JP2003183227A - New organic compounds - Google Patents

Abstract

(57) [Problem] To provide a novel organic compound which can be used for a resist material capable of producing a high-sensitivity and high-resolution pattern. SOLUTION: The compound of the present invention is an organic compound having an acid dissociable functional group, for example, as represented by the following formula. The organic compound of the present invention has an extremely small molecular size (about several hundreds to several thousands) as compared with a polymer compound, and can form a pattern with high sensitivity and high resolution by utilizing chemical amplification. By dissolving the organic compound and the acid generator of the present invention in a solvent and applying the solution on a silicon substrate or the like, a resist material of an amorphous thin film can be formed to form a resist substrate. A pattern with high sensitivity and high resolution can be formed by irradiating the resist substrate with light, an electron beam or radiation to draw and developing the resist substrate using an alkali developing solution. Embedded image

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organic compound usable as a resist material (pattern forming material) used for forming a fine pattern in a semiconductor manufacturing process.

[0002]

2. Description of the Related Art As a conventional resist material (pattern forming material), a polymer material capable of forming an amorphous thin film is generally used. For example, a pattern forming material prepared by dissolving polymethylmethacrylate in a solvent and coating it on a substrate is irradiated with radiation, and the irradiated part is dissolved with a developing solution to form a line pattern of about 0.1 μm. There is.

However, since a polymer has a large molecular weight (about 10,000 to 100,000) and a molecular weight distribution, there is a limit to miniaturization in lithography using a conventional polymer resist material. That is, in the lithography using a polymer-based resist material, as miniaturization progresses, roughness occurs on the pattern surface, which makes it difficult to control the pattern dimension and reduces the yield. In order to form a finer pattern, one method is to reduce the molecular size of the compound for resist material, and the limit is a low molecular weight resist. However, low molecular weight organic compounds generally have high crystallinity and it is difficult to form an amorphous thin film, so that it is difficult to apply them to resist materials.
In addition, although there are many examples of low molecular weight resist materials, their sensitivity is low and practical application is difficult.

[0004]

Therefore, an object of the present invention is to provide a novel organic compound which can be used, for example, as a resist material capable of producing a highly sensitive and high resolution pattern.

[0005]

To solve the above problems, the organic compound of the present invention is an organic compound represented by the following general formula (1).

[Chemical 10] However, in the formula, A ^{1 to} A ¹² are optional substituents, but at least one of them is present, and A ^{1 to} A 12 are
^At least one of ¹² is an acid-labile functional group.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Next, an embodiment of the present invention will be described.

(Compound) First, the organic compound of the present invention will be described.

In the present invention, the above-mentioned "acid-dissociable functional group"
The term means a substituent that is cleaved in the presence of an acid to generate an acidic group such as a phenolic hydroxyl group and a carboxyl group, and examples thereof include an alkoxy group, an alkylsulfanyl group, an acyloxy group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, There is a phenoxycarbonyloxy group and the like.
The acid-dissociable functional group causes a chain cleavage reaction in the presence of an acid in order to enable pattern formation with higher sensitivity and higher resolution (hereinafter, this may be referred to as “chemical amplification”). ) It is preferable to have a property.

The organic compound of the present invention is suitable for use in, for example, a resist material because of the property that the glass state is extremely stable without crystallizing for a long period of time. Then, for example, by a coating method from a solution, preferably a spin coating method, it is possible to easily form a uniform and transparent amorphous glass that is stable at room temperature or higher. The amorphous thin film formed by the organic compound of the present invention can sufficiently function as a resist material (pattern forming material).

Further, the organic compound of the present invention has a high glass transition temperature and excellent heat resistance, so that it can be heat-treated in the pattern forming step.

The organic compound of the present invention has a very small molecular size (several hundreds to several thousands) as compared with a polymer compound, and by utilizing chemical amplification, it is possible to form a pattern with high sensitivity and high resolution. is there.

In the organic compound of the present invention, in the above formula (1), A ^{1 to} A ¹² are hydrogen and the following general formula (2):
It is preferably at least one selected from the group consisting of the substituents represented by (4) to (4).

[Chemical 11] However, in the above formulas (2) to (4), Y is from 1 to 12
R is an integer^Y, R_A ^YAnd R_B ^YAre the same for Y
A^YCorresponding to where A^YIs the above A¹~ A^{1 2}Nozu
Rika, R¹~ R¹²Are hydrogen and unsubstituted
Or a substituted methyl group, an unsubstituted or 1-substituted ethyl group,
Unsubstituted or 1-substituted-n-propyl group, 1-branched
Alkyl group, silyl group, acyl group, alkoxycarbonyl
A group, an unsubstituted or 1-substituted alkoxymethyl group, or
Are cyclic substituents, which may be the same or different, and R
_A ¹~ R_A ¹²Are each an unsubstituted or substituted dimethylene group
Yes, they may be the same or different, R_B ¹~ R_B ¹²Haso
Each is an electron-withdrawing group, which may be the same or different.
And then A¹~ A¹²At least one of which is hydrogen
Is the atomic group outside and R¹~ R¹²Less of
At least one is the above atomic group other than hydrogen.

In the above formulas (2) to (4), in R ^{1 to} R ¹² , the substituted methyl group is methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, methoxyethoxymethyl group, benzyloxy. Methyl group, benzyl thiomethyl group, phenacyl group, 4-bromophenacyl group, 4-methoxyphenacyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, i-propoxycarbonylmethyl group , N-butoxycarbonylmethyl group and at least one type selected from the group consisting of t-butoxycarbonylmethyl group, 1-substituted ethyl group, 1-methoxyethyl group, 1-methylthioethyl group,
1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-
Ethylthioethyl group, 1,1-diethoxyethyl group, 1-
Phenoxyethyl group, 1-phenylthioethyl group, 1,1
-Diphenoxyethyl group, 1-cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group, at least one type selected from the group consisting of 1-phenylethyl group and 1,1-diphenylethyl group, 1-substituted- n−
The propyl group is a 1-methoxy-n-propyl group and 1-
At least one type selected from the group consisting of ethoxy-n-propyl groups, wherein the 1-branched alkyl group is i-propyl group, Sec-butyl group, t-butyl group, 1,1-dimethylpropyl group, At least one type selected from the group consisting of a 1-methylbutyl group and a 1,1-dimethylbutyl group, wherein the silyl group is a trimethylsilyl group, an ethyldimethylsilyl group, a methyldiethylsilyl group, a triethylsilyl group, or t-butyldimethyl. At least one selected from the group consisting of a silyl group, a t-butyldiethylsilyl group, a t-butyldiphenylsilyl group, a tri-t-butylsilyl group and a triphenylsilyl group, wherein the acyl group is an acetyl group or a phenoxyacetyl group. Group, propionyl group, butyryl group, heptanoyl group, hexanoyl group,
Valeryl group, pivaloyl group, isovaleryl group, lauriloyl group, at least one type selected from the group consisting of benzoyl group and naphthoyl group, an alkoxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i -Propoxycarbonyl group, at least one type selected from the group consisting of n-butoxycarbonyl group and t-butoxycarbonyl group, 1-substituted alkoxymethyl group, 1-cyclopentylmethoxymethyl, 1-cyclopentylethoxymethyl, 1 -Cyclohexylmethoxymethyl, 1-cyclohexylethoxyethyl, at least one selected from the group consisting of 1-cyclooctylmethoxymethyl and 1-adamantylmethoxymethyl group, the cyclic substituent is a cyclopentyl group, Chlohexyl group, cyclohexenyl group, adamantyl group, 4-methoxycyclohexyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 4-methoxytetrahydropyranyl group and 4-methoxytetrahydrothio group At least one selected from the group consisting of pyranyl groups, and _RA ¹ ~
R _A ¹² is a dimethylene group, a methoxydimethylene group, a methylthiodimethylene group, a dimethoxydimethylene group, an ethoxydimethylene group, an ethylthiodimethylene group, a diethoxydimethylene group, a phenoxydimethylene group, a phenylthiodimethylene group. More preferably, it is at least one selected from the group consisting of a diphenoxydimethylene group, a cyclopentyloxydimethylene group, a cyclohexyloxydimethylene group, a phenyldimethylene group and a diphenyldimethylene group.

In the above formula (4), R _B ^{1 to} R _B ¹² are
Each is a cyano group, an alkoxysulfonyl group, an acyl group, or an alkoxycarbonyl group, and it is more preferable that they are the same or different, and in R _B ^{1 to} R _B ¹² , the alkoxysulfonyl group is a methoxysulfonyl group, an ethoxysulfonyl group. , N-propoxysulfonyl group, i-propoxysulfonyl group, at least one type selected from the group consisting of n-butoxysulfonyl group and t-butoxysulfonyl group, the acyl group, acetyl group, phenoxyacetyl group, propionyl group , Butyryl group, heptanoyl group, hexanoyl group, valeryl group,
Pivaloyl group, isovaleryl group, lauriloyl group, at least one type selected from the group consisting of benzoyl group and naphthoyl group, the alkoxycarbonyl group,
Methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n
More preferably, it is at least one selected from the group consisting of -butoxycarbonyl group and t-butoxycarbonyl group.

Particularly preferred as the organic compound of the present invention are, for example, at least one of A ^{1 to} A ¹² selected from the group consisting of hydrogen and the substituents represented by the general formula (2), R ^{1 to} R ¹² are hydrogen, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, t-butoxycarbonylmethyl group, 1- At least one selected from the group consisting of methoxyethyl group, 1-ethoxyethyl group, 1-cyclohexyloxyethyl group, t-butyl group, trimethylsilyl group, tetrahydropyranyl group and 1-cyclohexylmethoxymethyl group. It is an organic compound.

The organic compound of the present invention is preferably represented by the following general formula (5).

[Chemical 12]

Of the compounds represented by the above formula (5), particularly preferred are compounds represented by the following formula (6):
It is a compound called 3,5-tris [3,5-di (4-tert-butoxycarbonyloxylphenyl) phenyl] benzene (hereinafter sometimes abbreviated as "BCOPhTPB"). BCOPhTPB has physical properties preferable for use in resist material formation, for example, it has a high glass transition temperature of about 140 ° C. and can sufficiently withstand heat treatment in a pattern forming step.

[Chemical 13]

The method for synthesizing the organic compound of the present invention is not particularly limited and can be synthesized by appropriately combining known reactions. In the case of BCOPhTPB, it can be obtained, for example, as follows. That is, first, 1,3,5-tris
[3,5-Di (4-hydroxyphenyl) phenyl] benzene is synthesized. Next, 1,3,5-tris [3,5-
Di (4-hydroxyphenyl) phenyl] benzene 50
g, pyrocarboxylic acid ditertiary butyl ester 1
10 g, 80 g potassium carbonate, and 100 g 18-
Crown-6 is mixed with tetrahydrofuran as a solvent and stirred at room temperature under a nitrogen atmosphere for 24 hours. And
After distilling off the solvent, the product is separated by silica gel column chromatography and then recrystallized from ethanol to obtain the desired BCOPhTPB.

(Resist Material) Next, a resist material using the organic compound of the present invention, and a resist substrate and a pattern forming substrate using the same will be described.

First, the composition of the present invention is a composition containing at least one kind of the above-mentioned organic compounds of the present invention and an acid generator, and can be suitably used, for example, for forming resist materials. . The acid generator is preferably a compound that directly or indirectly generates an acid by light, an electron beam or radiation.

The acid generator is represented by the following general formula (7)
It is preferable that at least one kind selected from the group consisting of compounds represented by

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 18] However, in the formula, R ^{13 to} R ²¹ are each a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group or a halogen atom, and even if the same. They can be different, X ^- is
A sulfonate ion having an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group, or a halide ion, wherein R ^{22 to} R ²⁷ are
Each is a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group or a halogen atom, which may be the same or different, and V is an alkylene group or arylene. Group or an alkoxylene group, R ²⁸ is an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group, and R ²⁹ and R ³⁰ are each an optionally substituted straight chain, branched or cyclic group. An alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group or an optionally substituted aralkyl group, which may be the same or different, and R ³¹ and R ³² are each optionally substituted A straight chain, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group or an aryl group A substituted aralkyl group,
It may be the same or different.

The acid generator in the composition of the present invention is
The compound represented by the formula (7) is triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate,
Triphenylsulfonium perfluoro-n-octane sulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, di-2,4
6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium nonafluoro-n-butanesulfonate, diphenyl-4-hydroxyphenylsulfonium trifluoromethanesulfonate, Bis (4-fluorophenyl) -4-hydroxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, bis (4-
Hydroxyphenyl) -phenylsulfonium trifluoromethanesulfonate, tri (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tri (4-fluorophenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium benzenesulfonate, diphenyl- 2,4,6-Trimethylphenyl-p-toluenesulfonate, diphenyl-
2,4,6-Trimethylphenylsulfonium-2-trifluoromethylbenzenesulfonate, diphenyl-
2,4,6-Trimethylphenylsulfonium-4-trifluoromethylbenzenesulfonate, diphenyl-
2,4,6-trimethylphenylsulfonium-2,4
-Difluorobenzene sulfonate, diphenyl-2,
4,6-Trimethylphenylsulfonium hexafluorobenzenesulfonate, diphenylnaphthylsulfonium trifluoromethanesulfonate, diphenyl-4
-Hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate and diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate, which is represented by the formula (8). Is a bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate,
Bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate , Bis (4-t-butylphenyl) iodonium benzene sulfonate, bis (4-
t-butylphenyl) iodonium-2-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-4-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-2,4-difluoro Benzene sulfonate,
Bis (4-t-butylphenyl) iodonium hexafluorobenzene sulfonate, bis (4-t-butylphenyl) iodonium 10-camphor sulfonate,
Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-
n-octane sulfonate, diphenyliodonium p-
Toluenesulfonate, diphenyliodonium benzenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium-2-trifluoromethylbenzenesulfonate, diphenyliodonium-4-trifluoromethylbenzenesulfonate, diphenyliodonium-2,4-difluorobenzenesulfonate, diphenyliodonium Hexafluorobenzenesulfonate, di (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, di (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, di (4-
Trifluoromethylphenyl) iodonium perfluoro-n-octane sulfonate, di (4-trifluoromethylphenyl) iodonium p-toluene sulfonate, di (4-trifluoromethylphenyl) iodonium benzene sulfonate and di (4-trifluoromethylphenyl) ) It is at least one kind selected from the group consisting of iodonium 10-camphorsulfonate, and the compound represented by the formula (9) is N- (trifluoromethylsulfonyloxy) succinimide, N-
(Trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) succinimide, N- (1
0-camphorsulfonyloxy) phthalimide, N-
(10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) ) Naphthylimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (n-octanesulfonyloxy) naphthylimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.
2.1] Hept-5-ene-2,3-dicarpoxyimide, N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] ] Hept-5
-Ene-2,3-dicarboximide, N- (perfluorobenzenesulfonyloxy) naphthylimide, N-
(1-Naphthalenesulfonyloxy) bicigulo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) naphthylimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept -5-en-2,
3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3- The compound represented by the formula (10) is at least one selected from the group consisting of dicarboximide and N- (perfluoro-n-octanesulfonyloxy) naphthylimide, and the compound represented by the formula (10) is diphenyldisulphone or di (4 -Methylphenyl) disulfone, dinaphthyldisulfone, di (4-t-butylphenyl) disulfone, di (4-hydroxyphenyl) disulfone, di (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl)
The compound represented by the formula (11) is at least one kind selected from the group consisting of disulfone, di (2-fluorophenyl) disulfone and di (4-tolufluoromethylphenyl) disulfone, and α- (methyl Sulfonyloxyimino) -phenylacetonitrile,
α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -phenylacetonitrile, α
-(Trifluoromethylsulfonyloxyimino) -4
-Methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -4
More preferably, it is at least one selected from the group consisting of -methylphenylacetonitrile and α- (methylsulfonyloxyimino) -4-bromophenylacetonitrile.

Particularly preferred as the composition of the present invention is, for example, the compound BCOPhTPB represented by the above formula (6).
And a diphenyliodonium trifluoromethanesulfonate.

The resist substrate of the present invention is a resist substrate in which a resist material comprising the composition of the present invention is formed on the substrate, and the patterned substrate of the present invention is the resist substrate of the present invention. It is a patterned substrate on which a pattern is formed. In the present specification, the "resist substrate" means a substrate before pattern formation, and the "pattern forming substrate" means a substrate after pattern formation. Also,
The “pattern forming material” means a composition which is formed on a resist substrate and can form a pattern by irradiation with light, an electron beam or radiation, and has the same meaning as “resist material”.

The method for producing the patterned substrate of the present invention is not particularly limited, but for example, it can be produced by a production method including the following steps (a) to (c). (A) First, a substrate is prepared, and then at least one kind of the organic compound of the present invention, at least one kind of the acid generator and a solvent for dissolving them are mixed,
A resist material forming step including applying the mixture onto the substrate. (B) A step of irradiating the resist material with light, an electron beam or radiation to perform drawing. (C) After the drawing, a step of developing the resist material with an alkaline developer to form a pattern.

The drawing and pattern forming mechanism in the steps (b) and (c) is explained as follows, for example.

That is, when the resist material formed in the step (a) is irradiated with light, an electron beam or radiation, an acid is generated from the acid generator, and the acid is generated, for example, in the scheme 1 below.
As shown in (3), the acid-dissociable functional group is cleaved to form a phenolic hydroxyl group. In addition, the following scheme 1
In, Ar is an acid-labile functional group (in the scheme,
It is an aryl group to which a tertiary butoxycarbonyloxy group) is bound.

[Chemical 19]

The irradiated region becomes soluble in the alkaline aqueous solution due to the formation of the phenolic hydroxyl group,
Development is performed by using an alkaline aqueous solution to form a positive pattern. In order to accelerate the reaction as shown in the scheme 1, heat treatment may be performed after the drawing (exposure) and before the development.

The organic compound of the present invention has the above-mentioned drawing (exposure) due to the presence of the acid dissociative functional group even if the phenolic hydroxyl group is present before the irradiation with light, electron beam or radiation. And development can be performed. This is because the acid-dissociable functional group is cleaved after irradiation to newly generate a phenolic hydroxyl group, and the solubility in an alkaline aqueous solution is increased as compared with that before irradiation. In this case, it is preferable that the difference in solubility in the alkaline aqueous solution before and after irradiation is as large as possible. It should be noted that the presence of the phenolic hydroxyl group before irradiation may be preferable because of good adhesion to a material having high polarity such as a silicon substrate. The above
BCOPhTPB and the like do not have a phenolic hydroxyl group, but have good adhesion to a silicon substrate.

The solvent used in the step (a) is not particularly limited as long as it can dissolve the organic compound of the present invention and the acid generator, and examples thereof include ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate. Ethylene glycol monoalkyl ether acetates, ethylene glycol monomethyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, and propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate And propylene glycol monomethyl ether such as propylene glycol monomethyl ether and propylene glycol monoethyl ether Ruki ethers and methyl lactate, and lactic acid esters such as ethyl lactate, methyl acetate, ethyl acetate, propyl acetate, and aliphatic carboxylic acid esters such as butyl acetate, methyl 3-methoxypropionate,
Other esters such as ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate, aromatic hydrocarbons such as toluene and xylene, 2-heptanone, 3-heptanone, 4- Ketones such as heptanone and cyclohexanone, and cyclic ethers such as tetrahydrofuran and dioxane are preferable. These solvents may be used alone or in combination of two or more. Further, as the alkaline developer,
For example, at least one of alkaline compounds such as mono-, di- or tri-alkylamines, mono-, di- or tri-alkanolamines, heterocyclic amines, tetramethylammonium hydroxide and choline.
The seed is preferably 1 to 10% by weight, more preferably 1
An alkaline aqueous solution dissolved to have a concentration of ˜5% by weight can be preferably used. Further, an appropriate amount of alcohol such as methanol, ethanol, isopropyl alcohol, or a surfactant can be added to the alkaline developer.

In the organic compound of the present invention, A ¹
~ A ¹² is at least one selected from the group consisting of hydrogen and a substituent represented by the general formula (4), in the composition and the resist material, a base generator is used instead of the acid generator. Agents can be used. The base generator is preferably a compound which directly or indirectly generates a base by light, electron beam or radiation. At this time, in the steps (a) to (c), the pattern forming substrate can be manufactured by using the base generator instead of the acid generator. The substituent represented by the general formula (4) is cleaved by a base by a mechanism such as the following scheme 2 to generate a phenolic hydroxyl group. In addition, the following scheme 2
In, Ar is the substituent (in the scheme, 2-
A cyanoethoxycarbonyloxy group) is bonded to the aryl group.

[Chemical 20]

According to the organic compound of the present invention, a pattern forming material having an extremely high sensitivity of, for example, about ² μC / cm ² can be formed on a resist substrate. And
An extremely fine line pattern of 25 nm can be formed by using the pattern forming material without generating surface roughness to manufacture a pattern forming substrate. Therefore, according to the patterned substrate of the present invention, it is possible to manufacture a semiconductor element having a high degree of integration.

[0033]

EXAMPLES Next, examples of the present invention will be described.

(Measurement method) The nuclear magnetic resonance (NMR) spectrum has a trade name of Inova-750 (Varian, 750 M at the time of ¹ H measurement).
Hz) or product name Inova-600 (Varian, ¹ H measurement 6
00 MHz). Chemical shifts are expressed in parts per million (ppm). Internal standard 0ppm,
Tetramethylsilane (TMS) was used. Coupling constants (J) are given in Hertz and are abbreviations s, d, t, q,
m and br are singlet and doublet, respectively
(doublet), triplet, quartet, multiplet and broad line. Mass spectrometry (MS) uses the product name JEOL JMS-DX303 (JEOL)
Method or FAB method. Elemental analysis is trade name CHN c
It was performed using order MT-5 (Yanagimoto Seisakusho). Silica gel (trade name: Wakogel C-300, Wako Pure Chemical Industries, Ltd.) was used for column chromatography separation. All chemicals are reagent grade, Tokyo Kasei Kogyo Co., Ltd.,
It was purchased from Wako Pure Chemical Industries, Ltd., Nakarai Tesque, Inc., Kanto Chemical Co., Inc. and Aldrich.

(Synthesis of BCOPhTPB) Steps 1 to 5 below
BCOPhTPB was synthesized according to.

1. Synthesis of 3,5-dibromoacetophenone 3,5-dibromoacetophenone was obtained as follows.
That is, first, 1,3,5-tribromobenzene (10 g, 31.
7 mmol) in diethyl ether (250 ml),
Cooled to 8 ° C. Next, n-hexane solution of n-butyllithium (1.6 mol dm ^-3 , 19.8 ml, 31.7 mmo was added to this solution.
l) was added, and the mixture was stirred at -78 ° C for 1 hr, and N, N-dimethylacetamide (3.03 g, 34.8 mmol) was added. Then, the temperature was gradually returned to room temperature, and the mixture was stirred at room temperature for 12 hours.
Furthermore, 10% hydrochloric acid aqueous solution was added to stop the reaction, and the mixture was extracted with an organic solvent. After removing the solvent, the product was separated by silica gel column chromatography (developing solvent: hexane), followed by recrystallization from methanol and purification to obtain the desired product (yield: 3.1 g, yield: 35%). Melting point: 62 ° C. ¹ H NMR
(750 MHz, CDCl ₃ , 25 ° C): δ (ppm) = 7.979 (1H,
s), 7,976 (1H, s), 7.835 (1H, s), 2.564 (3H, s).

2. Synthesis of 1,3,5-tris (3,5-dibromophenyl) benzene 1,3,5-tris (3,5-dibromophenyl) benzene
I got benzene. That is, first, 3,5-dibromoacetophenone (10 g, 36 mmol) and trifluoromethanesulfonic acid (1.4 ml) were dissolved in toluene and stirred at reflux temperature for 24 hours. After removing the solvent, the product was separated by silica gel column chromatography (developing solvent: toluene / hexane) and subsequently purified by recrystallization from a tetrahydrofuran / hexane mixed solvent to obtain the desired product (yield: 2.4 g, Yield: 25%). Mass spectrometry (EI): m / e = 780
(M ⁺ ).

3. Synthesis of 1,3,5-tris [3,5-bis (4-methoxyphenyl) phenyl] benzene 1,3,5-tris [3,5-bis (4-methoxyphenyl) phenyl] as follows I got benzene. That is, first,
3,5-Tris (3,5-dibromophenyl) benzene (1.4 g,
1.8 mmol) and 4-methoxyboronic acid (2.5 g, 16.1 mmo
l) in tetrahydrofuran containing tetrakis (triphenylphosphine) palladium (0) (0.35 g, 0.3 mmol)
And potassium carbonate aqueous solution were added, and the mixture was refluxed at 12
Stir for hours. Then, the organic layer was washed with water and dried. The solvent was removed, and the product was separated by silica gel column chromatography (developing solvent: toluene / ethyl acetate) and then purified by recrystallization from a toluene / ethyl acetate mixed solvent to obtain the desired product (yield: 1.1 g, yield Rate: 65%). Mass spectrum (EI): m / e = 942 (M ⁺ ).

4. Synthesis of 1,3,5-tris [3,5-bis (4-hydroxyphenyl) phenyl] benzene 1,3,5-tris [3,5-bis (4-hydroxyphenyl) phenyl] as follows I got benzene. That is, first,
1,3,5-Tris [3,5-bis (4-methoxyphenyl) phenyl]
Benzene (1.4 g, 1.4 mmol) and hydrobromic acid (500 m
The acetic acid solution containing l) was stirred at reflux temperature for 12 hours. Then, after removing the solvent and washing the product with water,
The product was obtained by drying under reduced pressure (yield: 0.9 g, yield: 7
Five %). Mass spectrometry (EI): m / e = 859 (M ⁺ ).

5. Synthesis of BCOPhTPB BCOPhTPB was obtained as follows. That is, first,
3,5-Tris [3,5-bis (4-hydroxyphenyl) phenyl]
Benzene (0.5 g, 0.6 mmol), pyrocarboxylic acid di-tert-butyl ester (1.1 g, 0.5 mmol), potassium carbonate (0.8 g, 5.7 mmol), and 18-crown-6 ether (1.0 g, 3.8 mmol) Was dissolved in tetrahydrofuran and stirred at 40 ° C. for 10 hours. Then, the reaction product was extracted and separated by silica gel column chromatography (developing solvent: ethyl acetate), followed by purification by recrystallization from a tetrahydrofuran / methanol mixed solvent to obtain the target product (yield: 0.4 g, yield Rate: 54%). Mass spectrometry (F
AB): m / e = 1460 (MH ⁺ ). ¹ H NMR (600 MHz, CDCl ₃ , 25
℃) δ (ppm) = 7.95 (3H, s), 7.85 (6H, s), 7.76 (3
H, s), 7.70 (12H, d), 7.28 (12H, d), 1.58 (54H,
s). ¹³ C NMR (150 MHz, CDCl ₃ , 25 ° C) δ (ppm) = 15
0.8,150.7, 142.6, 142.2, 141.8, 138.6, 128.4, 128.
3, 125.9, 125., 125.4, 121.7, 83.7, 27.7. Elemental analysis: Calculated value (C ₉₀ H ₉₀ O ₁₈ ): C, 74.06; H, 6.21; O, 19.7
3. Found: C, 73.96; H, 6.33.

(Resist material) Next, the synthesized BCOPhTPB
Was used to form a resist material, and a resist substrate and a patterned substrate were produced using this to evaluate the performance. That is, first, 5 g of BCOPhTPB and 0.1 g of diphenyliodonium trifluoromethanesulfonate (acid generator) were dissolved in 100 g of tetrahydrofuran. Then, this solution was spin-coated on a silicon substrate to form a resist material consisting of an amorphous thin film having a film thickness of 0.2 μm on the silicon substrate to prepare a resist substrate.

Then, the resist material formed on the silicon substrate was irradiated with an electron beam of 50 keV to draw a line pattern.

After that, heat treatment is performed at about 100 ° C. for about 90 seconds, and then development is performed for about 30 seconds with a mixed solvent of tetramethylammonium hydroxide aqueous solution and isopropyl alcohol to remove the area exposed to the electron beam. A patterned substrate was prepared by rinsing with deionized water for about 20 seconds.

FIG. 1 shows the sensitivity curve of the resist material of this example. As shown in the figure, the sensitivity was about ² μC / cm ² , which had a high practical level of sensitivity.

FIG. 2 shows a photomicrograph of the line pattern on the pattern-formed substrate of this example. As shown,
This line pattern had a high resolution with a line width of 25 nm and had a good pattern shape with extremely little roughness.

[0046]

As described above, by using the novel organic compound of the present invention, it is possible to form a resist material capable of producing a highly sensitive and high resolution pattern. By using the chemically amplified low-molecular-weight resist material according to the present invention, it is possible to fabricate a high resolution pattern with extremely low roughness with high sensitivity, and thus it is possible to fabricate a highly integrated semiconductor device. Becomes

[Brief description of drawings]

FIG. 1 is a graph showing a sensitivity curve in an example of the resist material of the present invention.

FIG. 2 is a photomicrograph of a line pattern in an example of the patterned substrate of the present invention.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toshiaki Kadota             3-5-19 Senriyama Higashi, Suita City, Osaka Prefecture             Excel Room 410 F-term (reference) 2H025 AA01 AA02 AB16 AC06 AD03                       BE10 CC20 FA03 FA12 FA17                 4H006 AA01 AA03 AB80 BJ50

Claims (28)

[Claims] 1. An organic compound represented by the following general formula (1). [Chemical 1] However, in the formula, A ^{1 to} A ¹² are optional substituents, but at least one of them is present, and A ^{1 to} A 12 are
^At least one of ¹² is an acid-labile functional group. 2. In the formula (1), A¹~ A¹²But hydrogen
And a substituent represented by the following general formulas (2) to (4)
In at least one type selected from the group
The organic compound described. [Chemical 2] However, in the above formulas (2) to (4), Y is from 1 to 12
R is an integer^Y, R_A ^YAnd R_B ^YAre the same for Y
A^YCorresponding to where A^YIs the above A¹~ A^{1 2}Nozu
Is that R¹~ R¹²Are hydrogen, unsubstituted or substituted methyl, respectively.
Group, unsubstituted or 1-substituted ethyl group, unsubstituted
Is a 1-substituted-n-propyl group, a 1-branched alkyl group,
Ryl group, acyl group, alkoxycarbonyl group, also unsubstituted
Or 1-substituted alkoxymethyl group, or cyclic substituent
And may be the same or different, R_A ¹~ R_A ¹²Is an unsubstituted or substituted dimethylene group
And may be the same or different, R_B ¹~ R_B ¹²Are electron withdrawing groups, the same or different
It may be, And A¹~ A¹²At least one of the
Is the atomic group, and R¹~ R¹²At least
The other is the above atomic group other than hydrogen. 3. In the formulas (2) to (4), in R ^{1 to} R ¹² , the substituted methyl group is a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group, a methoxyethoxymethyl group, Benzyloxymethyl group, benzyl thiomethyl group, phenacyl group, 4-bromophenacyl group, 4-methoxyphenacyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group,
n-propoxycarbonylmethyl group, i-propoxycarbonylmethyl group, at least one type selected from the group consisting of n-butoxycarbonylmethyl group and t-butoxycarbonylmethyl group, 1-substituted ethyl group is 1-methoxy Ethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group Group, 1,1-diphenoxyethyl group, 1-cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group, 1-phenylethyl group and at least one selected from the group consisting of 1,1-diphenylethyl group. , 1-substituted-n-propyl group is a group consisting of 1-methoxy-n-propyl group and 1-ethoxy-n-propyl group? At least one kind selected, wherein the 1-branched alkyl group is i-propyl group, Sec-butyl group, t-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group and 1,1-dimethyl group At least one selected from the group consisting of a butyl group, the silyl group is a trimethylsilyl group, an ethyldimethylsilyl group, a methyldiethylsilyl group, a triethylsilyl group,
At least one selected from the group consisting of t-butyldimethylsilyl group, t-butyldiethylsilyl group, t-butyldiphenylsilyl group, tri-t-butylsilyl group and triphenylsilyl group, wherein the acyl group is acetyl. Group, phenoxyacetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauriloyl group, benzoyl group and at least one selected from the group consisting of naphthoyl group, Alkoxycarbonyl group is methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-
At least one selected from the group consisting of propoxycarbonyl group, n-butoxycarbonyl group and t-butoxycarbonyl group, 1-substituted alkoxymethyl group, 1-cyclopentylmethoxymethyl, 1-cyclopentylethoxymethyl, 1- Cyclohexylmethoxymethyl, 1-cyclohexylethoxyethyl, 1-cyclooctylmethoxymethyl and 1
-At least one type selected from the group consisting of adamantyl methoxymethyl group, the cyclic substituent is a cyclopentyl group, cyclohexyl group,
Cyclohexenyl group, adamantyl group, 4-methoxycyclohexyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 4-methoxytetrahydropyranyl group and 4-methoxytetrahydrothiopyranyl group at least one selected from the group consisting of, and, R _a ¹ ~R _a ¹² is, dimethylene group, a methoxy dimethylene group, methylthio dimethylene group, dimethoxy methylene group, an ethoxy dimethylene group, Echiruchioji Methylene group,
Diethoxydimethylene group, phenoxydimethylene group, phenylthiodimethylene group, diphenoxydimethylene group,
The organic compound according to claim 2, which is at least one selected from the group consisting of a cyclopentyloxydimethylene group, a cyclohexyloxydimethylene group, a phenyldimethylene group, and a diphenyldimethylene group. 4. In the formula (4), R _B ^{1 to} R _B ¹² are each a cyano group, an alkoxysulfonyl group, an acyl group, or an alkoxycarbonyl group, and are the same or different. The organic compound according to. 5. In R _B ^{1 to} R _B ¹² , an alkoxysulfonyl group is a methoxysulfonyl group, an ethoxysulfonyl group, an n-propoxysulfonyl group, an i-
At least one type selected from the group consisting of propoxysulfonyl group, n-butoxysulfonyl group and t-butoxysulfonyl group, wherein the acyl group is an acetyl group, a phenoxyacetyl group, a propionyl group, a butyryl group, a heptanoyl group, At least one selected from the group consisting of a xanoyl group, a valeryl group, a pivaloyl group, an isovaleryl group, a lauriloyl group, a benzoyl group and a naphthoyl group, wherein the alkoxycarbonyl group is a methoxycarbonyl group, an ethoxycarbonyl group, or n-propoxycarbonyl Group, i-
The organic compound according to claim 4, which is at least one selected from the group consisting of a propoxycarbonyl group, an n-butoxycarbonyl group, and a t-butoxycarbonyl group. 6. A ^{1 to} A ¹² is at least one selected from the group consisting of hydrogen and a substituent represented by the general formula (2), and R ^{1 to} R ¹² are hydrogen and methoxycarbonyl. Group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, t-butoxycarbonylmethyl group, 1
At least one selected from the group consisting of -methoxyethyl group, 1-ethoxyethyl group, 1-cyclohexyloxyethyl group, t-butyl group, trimethylsilyl group, tetrahydropyranyl group and 1-cyclohexylmethoxymethyl group. The organic compound according to claim 2, wherein 7. The method according to claim 2, wherein A ^{1 to} A ¹² are at least one selected from the group consisting of hydrogen and a substituent represented by the general formula (4). Organic compounds. 8. The organic compound according to claim 1, which is represented by the following general formula (5). [Chemical 3] 9. The organic compound according to claim 8, which is represented by the following formula (6). [Chemical 4] 10. A composition comprising at least one kind of the compound according to claim 1 and an acid generator. 11. The composition according to claim 10, wherein the acid generator is a compound that directly or indirectly generates an acid by light, an electron beam or radiation. 12. The acid generator is represented by the following general formula (7):
The composition according to claim 10 or 11, which is at least one selected from the group consisting of the compounds represented by (11). [Chemical 5] [Chemical 6] [Chemical 7] [Chemical 8] [Chemical 9] However, in the formula, R ^{13 to} R ²¹ are each a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group or a halogen atom,
They may be the same or different, X ⁻ is a sulfonate ion having an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group, or a halide ion, and R ^{22 to} R ²⁷ are each a hydrogen atom. A linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group or a halogen atom,
V may be the same or different, V is an alkylene group, an arylene group or an alkoxylene group, R ²⁸ is an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group, and R ²⁹ and R ³⁰ are Each is an optionally substituted straight chain,
A branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group or an optionally substituted aralkyl group, which may be the same or different, and R ³¹ and R ³² are each , An optionally substituted straight chain,
A branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group or an optionally substituted aralkyl group, which may be the same or different. 13. The compound represented by the formula (7) is triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, diphenyl-4-. Methylphenylsulfonium trifluoromethanesulfonate, di-2,4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t
-Butoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium nonafluoro-n-butanesulfonate, diphenyl-4-hydroxyphenylsulfonium trifluoromethanesulfonate, bis (4-fluorophenyl) -4-hydroxyphenylsulfonium trifluoro Rmethanesulfonate, diphenyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, bis (4-hydroxyphenyl) -phenylsulfonium trifluoromethanesulfonate, tri (4-
Methoxyphenyl) sulfonium trifluoromethanesulfonate, tri (4-fluorophenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium benzenesulfonate, diphenyl-2,4
6-trimethylphenyl-p-toluenesulfonate,
Diphenyl-2,4,6-trimethylphenylsulfonium-2-trifluoromethylbenzenesulfonate,
Diphenyl-2,4,6-trimethylphenylsulfonium-4-trifluoromethylbenzenesulfonate,
Diphenyl-2,4,6-trimethylphenylsulfonium-2,4-difluorobenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium hexafluorobenzenesulfonate, diphenylnaphthylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium -P-
Toluenesulfonate, triphenylsulfonium 10
-Camphor sulfonate and diphenyl-4-hydroxyphenyl sulfonium 10-camphor sulfonate, which is at least one kind, and the compound represented by the formula (8) is bis (4-t-
Butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t
-Butylphenyl) iodonium perfluoro-n-octane sulfonate, bis (4-t-butylphenyl)
Iodonium p-toluenesulfonate, bis (4-t-
Butylphenyl) iodonium benzene sulfonate,
Bis (4-t-butylphenyl) iodonium-2-trifluoromethylbenzenesulfonate, bis (4-t
-Butylphenyl) iodonium-4-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-2,4-difluorobenzenesulfonate, bis (4-t-butylphenyl) iodonium hexafluorobenzenesulfonate, bis ( 4-t
-Butylphenyl) iodonium 10-camphorsulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-
n-butane sulfonate, diphenyl iodonium perfluoro-n-octane sulfonate, diphenyl iodonium p-toluene sulfonate, diphenyl iodonium benzene sulfonate, diphenyl iodonium 10-camphor sulfonate, diphenyl iodonium-2-trifluoromethylbenzene sulfonate, diphenyl iodonium-4- Trifluoromethylbenzenesulfonate, diphenyliodonium-2,4-difluorobenzenesulfonate, diphenyliodonium hexafluorobenzenesulfonate, di (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, di (4-trifluoromethylphenyl) iodonium nona Fluoro-n-butane sulfonate, di (4-trifluoro) Romethylphenyl) iodonium perfluoro-n-octane sulfonate, di (4-
Trifluoromethylphenyl) iodonium p-toluenesulfonate, di (4-trifluoromethylphenyl) iodoniumbenzenesulfonate and di (4-
Trifluoromethylphenyl) iodonium 10-camphor sulfonate is at least one type selected from the group consisting of, and the compound represented by the formula (9) is N
-(Trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] Hept-5
-Ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N-
To (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1]. Put-5-ene-
2,3-dicarboximide, N- (10-camphorsulfonyloxy) naphthylimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide, N- (n-octanesulfonyloxy) naphthylimide, N- (p-
Toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-
(P-Toluenesulfonyloxy) naphthylimide, N
-(2-Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4
-Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarpoxyimide, N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (per) Fluorobenzenesulfonyloxy) bicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximide, N-
(Perfluorobenzenesulfonyloxy) naphthylimide, N- (1-naphthalenesulfonyloxy) biciglo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy)
Naphthylimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N-
From the group consisting of (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and N- (perfluoro-n-octanesulfonyloxy) naphthylimide. The compound represented by the formula (10) is at least one selected from diphenyldisulphone, di (4-methylphenyl) disulphone, dinaphthyldisulphone,
Di (4-t-butylphenyl) disulfone, di (4-
At least selected from the group consisting of hydroxyphenyl) disulfone, di (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2-fluorophenyl) disulfone and di (4-tolufluoromethylphenyl) disulfone. One kind of the compound represented by the formula (11) is α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (trifluoromethyl). Sulfonyloxyimino) -phenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (pro- Le sulfonyloxy) -4-methylphenyl acetonitrile and α-
The composition according to claim 12, which is at least one selected from the group consisting of (methylsulfonyloxyimino) -4-bromophenylacetonitrile. 14. A composition comprising the compound according to claim 9 and diphenyliodonium trifluoromethanesulfonate. 15. A composition comprising at least one of the compounds according to claim 7 and a base generator. 16. The composition according to claim 15, wherein the base generator is a compound which directly or indirectly generates a base by light, an electron beam or radiation. 17. A resist substrate in which a resist material comprising the composition according to any one of claims 10 to 16 is formed on the substrate. 18. A pattern-formed substrate obtained by patterning the resist substrate according to claim 17. 19. A method of manufacturing a patterned substrate, which includes the following steps (a) to (c). (A) First, a substrate is prepared, and then at least one of the compounds according to any one of claims 1 to 9 and at least one of the acid generator according to any one of claims 10 to 14 are prepared. A step of forming a resist material, which comprises mixing types and a solvent for dissolving them and applying the mixture onto the substrate. (B) A step of irradiating the resist material with light, an electron beam or radiation to perform drawing. (C) After the drawing, a step of developing the resist material with an alkaline developer to form a pattern. 20. The method for manufacturing a pattern-formed substrate according to claim 19, wherein heat treatment is performed after drawing and before development. 21. At least one type of the compound according to claim 7 is used in place of at least one type of the compound according to any one of claims 1 to 9; 21. At least one kind of the base generator according to claim 15 or 16 is used in place of at least one kind of the acid generator of claim 19 or 20.
A method for manufacturing a pattern-formed substrate according to. 22. A solvent for dissolving the compound and the acid generator is ethylene glycol monoalkyl ether acetates, ethylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, lactic acid ester. , Aliphatic carboxylic acid esters,
21. The method for producing a patterned substrate according to claim 19, wherein the patterned substrate is at least one selected from the group consisting of: and other esters, aromatic hydrocarbons, ketones, and cyclic ethers. 23. The ethylene glycol monoalkyl ether acetates are at least one selected from the group consisting of ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, and the ethylene glycol monoalkyl ethers are ethylene glycol monomethyl ether. At least one selected from the group consisting of ether and ethylene glycol monoethyl ether, propylene glycol monoalkyl ether acetates are at least one selected from the group consisting of propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Propylene glycol monoalkyl ethers, propylene glycol monomethyl ether At least one selected from the group consisting of ether and propylene glycol monoethyl ether, the lactate ester is at least one of methyl lactate and ethyl lactate, and the aliphatic carboxylic acid ester is methyl acetate, ethyl acetate At least one kind selected from the group consisting of propyl acetate and butyl acetate, and the other ester is methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and 3-ethoxypropionate. At least one selected from the group consisting of ethyl acid, aromatic hydrocarbons are at least one of toluene and xylene, ketones from 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone Group The method for producing a patterned substrate according to claim 22, wherein the cyclic ether is at least one selected from the group consisting of tetrahydrofuran and dioxane. 24. The alkaline developing solution is an aqueous solution of an alkaline compound or an aqueous solution obtained by adding at least one of alcohols and a surfactant to the aqueous solution. A method for manufacturing a pattern-formed substrate according to. 25. A compound in which the alkaline compound consists of mono-, di- or tri-alkylamines, mono-, di- or tri-alkanolamines, heterocyclic amines, tetramethylammonium hydroxide and choline. The method for manufacturing a patterned substrate according to claim 24, wherein the method is at least one selected from the group. 26. The alcohol according to claim 24, wherein the alcohol is at least one selected from the group consisting of methanol, ethanol and isopropyl alcohol.
5. The method for manufacturing a patterned substrate according to item 5. 27. The method for producing a patterned substrate according to claim 24, wherein the concentration of the aqueous alkaline compound solution is 1 to 10% by weight. 28. The method for producing a patterned substrate according to claim 24, wherein the concentration of the alkaline compound aqueous solution is 1 to 5% by weight.