacic acid, citric acid, and 2. 6-naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, cis-methylbutenedioic acid, 1,10-sebacic acid, methylhexahydrophthalic anhydride, hexahydroortho Phthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, lactic acid, malic acid, glycolic acid, dimethylolpropionic acid, two Hydroxymethyl butyric acid and the like.

As a high molecular weight cation having a polyester skeleton Examples of the lactone of the polymerizable compound raw material include ε-caprolactone, δ-valerolactone, and γ-butyrolactone.

As the high molecular weight cationic polymerization having a polyester skeleton For example, as a commercial product, "PLACCEL 205U" can be obtained. "PLACCEL L205AL", "PLACCEL L208AL", "PLACCEL L212AL", "PLACCEL L220AL", "PLACCEL L230AL", "PLACCEL 220ED", "PLACCEL 220EC", "PLACCEL 220EB", "PLACCEL 303", "PLACCEL 305", "PLACCEL 308", "PLACCEL 312", "PLACCEL L312AL", "PLACCEL 320", "PLACCEL L320AL", "PLACCEL 320ML", "PLACCEL 410", "PLACCEL 410D", "PLACCEL P3403", "PLACCEL E227", "PLACCEL DC2009", "PLACCEL DC2016", "PLACCEL DC2209" (above, manufactured by Daicel Co., Ltd.), and "KURARAY POLYOL P-510" (manufactured by Kuraray Co., Ltd.).

As a high molecular weight cationic polymerization having the polydiene skeleton The conjugated compound may, for example, be a compound having a cationic hardening functional group at both ends of a molecular chain having a polybutadiene skeleton or a polyisoprene skeleton, or a polybutadiene skeleton or polyisoprene. A compound in which a part of a molecular chain double bond of a diene skeleton is epoxidized or the like. For example, the product name "EPOLEAD PB3600" (manufactured by Daicel Co., Ltd.) and the product name "Poly ip" (manufactured by Idemitsu Kogyo Co., Ltd.) can be obtained as a commercial product.

As a high molecular weight cationic polymerization having the phenolic skeleton For example, as a commercial product, the product names "EPICLON N-740", "EPICLON N-770", "EPICLON N-775", "EPICLON N-865", "EPICLON N-890", "EPICLON" can be obtained. 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-670-EXP-S", "EPICLON N-685-EXP-S" (above, DIC Corporation); "YDPN-638", "YDCN-700-2" , "YDCN-700-3", "YDCN-700-5", "YDCN-700-7", "YDCN-700-10", "YDCN-704", "YDCN-704A" (above, Nippon Steel Sumitomo Chemical Co., Ltd.) and so on.

High molecular weight cationic polymerizable compound having an alicyclic skeleton For example, the product name "EHPE3150" (made by Daicel Co., Ltd.), "EPICLON HP-7200L", "EPICLON HP-7200", "EPICLON HP-7200H", "EPICLON HP-7200HH", and " A dicyclopentadiene type epoxy resin such as EPICLON HP-7200HHHH (above, manufactured by DIC Corporation).

In the photocurable composition for nanoimprinting of the present invention The blending amount of the component (C) in the total amount (100% by weight) of the cationically polymerizable compound (for the case of using two or more kinds thereof) is, for example, about 10 to 50% by weight, preferably 20 to 40. % by weight, particularly preferably from 25 to 40% by weight.

(ingredient (D))

The cationically polymerizable compound may contain a photocurable composition for nanoimprinting of the present invention in addition to the above components (A) and (C), and may have a number average molecular weight of less than 500 (e.g., about 100 to 450, preferably The cationically polymerizable compound of 300 to 450) (excluding the compound represented by the above formula (a-1) (component (A)), and later referred to as "low molecular weight cationically polymerizable compound").

The low molecular weight cationically polymerizable compound is one molecule It contains one or more cationic hardening functional groups.

As the cation hardening functional group, for example, An electron donating group such as an epoxy group, an oxocyclobutyl group or a vinyl ether group. These may be contained alone or in combination of two or more.

Therefore, as a low molecular weight cationically polymerizable compound, For example, an epoxy compound other than the compound represented by the above formula (a-1), a compound having one or more oxocyclobutyl groups in the molecule, and a compound having one or more vinyl ether groups in the molecule may be mentioned. Wait. These can be used alone or in combination of two or more.

Epoxy other than the compound represented by the above formula (a-1) Examples of the compound include an aromatic epoxidized propyl ether epoxy compound such as a bisphenol A epoxy compound or a bisphenol F epoxy compound; and the aromatic epoxy propyl ether epoxy compound is hydrogenated. The obtained alicyclic epoxypropyl ether epoxy compound; an aliphatic epoxy propyl ether epoxy compound such as a mono- or polyepoxypropyl ether of an aliphatic polyol; a glycidyl ester epoxy a compound; a glycidylamine epoxy compound or the like.

As the above, there is one or more oxygen cyclobutyl groups in the molecule. Examples of the compound include 3,3-bis(vinyloxymethyl)oxycyclobutane, 3-ethyl-3-hydroxymethyloxycyclobutane, and 3-ethyl-3-(2- Ethylhexyloxymethyl)oxycyclobutane, 3-ethyl-3-(hydroxymethyl)oxycyclobutane, 3-ethyl-3-[(phenoxy)methyl]oxocyclobutane , 3-ethyl-3-(hexyloxymethyl)oxycyclobutane, 3-ethyl-3-(chloromethyl)oxycyclobutane, 3,3-bis(chloromethyl)oxetane Alkane, 1,4-bis[(3-ethyl-3-oxocyclobutylmethoxy)methyl]benzene, bis([1-ethyl(3-oxocyclobutyl))methyl)ether, 4, 4'-bis[(3-ethyl-3-oxocyclobutyl) Methoxymethyl]dicyclohexyl, 1,4-bis[(3-ethyl-3-oxocyclobutyl)methoxymethyl]cyclohexane, 1,4-bis([(3-ethyl) 3-oxocyclobutyl)methoxy]methyl)benzene, 3-ethyl-3-([(3-ethyloxycyclobutane-3-yl)methoxy]methyl)oxycyclobutane Alkane, xylene dioxycyclobutane, and the like. In the present invention, for example, commercially available products such as "OXT221", "OXT121" (above, manufactured by Toagosei Co., Ltd.), and trade name "OXBP" (manufactured by Ube Industries, Ltd.) can be used.

As the above, one or more vinyl ether groups are contained in the molecule. Examples of the compound include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, and 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-hydroxymethyl propyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-cyclohexanediol monovinyl ether, 1,4-cyclohexane dimethanol-ethylene Ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, p-xylylene glycol monovinyl ether, m-xylylene glycol monovinyl ether, O-phthalic acid 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, pentapropylene glycol monovinyl ether, propylene glycol monovinyl ether, polypropylene glycol monovinyl ether, and derivatives thereof Things and so on.

Based on the ability to increase the initial hardening speed, it can be further improved From the viewpoint of film hardenability, it is preferred that the photocurable composition for nanoimprint of the present invention contains the above component (A), preferably components (A) and (C). At the same time, the component (D) (especially, a compound having one or more oxocyclobutyl groups having a number average molecular weight of less than 500 in the molecule) is contained as a cationically polymerizable compound.

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

In addition to the above cationically polymerizable compound or photocationic polymerizable compound, the photocurable composition for nanoimprinting of the present invention may contain other components insofar as the effects of the present invention are not impaired. As other components, for example, a hydroxyl group-containing compound (for example, diethylene glycol or the like) and a photosensitizer (for example, 9-oxosulfuric acid) may be mentioned. Compound, etc.), antifoaming agent, leveling agent, coupling agent (for example, decane coupling agent, etc.), surfactant, inorganic filler, flame retardant, ultraviolet absorber, ion adsorbent, phosphor, release agent Conventional additives such as pigment dispersants and dispersing aids.

Content of other ingredients (including two or more cases) The total amount is about 10% by weight or less based on the total amount (100% by weight) of the photocurable composition for nanoimprinting.

As the photocurable composition for nanoimprinting of the present invention, From the viewpoint of improving the surface smoothness of the obtained cured product, it is preferred to contain a leveling agent.

As the leveling agent, for example, acrylic leveling can be mentioned. Agent, lanthanum leveling agent, etc. In the present invention, for example, it can be suitable for use A commercial item such as "BYK-350" or "BYK-UV3510" (manufactured by BYK Chemie Japan Co., Ltd.).

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

The photocurable composition for nanoimprinting of the present invention can be prepared, for example, by stirring at a predetermined ratio, mixing the above components, and defoaming under vacuum if 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 decrease. Moreover, the surface smoothness of the obtained cured product tends to be lowered. In addition, the viscosity of the present invention is measured using a rheometer (trade name "PHYSICA MCR301", manufactured by Anton Paar Co., Ltd.) at a temperature of 25 ° C and a rotation speed of 20 / sec.

[Manufacturing method of fine pattern substrate]

In the method for producing a fine pattern substrate of the present invention, the inorganic material substrate is etched by using a mask obtained by performing imprint processing on the photocurable composition for nanoimprinting.

The fine pattern substrate of the present invention can be produced, for example, by the following steps.

Step 1: A photocurable composition for nanoimprinting is applied to a surface of an inorganic material substrate in a thin layer to form a coating film.

Step 2: The patterned mold is brought into contact with the obtained coating film to transfer the pattern (imprint processing).

Step 3: The photocurable composition for nanoimprinting is cured by light irradiation, and then demolded to obtain a film having a shape of a transfer mold pattern.

Step 4: A film having the shape of the transferred mold pattern is used as a mask, and a fine pattern is obtained by etching the inorganic material substrate.

As the inorganic material substrate used in the step 1, for example, A tantalum substrate, a sapphire substrate, a ceramic substrate, an aluminum substrate, a gallium phosphide substrate, a gallium arsenide substrate, an indium phosphide substrate, a gallium nitride substrate, or the like can be used.

Applying a photocurable composition for nanoimprinting to the photo-curable composition Examples of the method of the surface of the inorganic material substrate include a screen printing method, a shower coating method, a spray method, and the like. At this time, if necessary, a diluent solvent (for example, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether B) can be used. a diol derivative such as an acid ester; a ketone such as acetone, methyl ethyl ketone, methyl butyl ketone or cyclohexanone; an ester of methyl lactate, ethyl lactate, ethyl acetate or butyl acetate; Etc) and adjust the concentration. The thickness of the coating film is, for example, about 0.1 to 10 μm, preferably 0.3 to 3 μm. In the present invention, since the photocurable composition for nanoimprinting described above is used, it has excellent film hardenability.

As the mold used in the step 2, for example, 矽 Oxygen mold, thermoplastic resin mold, curable resin mold, metal mold, and the like. The pressing force when the mold is brought into contact with the coating film is, for example, about 100 to 1000 Pa. The time for bringing the mold into contact with the coating film is, for example, about 1 to 100 seconds. In addition, the shape of the pattern of the mold is not particularly limited as long as it can improve the efficiency of light extraction occurring in the light-emitting layer, and examples thereof include a trapezoidal shape, a conical shape, and a circular shape.

As the light used for light irradiation in step 3 (active energy In the case of light for the polymerization reaction of the photocurable composition for nanoimprinting, infrared rays, visible light, ultraviolet rays, X rays, electron rays, α rays, β rays, γ rays, etc. may be used. Any of them. Among them, ultraviolet rays are preferred from the viewpoint of superior operability. For the irradiation of ultraviolet rays, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a 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 extremely fast and the film hardenability is excellent. In the case of irradiating ultraviolet light to form a film having a film thickness of 1 μm, the amount of ultraviolet light accumulated is preferably adjusted to, for example, about 100 to 3000 mJ/cm ² .

A post-hardening step can be provided between step 3 and step 4. The stability of the shape or the reproducibility of the etching can be improved by providing a post-hardening step. Post-hardening can be carried out by heating and/or light irradiation. In the case of post-hardening by heating, for example, it is preferably heated at 50 to 180 ° C for about 0.5 to 3 hours. Further, in the case where post-hardening is performed by light irradiation, for example, it is preferably irradiated for about 10 to 100 seconds with an irradiation intensity of about 10 to 100 mJ/cm ² .

As the etching method in the step 4, dry etching is exemplified Method, wet etching method, and the like. In the present invention, a dry etching method is preferably used, and a reactive ion etching (RIE: Reactive Ion Etching) is particularly preferable from the viewpoint of making high-precision microfabrication possible.

In the method of manufacturing the fine pattern substrate of the present invention, Irradiated by light for using the photocurable composition for nanoimprinting described above, It is possible to rapidly form a film having an extremely low hardening shrinkage rate on the surface of the inorganic material substrate. Further, since the film obtained by transferring the mold shape which has been accurately obtained in this manner is used as a mask, a fine pattern substrate which has been accurately transferred to the fine pattern of the mold can be obtained.

[semiconductor device]

A semiconductor device (for example, an LED) of the present invention is characterized by comprising the above-described fine pattern substrate.

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

Since the semiconductor device (particularly, LED) of the present invention has a fine pattern substrate formed using the photocurable composition for nanoimprint of the present invention, it has excellent light extraction efficiency and has high luminance, long life, and low Features such as power consumption and low heat dissipation.

Example

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited by the examples.

Preparation Example 1 (modulation of a compound represented by the formula (a-1))

A dehydration catalyst was prepared by stirring and mixing 70 g of sulfuric acid (70 g (0.68 mol)) and 1.8-dioxane [5.4.0] undecene-7 (DBU) 55 g (0.36 mol).

Adding 1000 g (5.05 mol) of hydrogenated biphenyl (=4,4'-dihydroxydicyclohexyl) to a 3-liter flask equipped with a distillation tube equipped with a stirrer, a thermometer, and a dehydration tube The prepared dehydration catalyst was 125 g (0.68 mol of sulfuric acid) and 1500 g of metaxylene, and the flask was heated. From When the temperature exceeded 115 ° C, the formation of water was confirmed. Further, the temperature is raised to increase the temperature until the boiling point of the trimylbenzene (internal temperature 162 to 170 ° C), and the dehydration reaction is carried out under normal pressure. The by-produced water is distilled off and discharged to the outside of the system by the dehydration tube. Further, the dehydration catalyst is slightly dispersed in the reaction liquid as a liquid under the reaction conditions. After 3 hours, the theoretical end amount of water (180 g) was almost distilled off and the reaction was considered to be completed.

After the completion of the reaction, a 10-stage Oldershaw type distillation column was used for the solution in the reactor, and after the meta-trimethylbenzene was distilled off, the internal pressure was 10 Torr (1.33 kPa) and the internal temperature was 137 to 140 ° C. Distillation gave 731 g of dicyclohexyl-3,3'-diene.

243 g of the obtained dicyclohexyl-3,3'-diene and 730 g of ethyl acetate were fed into the reactor, and nitrogen gas was injected into the gas phase portion while controlling the temperature in the reaction system to 37.5 ° C. An acid solution (water content: 0.41% by weight) of 30% by weight of peracetic acid was dropped over 274 g over about 3 hours. After the completion of the dropwise addition of the peracetic acid solution, the reaction was completed by aging at 40 ° C for 1 hour. Further, the unpurified solution at the end of the reaction was washed at 30 ° C, and the low boiling point compound was removed at 70 ° C / 200 mmHg to obtain 270 g of an alicyclic epoxy compound. The resulting alicyclic epoxy compound had an oxygen cyclobutane oxygen concentration of 15.0% by weight. Further, in the measurement of ¹ H-NMR, the peak derived from the internal double bond in the vicinity of δ 4.5 to 5 ppm has disappeared, and it has been confirmed that the proton peak derived from the epoxy group is generated in the vicinity of δ 3.1 ppm. It was confirmed to be 3,4,3',4'-dicyclooxybicyclohexyl.

Examples 1 to 9 and Comparative Examples 1 to 6

The components were 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 photocurable composition for uniform nanoimprinting.

The obtained photocurable composition for nanoimprinting and the cured product obtained by curing the photocurable composition for nanoimprinting were evaluated by the following methods: (1) viscosity, (2) hardenability, (3) shape transferability, and (4) surface uniformity. The results of the assessment are summarized in Table 1 below.

(1) Determination of viscosity

The viscosity (Pa s) of the photocurable composition for nanoimprint obtained in the examples and the comparative examples was rotated at a temperature of 25 ° C using a rheometer (trade name "PHYSICA MCR301", manufactured by Anton Paar Co., Ltd.). The speed was measured at 20 rotations/second.

(2) Assessment of hardenability

60 parts by weight of propylene glycol monomethyl ether acetate (trade name "MMPGAC", manufactured by Daicel Co., Ltd., and later referred to as "MMPGAC") was added to the nanoimprints obtained in the examples and comparative examples. In 103 parts by weight of the photocurable composition, a coating film (film thickness: 1 μm) was formed by applying a spin coating machine to the number of revolutions of the spin coating described in the table, and applying the obtained diluted solution onto a tantalum wafer.

By using a polydimethylcyclohexane mold (the height of the pattern to the aspect ratio (= aspect ratio) 2:1) was pressed at 200 Pa on the obtained coating film and allowed to contact for 60 seconds, by using An ultraviolet ray irradiation device (UV or UV-LED irradiation device) illuminates the ultraviolet ray of the amount of light described in the table, and then demolds the film to obtain a film on which a polydimethyl decane mold pattern is embossed.

The obtained film was immersed in acetone at 25 ° C for 5 seconds, and the subsequent film was visually observed, and the hardenability was evaluated in accordance with the following criteria.

Evaluation basis

○ (good): The shape of the pattern is maintained without being disordered.

△ (slightly good): One of the patterns was partially dissolved in acetone, and the remaining resin remained white on the substrate, and defects were observed in the pattern.

× (bad): The pattern disappears completely.

(3) Evaluation of shape transferability

With respect to the film on which the surface of the oxime mold pattern obtained by the evaluation of the above (2) hardenability was evaluated, the height-to-width ratio (= aspect ratio) of the pattern was measured, and the shape transfer property was evaluated in accordance with the following criteria.

Evaluation basis

○ (good): The aspect ratio is 2:1 to 1.9:1.

△ (slightly good): The aspect ratio is 1.5:1 or more and less than 1.9:1.

× (bad): The case where the aspect ratio is lower than 1.5:1, or there is a case where the pattern has collapsed.

(4) Evaluation of surface uniformity

60 parts by weight of MMPGAC was added to 103 parts by weight of the photocurable composition for nanoimprint obtained in the examples and the comparative examples to obtain a diluted solution, and the number of rotations of the spin coating described in the table was obtained using a spin coater. This diluted solution was applied onto a tantalum wafer to form a coating film (film thickness: 1 μm). Using a UV irradiation device (UV or UV-LED irradiation device), ultraviolet rays of the amount of light described in the table were irradiated to the obtained coating film to obtain a film.

The film thickness was measured using a height difference meter (trade name "T-4000", manufactured by Otaru Research Co., Ltd.), and the thickness (T ₁ ) at the thickest portion and the thickness (T ₂ ) at the thinnest portion of the film were measured. The difference (T _{1 -} T ₂ ) was set to the height difference, and the surface uniformity was evaluated in accordance with the following criteria.

Evaluation basis

○ (good): The case where the height difference (T _{1 -} T ₂ ) is 0.02 μm or less.

△ (slightly good): The case where the height difference (T _{1 -} T ₂ ) is more than 0.02 μm and 0.050 μm or less.

× (bad): The case where the height difference (T _{1 -} T ₂ ) is more than 0.050 μm.

Further, the components used in the examples and comparative examples are as follows.

<Cationic Polymerizable Compound>

Bicyclic diepoxide compound (a-1): 3,4,3',4'-dicyclooxybicyclohexyl (using the compound obtained in the above Preparation Example 1), number average molecular weight: 194

OXT-221: 3-ethyl-3-([(3-ethyloxycyclobutane-3-yl)methoxy]methyl)oxycyclobutane, trade name "OXT-221", East Asia Synthetic Shares Co., Ltd., number average molecular weight: 214

OXBP: an oxocyclobutane compound having a biphenyl skeleton, trade name "OXBP", manufactured by Ube Industries, Ltd., number average molecular weight: 383

N-890: Modified phenolic 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", manufactured by DIC Corporation, number average molecular weight: 550

PB3600: Liquid epoxidized polybutadiene, trade name "EPOLEAD PB3600", manufactured by Daicel Co., Ltd., number average molecular weight: 5900

EHPE3150: Transparent solid epoxy compound, trade name "EHPE3150", manufactured by Daicel Co., Ltd., number average molecular weight: 500 or more

<Photocationic polymerization initiator>

B-1: an initiator containing a fluoroalkyl fluorophosphate anion, and [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonyl tris(5) using propylene carbonate Diluted into 50% by fluoroethyl)trifluorophosphate

B-2: an initiator containing a fluoroalkyl fluorophosphate anion, diphenyl[4-(phenylthioindolyl)phenyl]tris(pentafluoroethyl)trifluorophosphate

654027: A 50% mixture of allyl hexafluoroantimonate and diallyl hexafluoroantimonate diluted to 50% by propylene carbonate, manufactured by Sigma Aldrich Japan

407216: A 50% mixture of allyl sulfonium hexafluorophosphate and diallyl hexafluorophosphate diluted to 50% by propylene carbonate, manufactured by Sigma Aldrich Japan

IRGACURE250: bismuth salt photocationic polymerization initiator, trade name "IRGACURE250", manufactured by BASF

<additive>

BYK-350: Leveling agent, acrylic copolymer, trade name "BYK-350", manufactured by BYK Chemie Japan Co., Ltd.

BYK-UV3510: a leveling agent, a mixture of polyether modified polydimethyl siloxane and polyether, trade name "BYK-UV350", manufactured by BYK Chemie Japan Co., Ltd.

[Possibility of industrial use]

Even if the photocurable composition for nanoimprinting of the present invention is applied to a substrate in a thin atmosphere and irradiated with light, it can be cured while rapidly suppressing the curing shrinkage, and is excellent in hardenability. Film. Therefore, the fine pattern can be transferred quickly and accurately. Further, when the nano-imprinting photocurable composition of the present invention is used for nanoimprinting, a mask which has been accurately transferred to the fine pattern of the mold can be formed, and the inorganic material substrate is etched by using the same. A fine pattern having dimensional reproducibility as excellent as a design pattern can be formed on the surface of the inorganic material substrate.

Claims (5)

A photocurable composition for nanoimprinting comprising the following components (A), (B), (C), and (D), which are contained in a photocurable composition for nanoimprinting The blending amount of the component (C) in the total amount of the cationically polymerizable compound is 10 to 50% by weight, and the content of the component (D) in the total amount of the photocurable composition for nanoimprinting is 5 to 40% by weight. ; component (A): 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, a hydrocarbon group which may contain an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent, and X represents a single bond or a linking group. Component (B): Photocationic polymerization initiator component (C) having a fluoroalkyl fluorophosphate anion: a cationically polymerizable compound having a number average molecular weight of 500 or more (except for the compound contained in the component (A)) Component (D): a cationically polymerizable compound having a number average molecular weight of less than 500 (except for the compound contained in the component (A)). The photocurable composition for nanoimprinting according to claim 1, wherein the component (C) is a cationically polymerizable compound having a polycarbonate skeleton, a polyester skeleton, a polydiene skeleton, a phenol skeleton, or an alicyclic skeleton. A method for manufacturing a fine pattern substrate, which is used for requesting The photocurable composition for nanoimprinting of the item 1 or 2 is subjected to a mask obtained by imprinting to etch the inorganic material substrate. A fine pattern substrate obtained by the method of producing a fine pattern substrate of claim 3. A semiconductor device comprising the fine pattern substrate of claim 4.