JP2000147773A - Radiation-sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a radiation-sensitive resin compsn. useful as a fine resist pattern with high accuracy by incorporating a resin having individually specified two kinds of repeating units as the essential units, a radiation-sensitive acid producing agent and at lest one kind of basic compd. selected from a group of specified compds. SOLUTION: This radiation-sensitive compsn. contains a resin having a repeating unit expressed by formula I and a repeating unit expressed by formula II as the essential units, a radiation-sensitive acid producing agent and at least one kind of basic compd. selected from a group of compds. expressed by formula III. In formula I, R1 is a hydrogen atom or methyl group, each of R2 and R3 is independently hydrogen atom or 1-6C straight-chain, branched or cyclic alkyl group. In formula II, R4 is a hydrogen atom or methyl group. In formula III, X1 is a polymethylene chain having 2 to 8 carbon atoms in the main chain, each of R5 to R8 is independently 1-12C straight-chain, branched or cyclic alkyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive resin composition, and more particularly, it is useful as a chemically amplified resist suitable for ultrafine processing using radiation such as far ultraviolet rays, X-rays and charged particle beams. The present invention relates to a novel radiation-sensitive resin composition.

[0002]

2. Description of the Related Art In the field of microfabrication represented by the manufacture of integrated circuit elements, design rules in lithography have been rapidly miniaturized in order to obtain a higher degree of integration of integrated circuits. The development of a lithography process capable of stably performing high-precision fine processing with a line width of 0.5 μm or less has been strongly promoted. For this reason, resists used for microfabrication are required to be able to accurately form a resist pattern having a line width of 0.5 μm or less. However, conventional visible light (wavelength 800 to 400 nm) and near ultraviolet (wavelength) 400 ~
In the method using (300 nm), it is extremely difficult to form such a fine pattern with high accuracy. Therefore, a lithography process using radiation of a short wavelength (wavelength of 300 nm or less) that can achieve a wider depth of focus and is effective for miniaturization of design rules has been proposed. A lithography process using such short-wavelength radiation includes, for example, a bright line spectrum of a mercury lamp (wavelength 2).
54 nm), KrF excimer laser (wavelength 248 n)
m), a method using a charged particle beam such as an X-ray such as far ultraviolet rays represented by an ArF excimer laser (wavelength 193 nm), synchrotron radiation or an electron beam, or the like. As a high-resolution resist corresponding to these short-wavelength radiations, a “chemically amplified resist” has been proposed, and improvements in the chemically amplified resist are being actively pursued. The chemically amplified resist is irradiated with radiation to a radiation-sensitive acid generator contained therein (hereinafter, referred to as “radiation-sensitive acid generator”).
This is called "exposure". ) To generate an acid, and a catalytic reaction of the acid causes a chemical reaction (for example, change in polarity, cleavage of chemical bond, cross-linking reaction, etc.) in the resist film, and the solubility in the developing solution changes in the exposed portion. A pattern is formed using the phenomenon. Conventionally, as such a chemically amplified resist, a resin in which an alkali-affinity group in an alkali-soluble resin is protected by a t-butyl ester group or a t-butoxycarbonyl group as a resin component (see JP-B-2-27660). ), A resin in which an alkali-affinity group in an alkali-soluble resin is protected by a silyl group (Japanese Patent Publication No.
JP-A-44290), a resin in which an alkali-affinity group in an alkali-soluble resin is protected by a ketal group.
Chemical amplification such as a resist using a resin in which an alkali-affinity group in an alkali-soluble resin is protected with an acetal group (see JP-A-2-161436 and JP-A-5-249682). There have been many reports on mold resists. However, these chemically amplified resists have their own problems, and it has been pointed out that various difficulties are involved particularly in practical application to fine processing with a design size of 0.25 μm or less. When performing fine processing with a thickness of about 20 μm with a small film thickness, the surface and side surfaces of the resist film after pattern formation become large and uneven, which hinders fine processing according to design dimensions, so-called “nano edge roughness” or “ The problem of "film surface roughness" has begun to be pointed out. On the other hand, in a radiation-sensitive resin composition for a chemically amplified resist, by using a combination of a radiation-sensitive acid generator as a photosensitive component and a compound which can be decomposed into a neutral compound by exposure, the line width is particularly controlled. (See JP-A-9-43837), and contains a resin which becomes alkali-soluble by the action of an acid, a radiation-sensitive acid generator, and a tertiary amine compound having an aliphatic hydroxyl group. It is disclosed that the composition is particularly excellent in resistance to the time delay effect (see JP-A-10-177250). However, these compositions are unsatisfactory in terms of suppression of “nano edge roughness” or “roughness of the film surface”, which is a major problem particularly when performing fine processing with a design dimension of about 0.20 μm with a small film thickness. Therefore, there is a strong demand for the development of a chemically amplified resist that is excellent in sensitivity, resolution, and pattern shape and that can solve the problem of “nano edge roughness” or “film surface roughness”.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to effectively respond to various kinds of radiation such as far ultraviolet rays, X-rays and charged particle beams, to have excellent sensitivity, resolution and pattern shape. An object of the present invention is to provide a radiation-sensitive resin composition useful as a chemically amplified resist capable of stably forming a high-precision fine resist pattern without causing "film surface roughness".

[0004]

According to the invention of the present application, the object is to provide (a) (I) a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2): (B) a radiation-sensitive acid generator, and (c) at least one basic compound selected from the group consisting of compounds represented by the following general formulas (3) to (8). It is achieved by a radiation-sensitive resin composition characterized by containing.

[0005]

Embedded image [In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Show. ]

[0006]

Embedded image [In the general formula (2), R ⁴ represents a hydrogen atom or a methyl group. ]

[0007]

Embedded image [In the general formula (3), X ¹ represents a polymethylene chain having a main chain carbon number of 2 to 8, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a linear chain having 1 to 12 carbon atoms. Or a branched or cyclic alkyl group, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, or R ⁵ and R ⁶ are bonded, or R ⁷ and R ⁸ are bonded. Each of which forms a 5- to 8-membered heterocyclic structure together with one nitrogen atom in the general formula (3), and the rest of R ^{5 to} R ⁸ are each independently a straight-chain having 1 to 12 carbon atoms; A branched or cyclic alkyl group, an aryl group having 6 to 12 carbon atoms, or 7 to 1 carbon atoms
2 represents an aralkyl group, and at least one of the polymethylene chain, alkyl group, aryl group, aralkyl group and heterocyclic structure has at least one hydroxyl group bonded to a carbon atom. However, the polymethylene chain, the alkyl group, the aryl group, the aralkyl group and the heterocyclic structure may have an oxygen atom, a sulfur atom or a carbonyl group between any of their carbon-carbon bonds. A hydrogen atom bonded to an atom may be substituted with one or more substituents other than a hydroxyl group such as an alkoxyl group and a phenoxy group. ]

[0008]

Embedded image [In the general formula (4), R ⁹ and R ¹⁰ are each independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a C ^{7 to} C
12 represents an aralkyl group, and has at least one of the alkyl group, the aryl group, the aralkyl group, and at least one hydroxyl group bonded to a carbon atom in the general formula (4). However, the alkyl group, aryl group and aralkyl group may have an oxygen atom, a sulfur atom or a carbonyl group between any of their carbon-carbon bonds, and a hydrogen atom bonded to any of those carbon atoms It may be substituted with one or more substituents other than a hydroxyl group such as an alkoxyl group and a phenoxy group. ]

[0009]

Embedded image [In the general formula (5), X ² represents a polymethylene chain having a main chain carbon number of 2 to 8, and R ¹¹ and R ¹² independently of each other have a linear, branched or cyclic shape having 1 to 12 carbon atoms. Alkyl group, aryl group having 6 to 12 carbon atoms or 7 to 7 carbon atoms
12 aralkyl groups, and said polymethylene chain,
An alkyl group, an aryl group, an aralkyl group, and at least one hydroxyl group in which at least one of one or two piperidine rings in formula (5) is bonded to a carbon atom. However, the polymethylene chain, the alkyl group, the aryl group and the aralkyl group can have an oxygen atom, a sulfur atom or a carbonyl group between any of their carbon-carbon bonds, and are bonded to any of those carbon atoms. A hydrogen atom may be substituted with one or more substituents other than a hydroxyl group such as an alkoxyl group and a phenoxy group. ]

[0010]

Embedded image [In the general formula (6), X ³ and X ⁴ independently represent a polymethylene chain having a main chain carbon number of 2 to 8, and R ¹³ ,
R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ independently of one another have 1 to 1 carbon atoms
12 linear, branched or cyclic alkyl group, or an aryl group or an aralkyl group having 7 to 12 carbon atoms of 6 to 12 carbon atoms, or R ¹³ and R ¹⁴ are bonded to each other or R ^16, And R ¹⁷ are mutually bonded to form a 5- to 8-membered heterocyclic structure together with one nitrogen atom in the general formula (6), and the rest of R ^{13 to} R ¹⁷ are each independently a carbon atom. Number 1
A linear, branched or cyclic alkyl group, an aryl group having 6-12 carbon atoms or an aralkyl group having 7-12 carbon atoms, and the polymethylene chain, alkyl group, aryl group, aralkyl group and At least one of the ring structures has at least one hydroxyl group bonded to a carbon atom. However, the polymethylene chain, the alkyl group, the aryl group, the aralkyl group and the heterocyclic structure may have an oxygen atom, a sulfur atom or a carbonyl group between any of their carbon-carbon bonds. A hydrogen atom bonded to an atom may be substituted with one or more substituents other than a hydroxyl group such as an alkoxyl group and a phenoxy group. ]

[0011]

Embedded image [In the general formula (7), R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R
²² and R ²³ are each independently a linear group having 1 to 12 carbon atoms;
A branched or cyclic alkyl group, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, or R ¹⁸ and R ¹⁹ are mutually bonded, or R ²⁰ and R ²¹ are mutually R ²² and R ²³ are bonded to each other to form a 5- to 8-membered heterocyclic structure together with one nitrogen atom in the general formula (7), and the remaining R ^{18 to} R ²³ Each independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. However, the alkyl group, the aryl group, the aralkyl group and the heterocyclic structure may have at least one hydroxyl group having at least one of them bonded to a carbon atom, and an oxygen atom between any of the carbon-carbon bonds. , A sulfur atom or a carbonyl group, and a hydrogen atom bonded to any carbon atom thereof may be substituted with one or more substituents other than a hydroxyl group such as an alkoxyl group and a phenoxy group. ]

[0012]

Embedded image [In the general formula (8), R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ each independently represent a hydrogen atom, a hydroxyl group, a carbon number of 1 to 1
2 linear, branched or cyclic alkyl group, or an aryl group or an aralkyl group having 7 to 12 carbon atoms of 6 to 12 carbon atoms, or R ²⁴ and R ²⁵ are bonded to each other or R ^25, And R ²⁶ are mutually bonded, or R ²⁶ and R ²⁷ are mutually bonded, or R ²⁷ and R ²⁸ are mutually bonded,
Each of the two carbon atoms in the general formula (8) forms a 6-membered aromatic ring structure together with the two carbon atoms, and the rest of R ^{24 to} R ²⁸ are independently a hydrogen atom, a hydroxyl group, a straight chain having 1 to 12 carbon atoms. , A branched or cyclic alkyl group, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms;
Or that at least one hydroxyl group of ²⁴ to R ^28, or having the alkyl group, an aryl group, at least one aralkyl group and aromatic ring structures wherein one or more hydroxyl groups bonded to a carbon atom. However, when at least one of R ^{24 to} R ²⁸ is a hydroxyl group, at least one of the remaining alkyl groups, aryl groups, aralkyl groups and aromatic ring structures of R ^{24 to} R ²⁸ can have one or more hydroxyl groups. The alkyl group, the aryl group, the aralkyl group and the aromatic ring structure may have an oxygen atom, a sulfur atom or a carbonyl group between any of their carbon-carbon bonds, and may be bonded to any of those carbon atoms. A hydrogen atom other than a hydroxyl group such as an alkoxyl group, a phenoxy group or a pyridyl group;
It may be substituted with one or more substituents. ]

Hereinafter, the present invention will be described in detail. (A) Component In the present invention, the component (A) is a repeating unit represented by the general formula (1) (hereinafter referred to as “repeating unit (1)”) and a repeating unit represented by the general formula (2). A unit (hereinafter, referred to as “repeating unit (2)”) as an essential unit, and in some cases, a resin having another repeating unit (hereinafter, referred to as “resin (a)”). In resin (a), repeating unit (1), repeating unit (2)
And other repeating units may be present alone or in combination of two or more. The resin (a) is a resin having an acid dissociable acetal group represented by the following formula (9) (hereinafter, referred to as “acetal group (9)”).

[0014]

Embedded image In [Equation (9), R ² and R ³ have the same meanings as R ² and R ³ respectively in general formula (1). In addition, the resin (a) may have a structure partially cross-linked with an appropriate cross-linking group (for example, a cross-linking group having a diethylene glycol skeleton).

In the general formula (1), examples of the linear, branched or cyclic C1-C6 alkyl group of R ² and R ³ include a methyl group, an ethyl group, an n-propyl group and an i-type group. -Propyl group, n-butyl group, i-butyl group,
sec-butyl group, t-butyl group, n-pentyl group, n
-Hexyl group, cyclopentyl group, cyclohexyl group and the like. As R ² and R ³ in the general formula (1), a hydrogen atom, a methyl group, and an ethyl group are particularly preferable.

In the resin (A), the content of the repeating unit (1) is preferably from 5 to 70, based on all repeating units.
Mol%, more preferably 5 to 60 mol%, and the content of the repeating unit (2) is preferably 10 to 95 mol%, more preferably 40 to 95 mol%, based on all repeating units.
Mol%, and the content of other repeating units is preferably 70 mol% or less, more preferably 40 mol% or less, based on all repeating units. In this case, if the content of the repeating unit (1) in the resin (a) is less than 5 mol%, it tends to be difficult to obtain sufficient resolution performance, while 70
If it exceeds mol%, the heat resistance tends to decrease. If the content of the repeating unit (2) is less than 10 mol%,
Adhesion with the substrate tends to decrease, while 95 mol%
If it exceeds 300, the unexposed portion is also easily dissolved, and it becomes difficult to form a resist pattern, or the pattern shape tends to be damaged.

Examples of the resin (a) include 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2-hydroxy-α-methylstyrene,
At least one compound selected from the group consisting of -hydroxy-α-methylstyrene and 4-hydroxy-α-methylstyrene, optionally with another polymerizable unsaturated compound (provided that the compound corresponding to the repeating unit (1) is ), A resin having a structure in which a hydrogen atom of a phenolic hydroxyl group in a (co) polymerized (co) polymer is partially substituted with an acetal group (3), or diethylene glycol. Examples of the resin include a resin having a structure partially crosslinked by a crosslinking group having a skeleton.

In some cases, the resin (a) may partially substitute a hydrogen atom of a phenolic hydroxyl group in the (co) polymer with an acid dissociable group other than the acetal group (9) (hereinafter referred to as “others”). (Hereinafter referred to as “acid dissociable group”). As other acid dissociable groups, for example, t-butyl group, benzyl group, t-butoxycarbonyl group, t-butoxycarbonylmethyl group, tetrahydrofuranyl group,
Examples thereof include a tetrahydropyranyl group.

Examples of the other polymerizable unsaturated compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene,
Methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-benzyloxystyrene, 4-t-butoxycarbonyloxystyrene, 4-t-butoxycarbonylmethyloxystyrene, 4- (2 ′ Vinyl aromatic compounds such as -t-butoxycarbonylethyloxy) styrene, 4-tetrahydrofuranyloxystyrene, 4-tetrahydropyranyloxystyrene; methyl (meth) acrylate, (meth) methyl
Ethyl acrylate, n-propyl (meth) acrylate,
I-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (meth)
Sec-butyl acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( Meta)
2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, cyclopentyl (meth) acrylate,
Cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate,
Tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, adamantyl methyl (meth) acrylate, tetrahydrofuranyl (meth) acrylate, tetrahydropyranyl (meth) acrylate (Meth) acrylic esters such as phenyl (meth) acrylate, benzyl (meth) acrylate, and phenethyl (meth) acrylate; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid,
Unsaturated carboxylic acids such as cinnamic acid; carboxyalkyl esters of unsaturated carboxylic acids such as 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate and 3-carboxypropyl (meth) acrylate An unsaturated nitrile compound such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonitrile, maleinitrile, fumaronitrile; (meth) acrylamide, N, N-dimethyl (meth) acrylamide;
Unsaturated amide compounds such as crotonamide, maleamide, fumaramide; unsaturated imide compounds such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide; N-vinyl-ε-caprolactam, N-vinylpyrrolidone, 2-vinylpyridine, 3-vinylpyridine,
Other nitrogen-containing vinyl compounds such as 4-vinylpyridine, 2-vinylimidazole, and 4-vinylimidazole can be exemplified.

As the resin (a), poly (4-hydroxystyrene), poly (4-hydroxy-α-methylstyrene), 4-hydroxystyrene / 4-hydroxy-α
A part of hydrogen atoms of phenolic hydroxyl groups in a methylstyrene copolymer or a copolymer of 4-hydroxystyrene and / or 4-hydroxy-α-styrene with styrene and / or α-methylstyrene, A resin having a structure substituted with the group (9), a resin having a structure in which the resin is partially cross-linked with a cross-linking group having a diethylene glycol skeleton, and the like are preferable.

The resin (a) is prepared, for example, by introducing an acetal group (9) into a part of hydrogen atoms of a phenolic hydroxyl group in a (co) polymer of hydroxy (α-methyl) styrenes prepared in advance. Optionally, a method of further introducing another acid dissociable group to a part of the hydrogen atom of the phenolic hydroxyl group in the (co) polymer, (b) converting the hydrogen atom of the phenolic hydroxyl group with an acetal group (9). The substituted hydroxy (α-methyl) styrene derivatives and hydroxy (α-methyl) styrenes can be produced, for example, by a method of copolymerizing with the other polymerizable unsaturated compound, if necessary. The structure partially cross-linked by the cross-linking group having a diethylene glycol skeleton in the resin (a) may be prepared, for example, by introducing an appropriate amount of an acetal group (9) and / or another acid dissociable group in the method (a). It can be introduced by simultaneously reacting diethylene glycol divinyl ether.

The polystyrene-equivalent weight average molecular weight (hereinafter, referred to as “Mw”) of the resin (a) determined by gel permeation chromatography (hereinafter, referred to as “GPC”) does not have the partially crosslinked structure. , Preferably 1,000 to 150,000, more preferably 3,000 to 100,000, and when having the partially crosslinked structure, preferably 8,000 to 5
00,000, more preferably 12,000 to 30
It is 0000. By setting the Mw of the resin (a) in the above range, a radiation-sensitive resin composition particularly excellent in resolution, developability, and the like can be obtained. In the present invention, the resin (a) can be used alone or in combination of two or more.

(B) Component The (B) component in the present invention comprises a radiation-sensitive acid generator that generates an acid upon exposure (hereinafter, referred to as “acid generator (B)”). Examples of the acid generator (b) include onium salt compounds, sulfone compounds, sulfonic ester compounds, sulfonimide compounds, and diazomethane compounds. Hereinafter, examples of the acid generator (b) will be described. Onium salt: Examples of the onium salt include an iodonium salt, a sulfonium salt, a phosphonium salt, a diazonium salt, an ammonium salt, a pyridinium salt and the like. Specific examples of the onium salt compound include bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate,
Bis (4-t-butylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, bis (4-t-butyl
Butylphenyl) iodonium pyrene sulfonate, bis (4-t-butylphenyl) iodonium n-dodecylbenzenesulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, bis (4
-T-butylphenyl) iodoniumbenzenesulfonate, bis (4-t-butylphenyl) iodonium 1
0-camphorsulfonate, bis (4-t-butylphenyl) iodonium n-octanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium 2-trifluoromethylbenzenesulfonate, diphenyliodonium pyrene sulfonate Diphenyliodonium n-dodecylbenzenesulfonate, diphenyliodonium p-
Toluenesulfonate, diphenyliodonium benzenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium n-octanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium 2-trifluoromethylbenzenesulfonate Triphenylsulfonium pyrene sulfonate, triphenylsulfonium n-dodecylbenzenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium n-octanesulfonate, 4-t- Spot Phenyl-diphenylsulfonium nonafluoro -n- butane sulfonate, 4-t-
Butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium 2-trifluoromethylbenzenesulfonate, 4-t-butoxyphenyl diphenylsulfonium pyrene sulfonate, 4-t-butoxyphenyl diphenylsulfonium n-dodecyl Benzenesulfonate, 4-t-butoxyphenyl / diphenylsulfonium p-toluenesulfonate, 4-t-butoxyphenyl / diphenylsulfonium benzenesulfonate, 4-t-butoxyphenyl / diphenylsulfonium 10-camphorsulfonate, 4-t-butoxyphenyl. Examples thereof include diphenylsulfonium n-octanesulfonate.

Sulfone compound: Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof. Specific examples of the sulfone compound include phenacylphenylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, 4-trisphenacylsulfone, and the like. Sulfonic acid ester compound: Examples of the sulfonic acid ester compound include alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, and iminosulfonates.
Specific examples of the sulfonic acid ester compound include α-methylol benzoin perfluorobutane sulfonate, α
-Methylol benzoin trifluoromethanesulfonate, α-methylol benzoin 2-trifluoromethylbenzenesulfonate, phenacyl phenyl sulfone,
Mesityl phenacyl sulfone, bis (phenylsulfonyl) methane, 4-trisphenacyl sulfone and the like can be mentioned. Sulfonimide compound: As the sulfonimide compound, for example, the following formula (10)

[0025]

Embedded image [In the formula (10), Z represents a divalent group such as an alkylene group, an arylene group, or an alkoxylene group, and R ²⁹ represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group. Represents a group. )).

Specific examples of the sulfonimide compound include:
N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy)
Phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( Trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (camphorsulfonyloxy) succinimide , N- (camphorsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N −
(Camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-5 6-oxy-2,3-
Dicarboximide, N- (camphorsulfonyloxy) naphthylimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) phthalimide, N- (4-methylphenylsulfonyloxy) diphenylmaleimide , N
-(4'-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4'-methylphenylsulfonyloxy) -7-oxabicyclo [2 2.1] Hept-5-
Ene-2,3-dicarboximide, N- (4'-methylphenylsulfonyloxy) bicyclo [2.2.1]
Heptane-5,6-oxy-2,3-dicarboximide, N- (camphorsulfonyloxy) naphthylimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyl) Oxy) phthalimide, N- (2
-Trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (2'-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-
(2′-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide, N- (2'-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- ( 2-trifluoromethylphenylsulfonyloxy) naphthylimide, N- (4-fluorophenylsulfonyloxy) succinimide, N
-(4-fluorophenyl) phthalimide, N- (4-
Fluorophenylsulfonyloxy) diphenylmaleimide, N- (4′-fluorophenylsulfonyloxy) bicyclo [2.1.1] hept-5-ene-2,3
-Dicarboximide, N- (4'-fluorophenylsulfonyloxy) -7-oxabicyclo [2.1.
1] hept-5-ene-2,3-dicarboximide,
N- (4'-fluorophenylsulfonyloxy) bicyclo [2.1.1] heptane-5,6-oxy-2,3
-Dicarboximide, N- (4-fluorophenylsulfonyloxy) naphthylimide and the like. Diazomethane compound: As the diazomethane compound,
For example, the following equation (11)

[0027]

Embedded image [In the formula (11), R ³⁰ and R ³⁰ each independently represent a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, and a halogen-substituted aryl group. ] Can be mentioned.

Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, and bis (p-toluenesulfonyl) Diazomethane, bis (1,4-dioxaspiro
[4.5] Decane-7-sulfonyl) diazomethane, cyclohexylsulfonyl / t-butylsulfonyldiazomethane, methylsulfonyl / p-toluenesulfonyldiazomethane and the like.

As the acid generator (b) in the present invention,
Onium salt compounds and diazomethane compounds are preferred, and bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-
t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate , Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-
Toluenesulfonate, triphenylsulfonium 10
-Camphorsulfonate, 4-t-butoxyphenyl / diphenylsulfonium nonafluoro-n-butanesulfonate, 4-t-butoxyphenyl / diphenylsulfonium trifluoromethanesulfonate, 4-t-
Butoxyphenyl diphenylsulfonium p-toluenesulfonate, 4-t-butoxyphenyl diphenylsulfonium 10-camphorsulfonate, bis (t-butylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (1,4-dioxaspiro [4. 5] Decane-7-sulfonyl) diazomethane and the like are preferred.

In the present invention, the acid generator (b) can be used alone or in combination of two or more. The amount of the acid generator (b) used in the present invention is as follows.
The amount is preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, per 100 parts by weight. In this case, if the amount of the acid generator (b) is less than 0.1 part by weight, the sensitivity tends to decrease, while if it exceeds 20 parts by weight, the coatability of the resist tends to decrease.

(C) Component The (C) component in the present invention is a compound represented by the above general formula (3) (hereinafter referred to as “basic compound (3)”) and a compound represented by the above general formula (4). Compound (hereinafter, referred to as
It is called "basic compound (4)." ), The general formula (5)
(Hereinafter, referred to as “basic compound (5)”), a compound represented by the general formula (6) (hereinafter, referred to as “basic compound (5)”).
It is referred to as "basic compound (6)". ), The general formula (7)
(Hereinafter, referred to as “basic compound (7)”) and a compound represented by the general formula (8) (hereinafter, referred to as “basic compound (8)”). It is composed of at least one basic compound (hereinafter, the basic compounds (3) to (8) may be collectively referred to as “basic compound (c)”). In a chemically amplified radiation-sensitive resin composition containing a radiation-sensitive acid generator, by adding a basic substance as an acid diffusion control agent, the pattern shape, the prevention of the occurrence of eaves in the upper layer of the pattern can be further improved. Is already known. The present inventors have intensively studied a method for improving “nano edge roughness” or “film surface roughness” in a chemically amplified radiation-sensitive resin composition containing the resin (a), and found that an acid diffusion controller By using the basic compound (c) as a component, it has been found that various properties of the radiation-sensitive resin composition are remarkably improved, and the present invention has been accomplished.

Hereinafter, examples of the basic compound (c) will be specifically described. Specific examples of the basic compound (3) include N,
N, N'-trimethyl-N '-(2-hydroxyethyl) ethylenediamine, N, N, N'-triethyl-
N ′-(2-hydroxyethyl) ethylenediamine,
N, N, N'-trimethyl-N '-(2-hydroxypropyl) ethylenediamine, N, N, N'-triethyl-N'-(2-hydroxypropyl) ethylenediamine, N, N, N'-triphenyl- N '-(2-hydroxyethyl) ethylenediamine, N, N, N'-tribenzyl-N'-(2-hydroxyethyl) ethylenediamine, N, N, N'-tribenzyl-N '-(2-hydroxypropyl) ethylenediamine N, N, N'-trimethyl-N '-(4-hydroxyphenyl) ethylenediamine, N, N, N'-trimethyl-N'-(4-hydroxybenzyl) ethylenediamine, N, N, N'-
Trimethyl-N '-(2-hydroxyethyl) trimethylenediamine, N, N, N'-trimethyl-N'-(2
-Hydroxyethyl) tetramethylenediamine, N,
N, N'-trimethyl-N '-(2-hydroxyethyl) pentamethylenediamine, N, N, N'-trimethyl-N'-(2-hydroxyethyl) hexamethylenediamine, N, N, N'-trimethyl -N '-(2-hydroxyethyl) heptamethylenediamine, N, N, N'
-Trimethyl-N '-(2-hydroxyethyl) octamethylenediamine, 1,3-bis (dimethylamino)-
2-propanol, 1,3-bis (diethylamino)-
2-propanol, 1-dimethylamino-2- (3'-
(Hydroxypyrrolidino) ethane, 1-dimethylamino-
2- (3'-hydroxymethylpyrrolidino) ethane, 1
-Dimethylamino-2- {3 ′-(2 ″ -hydroxyethyl) pyrrolidino} ethane, 1-dimethylamino-2-
A hydroxyl group such as (4'-hydroxypiperidino) ethane
Compounds having;

N, N'-dimethyl-N, N'-bis (2
-Hydroxyethyl) ethylenediamine, N, N'-diethyl-N, N'-bis (2-hydroxyethyl) ethylenediamine, N, N'-dimethyl-N, N'-bis (2-hydroxypropyl) ethylenediamine,
N'-diethyl-N, N'-bis (2-hydroxypropyl) ethylenediamine, N, N'-dimethyl-N,
N′-bis (4-hydroxyphenyl) ethylenediamine, N, N′-dimethyl-N, N′-bis (4-hydroxybenzyl) ethylenediamine, 1,2-bis (3 ′
-Hydroxypyrrolidino) ethane, 1,2-bis (3 '
-Hydroxymethylpyrrolidino) ethane, 1,2-bis {(3 ′-(2 ″ -hydroxyethyl) pyrrolidino) ethane, 1,2-bis (4′-hydroxypiperidino) ethane, 1,2- Bis (4′-hydroxymethylpiperidino) ethane, 1,2-bis {(4 ′-(2 ″ -hydroxyethyl) piperidino} ethane, 1-morpholino-2-
Compounds having two hydroxyl groups, such as {bis (2'-hydroxyethyl) amino} ethane;

N-methyl-N, N ', N'-tris (2
-Hydroxyethyl) ethylenediamine, Nn-dodecyl-N, N ', N'-tris (2-hydroxyethyl) ethylenediamine, N-methyl-N, N', N'-
Tris (4-hydroxyphenyl) ethylenediamine,
N-methyl-N, N ', N'-tris (4-hydroxybenzyl) ethylenediamine, 1- (3'-hydroxypyrrolidino) -2- {bis (2'-hydroxyethyl)
Amino diethane, 1- (4'-hydroxypiperidino)
Compounds having three hydroxyl groups such as -2- {bis (2'-hydroxyethyl) amino} ethane;

N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine, N, N, N',
N′-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N ′, N′-tetrakis (4-hydroxyphenyl) ethylenediamine, N, N, N ′,
N′-tetrakis (4-hydroxybenzyl) ethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxy-3-methoxypropyl) ethylenediamine,
N, N, N ', N'-tetrakis (2-hydroxy-3
-Ethoxypropyl) ethylenediamine, N, N,
N ′, N′-tetrakis (2-hydroxy-3-n-propoxypropyl) ethylenediamine, N, N, N ′,
N'-tetrakis (2-hydroxy-3-phenoxypropyl) ethylenediamine, N, N'-dimethyl-N,
N′-bis (2,3-dihydroxypropyl) ethylenediamine, N, N′-diethyl-N, N′-bis (2,
3-dihydroxypropyl) ethylenediamine, N-methyl-N, N ', N'-tris (2,3-dihydroxypropyl) ethylenediamine, N, N, N', N'-tetrakis (2,3-dihydroxypropyl) ethylenediamine And the like having 4 or more hydroxyl groups.

Specific examples of the basic compound (4) include N
-Methyl-N '-(2-hydroxyethyl) piperazine, N-ethyl-N'-(2-hydroxyethyl) piperazine, Nn-propyl-N '-(2-hydroxyethyl) piperazine, Nn- Butyl-N '-(2-hydroxyethyl) piperazine, Nn-hexyl-N'-
(2-hydroxyethyl) piperazine, Nn-octyl-N ′-(2-hydroxyethyl) piperazine, N-
n-decyl-N '-(2-hydroxyethyl) piperazine, Nn-dodecyl-N'-(2-hydroxyethyl) piperazine, N-methyl-N '-(2-hydroxypropyl) piperazine, N-methyl -N '-(3-hydroxypropyl) piperazine, N-phenyl-N'-
(2-hydroxyethyl) piperazine, N-benzyl-
N '-(2-hydroxyethyl) piperazine, N-methyl-N'-(4-hydroxyphenyl) piperazine, N
A compound having one hydroxyl group, such as -methyl-N '-(4-hydroxybenzyl) piperazine;

N, N'-bis (2-hydroxyethyl)
Piperazine, N, N'-bis (2-hydroxypropyl) piperazine, N, N'-bis (4-hydroxyphenyl) piperazine, N, N'-bis (4-hydroxybenzyl) piperazine, N-methyl-N ' -(2,3-dihydroxypropyl) piperazine, N-ethyl-N'-
Compounds having two hydroxyl groups such as (2,3-dihydroxypropyl) piperazine;

N- (2-hydroxyethyl) -N'-
(2,3-dihydroxypropyl) piperazine, N-
(2-hydroxypropyl) -N '-(2,3-dihydroxypropyl) piperazine, N- (4-hydroxyphenyl) -N'-(2,3-dihydroxypropyl) piperazine, N- (4-hydroxybenzyl) -N'-
Compounds having three hydroxyl groups such as (2,3-dihydroxypropyl) piperazine;

N, N'-bis (2,3-dihydroxypropyl) piperazine, N, N'-bis (3,4-dihydroxyphenyl) piperazine, N, N'-bis (3
4,5-trihydroxyphenyl) piperazine, N,
Compounds having four or more hydroxyl groups such as N'-bis (3,4-dihydroxybenzyl) piperazine and N, N'-bis (3,4,5-trihydroxybenzyl) piperazine can be mentioned.

Specific examples of the basic compound (5) include 1
-{4 ′-(N-methylpiperidinyl)}-2- [4 ′
-{N- (2 ''-hydroxyethyl) piperidinyl}]
Ethane, 1- {4 ′-(Nn-dodecylpiperidinyl)}-2- [4 ′-{N- (2 ″ -hydroxyethyl) piperidinyl}] ethane, 1- {4 ′-(N -Benzylpiperidinyl) {-2- [4 '-{N- (2 "-hydroxyethyl) piperidinyl}] ethane, 1,3-bis {4'-(N-methylpiperidinyl)}-2 -Propanol, 1- {4 '-(N-methylpiperidinyl)}-
3- [4 '-{N- (2 "-hydroxyethyl) piperidinyl}] propane, 1- {4'-(N-methylpiperidinyl)}-6- [4 '-{N- (2''-Hydroxyethyl) piperidinyl}] hexane, 1- {4'-(N-
Methylpiperidinyl)}-8- [4 ′-{N- (2 ″-
Compounds having one hydroxyl group such as hydroxyethyl) piperidinyl}] octane;

1,2-bis [4 '-{N- (2 "-hydroxyethyl) piperidinyl}] ethane, 1,2-bis [4'-{N- (2" -hydroxypropyl) piperidinyl} ] Ethane, 1,2-bis [4′-ΔN- (2 ″-
Hydroxyethyl) piperidinyl}] propane, 1,2
A compound having two hydroxyl groups such as -bis [4 '-{N- (2 "-hydroxypropyl) piperidinyl}] propane;

1- [4 '-{N- (2 "-hydroxyethyl) piperidinyl}]-2- [4'-{N'-
(2 ″, 3 ″ -dihydroxypropyl) piperidinyl}] ethane, 1- [4 ′-{N- (2 ″ -hydroxypropyl) piperidinyl}]-2- [4 ′-{N′-
(2 ″, 3 ″ -dihydroxypropyl) piperidinyl}] ethane, 1- [4 ′-{N- (2 ″ -hydroxyethyl) piperidinyl}]-2- [4 ′-{N′-
(2 ″, 3 ″ -dihydroxypropyl) piperidinyl}] propane, 1- [4 ′-{N- (2 ″ -hydroxypropyl) piperidinyl}]-2- [4 ′-{N′-
(2 '', 3 ''-dihydroxypropyl) piperidinyl {] a compound having three hydroxyl groups such as propane;

1,2-bis {N- (2 ', 3'-dihydroxypropyl) piperazinyl} ethane, 1,2-bis {N- (3', 4'-dihydroxyphenyl) piperazinyl} ethane, 1,2 -Bis @ N- (3 ', 4', 5 '
-Trihydroxyphenyl) piperazinylethane,
1,2-bis {N- (3 ', 4'-dihydroxybenzyl) piperazinyl} ethane, 1,2-bis {N-
Compounds having four or more hydroxyl groups, such as (3 ', 4', 5'-trihydroxybenzyl) piperazinyldiethane, can be mentioned.

Specific examples of the basic compound (6) include bis (2-dimethylaminoethyl) -2-hydroxyethylamine, bis (2-dimethylaminoethyl) -2-hydroxypropylamine, N, N, N ' -Trimethyl-
N '-{2- (3'-hydroxypyrrolidino) ethyl)} ethylenediamine, bis (2-pyrrolidinoethyl) -2-hydroxyethylamine, bis (2-pyrrolidinoethyl) -2-hydroxypropylamine, methyl 2-pyrrolidinoethyl 2- (3'-hydroxypyrrolidino) ethylamine, N, N, N'-trimethyl-
N '-{2- (4'-hydroxypiperidino) ethyl)} ethylenediamine, N, N-dimethyl-N'-
A compound having one hydroxyl group such as (2-piperidinoethyl) -N ′-(2-hydroxyethyl) ethylenediamine;

N, N ', N "-trimethyl-N, N"-
Bis (2-hydroxyethyl) diethylenetriamine,
N, N, N ″, N ″ -tetramethyl-N ′-(2,3-
Dihydroxypropyl) diethylenetriamine, N-methyl-N- (2-pyrrolidinoethyl) -N ′, N′-bis (2-hydroxyethyl) ethylenediamine, methyl bis {2- (3′-hydroxypyrrolidino) ethyl}
Amine, bis (2-pyrrolidinoethyl) · 2,3-dihydroxypropylamine, N-methyl-N- (2-piperidinoethyl) -N ′, N′-bis (2-hydroxyethyl) ethylenediamine, methyl bis 2- (4'-
Compounds having two hydroxyl groups such as hydroxypiperidino) ethyl diamine, bis (2-morpholinoethyl) .2,3-dihydroxypropylamine;

N, N ″ -dimethyl-N, N ′, N ″ -tris (2-hydroxyethyl) diethylenetriamine,
N, N "-dimethyl-N, N ', N" -tris (2-hydroxypropyl) diethylenetriamine, N- (2-
Pyrrolidinoethyl) -N, N ', N'-tris (2-hydroxyethyl) ethylenediamine, N- (2-piperidinoethyl) -N, N', N'-tris (2-hydroxyethyl) ethylenediamine, bis {2 Compounds having three hydroxyl groups, such as-(3'-hydroxypyrrolidino) ethyl} .2-hydroxyethylamine, bis {2- (4'-hydroxypiperidino) ethyl} .2-hydroxyethylamine;

N'-methyl-N, N, N ", N" -tetrakis (2-hydroxyethyl) diethylenetriamine, N'-ethyl-N, N, N ", N" -tetrakis (2- Hydroxyethyl) diethylenetriamine, N '
-N-butyl-N, N, N ", N" -tetrakis (2-
Hydroxyethyl) diethylenetriamine, N'-n-
Hexyl-N, N, N ", N" -tetrakis (2-hydroxyethyl) diethylenetriamine, N'-n-octyl-N, N, N ", N" -tetrakis (2-hydroxyethyl) diethylenetriamine , N'-n-decyl-
N, N, N ″, N ″ -tetrakis (2-hydroxyethyl) diethylenetriamine, N′-n-dodecyl-N,
N, N ", N" -tetrakis (2-hydroxyethyl)
Diethylenetriamine, N'-phenyl-N, N,
N ″, N ″ -tetrakis (2-hydroxyethyl) diethylenetriamine, N′-benzyl-N, N, N ″,
N "-tetrakis (2-hydroxyethyl) diethylenetriamine, N, N, N ', N", N "-pentakis (2-hydroxyethyl) diethylenetriamine,
N, N ′, N ″, N ″ -pentakis (2-hydroxypropyl) diethylenetriamine, N, N, N ′, N ″,
N "-pentakis (4-hydroxyphenyl) diethylenetriamine, N, N, N ', N", N "-pentakis (4-hydroxybenzyl) diethylenetriamine,
N, N, N ′, N ″, N ″ -pentakis (2-hydroxy-3-methoxypropyl) diethylenetriamine,
N, N, N ′, N ″, N ″ -pentakis (2-hydroxy-3-ethoxypropyl) diethylenetriamine,
N, N, N ′, N ″, N ″ -pentakis (2-hydroxy-3-n-propoxypropyl) diethylenetriamine, N, N, N ′, N ″, N ″ -pentakis (2-hydroxy -3-phenoxypropyl) diethylenetriamine, N, N "-dimethyl-N, N ', N" -tris (2,3-dihydroxypropyl) diethylenetriamine, N'-methyl-N, N, N ", N '' -Tetrakis (2,3-dihydroxypropyl) diethylenetriamine, N, N, N ′, N ″, N ″ -pentakis (2,3-
Compounds having four or more hydroxyl groups, such as dihydroxypropyl) diethylenetriamine, may be mentioned.

Specific examples of the basic compound (7) include:
2,4,6-tris (dimethylaminomethyl) phenol, 2,4,6-tris (diethylaminomethyl) phenol, 2,4,6-tris (diphenylaminomethyl) phenol, 2,4,6-tris (di (Benzylaminomethyl) phenol, 2,4,6-tris (pyrrolidinomethyl) phenol, 2,4,6-tris (piperidinomethyl) phenol, 4-morpholinomethyl-2,6
-Bis (dimethylaminomethyl) phenol, 2,4
A compound having one hydroxyl group such as 6-tris (morpholinomethyl) phenol;

2,6-bis (dimethylaminomethyl)-
4-[{methyl- (2'-hydroxyethyl) amino}
Methyl] phenol, 2,6-bis (dimethylaminomethyl) -4-[{methyl • (2′-hydroxypropyl) amino} methyl] phenol, 2,6-bis (dimethylaminomethyl) -4- (3 ′ -Hydroxypyrrolidinomethyl) phenol, 2,6-bis (dimethylaminomethyl) -4- (4'-hydroxypiperidinomethyl)
Compounds having two hydroxyl groups such as phenol;

2,6-bis (dimethylaminomethyl)-
4-[{bis (2'-hydroxyethyl) amino} methyl] phenol, 2,6-bis (dimethylaminomethyl) -4-[{bis (2'-hydroxypropyl) amino} methyl] phenol, 4- ( Dimethylaminomethyl) -2,6-bis (3′-hydroxypyrrolidinomethyl) phenol, 4- (dimethylaminomethyl) -2,
6-bis (4′-hydroxypiperidinomethyl) phenol, 2,6-bis (pyrrolidinomethyl) -4-[{bis (2′-hydroxyethyl) amino} methyl] phenol, 2,6-bis ( Compounds having three hydroxyl groups such as piperidinomethyl) -4-[{bis (2'-hydroxyethyl) amino} methyl] phenol;

4-dimethylaminomethyl-2,6-bis [{bis (2'-hydroxyethyl) amino} methyl]
Phenol, 4-dimethylaminomethyl-2,6-bis [{bis (2'-hydroxypropyl) amino} methyl] phenol, 2,4,6-tris [bis (2'-
Hydroxyethyl) aminodimethyl] phenol, 2,
4,6-tris [bis (2'-hydroxypropyl)
Amino [methyl] phenol, 2,4,6-tris (3′-hydroxypyrrolidinomethyl) phenol,
2,4,6-tris (3′-hydroxymethylpyrrolidinomethyl) phenol, 2,4,6-tris [{3′-
(2 ″ -hydroxyethyl) pyrrolidino dimethyl] phenol, 2,4,6-tris (4′-hydroxypiperidinomethyl) phenol, 2,4,6-tris (4′-
Hydroxymethylpiperidinomethyl) phenol, 2,
4,6-tris [｛4 ′-(2 ″ -hydroxyethyl)
Compounds having four or more hydroxyl groups, such as piperidino dimethyl] phenol and 2,4,6-tris [{4 ′-(2 ″, 3 ″ -dihydroxypropyl) piperidino} methyl] phenol, may be mentioned. .

Specific examples of the basic compound (8) include 2
-Hydroxypyridine, 3-hydroxypyridine, 4-
Hydroxypyridine, 2-hydroxy-3-methylpyridine, 2-hydroxy-4-methylpyridine, 2-hydroxy-5-methylpyridine, 2-hydroxy-6-methylpyridine, 3-hydroxy-2-methylpyridine,
3-hydroxy-4-methylpyridine, 3-hydroxy-5-methylpyridine, 3-hydroxy-6-methylpyridine, 4-hydroxy-2-methylpyridine, 4-hydroxy-3-methylpyridine, 2-hydroxy-4 −
Ethylpyridine, 2-hydroxy-4-n-propylpyridine, 2-hydroxy-4-i-propylpyridine,
2-hydroxy-4-n-butylpyridine, 2-hydroxy-4-n-dodecylpyridine, 2-hydroxy-4
-Phenylpyridine, 2-hydroxy-4-benzylpyridine, 2-hydroxymethylpyridine, 3-hydroxymethylpyridine, 4-hydroxymethylpyridine,
-(2'-hydroxyethyl) pyridine, 3- (2'-
(Hydroxyethyl) pyridine, 4- (2′-hydroxyethyl) pyridine, 2- (2′-hydroxypropyl)
Pyridine, 3- (2′-hydroxypropyl) pyridine, 4- (2′-hydroxypropyl) pyridine, 4-
(4′-hydroxyphenyl) pyridine, 4- (4′-
Hydroxybenzyl) pyridine, 2-quinolinol, 3
-Quinolinol, 4-quinolinol, 1-isoquinolinol, 3-isoquinolinol, 4-isoquinolinol,
compounds having one hydroxyl group such as α-pyridoin;

2,3-dihydroxypyridine, 2,4-
Dihydroxypyridine, 2,5-dihydroxypyridine, 2,6-dihydroxypyridine, 3,4-dihydroxypyridine, 3,5-dihydroxypyridine, 2-hydroxy-3-hydroxymethylpyridine, 2-hydroxy-4-hydroxymethylpyridine , 2-hydroxy-5-hydroxymethylpyridine, 2-hydroxy-6
-Hydroxymethylpyridine, 3-hydroxy-4-hydroxymethylpyridine, 3-hydroxy-5-hydroxymethylpyridine, 2-hydroxy-3- (2'-hydroxyethyl) pyridine, 2-hydroxy-4-
(2′-hydroxyethyl) pyridine, 2-hydroxy-5- (2′-hydroxyethyl) pyridine, 2-hydroxy-6- (2′-hydroxyethyl) pyridine, 3
-Hydroxy-4- (2'-hydroxyethyl) pyridine, 3-hydroxy-5- (2'-hydroxyethyl)
Pyridine, 2,3-bis (hydroxymethyl) pyridine, 2,4-bis (hydroxymethyl) pyridine, 2,
5-bis (hydroxymethyl) pyridine, 2,6-bis (hydroxymethyl) pyridine, 3,4-bis (hydroxymethyl) pyridine, 3,5-di (hydroxymethyl) pyridine, 2,3-bis (2 ′ -Hydroxyethyl) pyridine, 2,4-bis (2′-hydroxyethyl) pyridine, 2,5-bis (2′-hydroxyethyl) pyridine, 2,6-bis (2′-hydroxyethyl) pyridine, 3, 4-bis (2'-hydroxyethyl) pyridine, 3,5-bis (2'-hydroxyethyl) pyridine, 3- (2'-pyridyl) -1,2-propanediol, 3- (3'-pyridyl) -1,2-propanediol, 3- (4'-pyridyl) -1,2-propanediol, 2- (2'-pyridyl) -1,3-propanediol, 2- (3'-pyridyl) -1 , 3 Propanediol, 2- (4'-pyridyl) -1,3-propanediol, 2- (2'-pyridyl) -1,4-butanediol, 2- (3'-pyridyl) -1,4-butanediol 2- (4'-pyridyl) -1,4-butanediol, 2- (2'-pyridyl) -2,3-butanediol, 2- (3'-pyridyl) -2,3-butanediol, -(4'-pyridyl) -2,3-butanediol, 2,3-di (2'-pyridyl) -1,4-butanediol, 2,3-di (3'-pyridyl) -1,4- Butanediol, 2,3-bis (4′-pyridyl) -1,4
-Butanediol, 2,3-bis (2'-pyridyl)-
2,3-butanediol, 2,3-bis (3′-pyridyl) -2,3-butanediol, 2,3-bis (4′-
Compounds having two hydroxyl groups, such as pyridyl) -2,3-butanediol;

2,6-dihydroxy-4-hydroxymethylpyridine, 3,5-dihydroxy-4-hydroxymethylpyridine, 2,6-dihydroxy-4- (2'-
Hydroxyethyl) pyridine, 3,5-dihydroxy-
4- (2′-hydroxyethyl) pyridine, 4-hydroxy-2,6-bis (hydroxymethyl) pyridine,
-Hydroxy-3,5-bis (hydroxymethyl) pyridine, 4-hydroxy-2,6-bis (2'-hydroxyethyl) pyridine, 4-hydroxy-3,5-bis (2'-hydroxyethyl) pyridine, 2,4,6-tris (hydroxymethyl) pyridine, 3,4,5-tris (hydroxymethyl) pyridine, 2,4,6-tris (2′-hydroxyethyl) pyridine, 3,4,5-tris ( Compounds having three hydroxyl groups such as 2′-hydroxyethyl) pyridine;

2,6-bis (2'-hydroxyethyl)
-4- (2 ', 3'-dihydroxypropyl) pyridine, 2,6-bis (2', 3'-dihydroxypropyl) pyridine, 2,6-bis (2 ', 3'-dihydroxypropyl) -4- (2′-hydroxyethyl) pyridine, 2,6-bis (2 ′, 3′-dihydroxypropyl) -4- (2′-hydroxypropyl) pyridine,
Compounds having four or more hydroxyl groups, such as 2,4,6-tris (2 ′, 3′-dihydroxypropyl) pyridine and 3,4,5-tris (2 ′, 3′-dihydroxypropyl) pyridine, and the like. Can be.

In the present invention, the basic compounds (3) to (3)
As (8), a compound having 2 to 3 carbon atoms between each nitrogen atom and each hydroxyl group is preferable, and the number of hydroxyl groups is more preferably 1 to (number of nitrogen atoms × 3), respectively. In particular, each of 1 to (the number of nitrogen atoms × 2 +
1) is preferred. Particularly preferred basic compound (c) in the present invention is 1,3-bis (dimethylamino) -2-
Propanol, 1,2-bis [4 ′-{N- (2 ″ -hydroxyethyl) piperidinyl}] propane, N, N,
N ′, N′-tetrakis (2-hydroxyethyl) ethylenediamine, N, N, N ′, N′-tetrakis (2-
(Hydroxypropyl) ethylenediamine, N, N′-bis (2-hydroxyethyl) piperazine, N, N′-bis (2-hydroxypropyl) piperazine, N, N,
N ′, N ″, N ″ -pentakis (2-hydroxyethyl) diethylenetriamine, N, N, N ′, N ″, N ″
-Pentakis (2-hydroxypropyl) diethylenetriamine, 2,4,6-tris (dimethylaminomethyl) phenol, 2,4,6-tris [{(2-hydroxyethyl) amino} methyl] phenol, 2,4,6
-Tris [{bis (2'-hydroxyethyl) amino}
Methyl] phenol, 3-hydroxypyridine, 4-hydroxypyridine and the like.

In the present invention, the basic compound (c) is
They can be used alone or in combination of two or more. The amount of the basic compound (c) used in the present invention is preferably 0.01 to 1 part by weight, particularly preferably 0.02 to 0.5 part by weight, per 100 parts by weight of the resin (a).
By setting the use amount of the basic compound (c) in the above range, a rectangular resist pattern having high sensitivity and in which "nano edge roughness" or "film surface roughness" is significantly suppressed can be obtained.

In the present invention, an acid diffusion controller other than the basic compound (c) (hereinafter referred to as "another acid diffusion controller") may be used together with the basic compound (c). . As other acid diffusion control agents, for example,
Tri-n-butylamine, tri-n-pentylamine,
Tri-n-hexylamine, tri-n-octylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, ethylenediamine, tetramethylenediamine,
Hexamethylenediamine, pyrrolidine, piperidine, imidazole, 4-methylimidazole, benzimidazole, 2-phenylbenzimidazole, pyridine, 2
-Methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-phenylpyridine, 3-phenylpyridine, 4-phenylpyridine, 2-benzylpyridine, 3
-Benzylpyridine, 4-benzylpyridine, nicotinamide, ribofuramine tetrabutyrate, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, , 2-Bis (4'-aminophenyl) propane, 2- (3'-aminophenyl)-
2- (4'-aminophenyl) propane,

2-di-n-propylamino-1-ethanol, 2-di-i-propylamino-1-ethanol,
3-di-n-propylamino-1-propanol, 3-
Di-i-propylamino-1-propanol, 2-di-
n-propylamino-1-propanol, 2-di-i-
Propylamino-1-propanol, 1-di-n-propylamino-2-propanol, 1-di-i-propylamino-2-propanol, 2- (4′-aminophenyl) -2- (3′-hydroxy Phenyl) propane, 2
-(4'-aminophenyl) -2- (4'-hydroxyphenyl) propane, N- (2-hydroxyethyl) pyrrolidine, N- (2-hydroxypropyl) pyrrolidine, N- (2-hydroxyethyl) piperidine, N-
(2-hydroxypropyl) piperidine, N- (2-hydroxyethyl) morpholine, N- (2-hydroxypropyl) morpholine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, α-pyridoin, methyl diethanolamine , Ethyl diethanolamine, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2,3-dihydroxypyridine, 2,4-dihydroxypyridine, 2,5-dihydroxypyridine, ,
Examples thereof include 6-dihydroxypyridine, 3,4-dihydroxypyridine, 3,5-dihydroxypyridine, triethanolamine, and tri-2-propanolamine.

Of these other acid diffusion controllers, tri-
n-butylamine, tri-n-pentylamine, tri-
n-hexylamine, tri-n-octylamine, dicyclohexylmethylamine, N, N-dimethylaniline, benzimidazole, 2-phenylbenzimidazole, 2-phenylpyridine, 4-phenylpyridine,
2-benzylpyridine, 4-benzylpyridine, nicotinamide, 4,4′-diaminodiphenyl ether,
N- (2-hydroxyethyl) piperidine, N- (2-
Preferred are (hydroxypropyl) piperidine, N- (2-hydroxyethyl) morpholine, N- (2-hydroxypropyl) morpholine, α-pyridoin, triethanolamine and the like.

The other acid diffusion controlling agent may be used alone or
A mixture of more than one species can be used. The amount of the other acid diffusion controlling agent to be used is generally 70% by weight or less, preferably 60% by weight or less, based on the total amount of the basic compound (c) and the other acid diffusion controlling agent. In this case, when the use amount of the other acid diffusion controller exceeds 70% by weight, the effect of suppressing "nano edge roughness" or "film surface roughness" in the present invention tends to decrease.

The radiation-sensitive resin composition of the present invention may optionally contain the following dissolution controlling agent. The dissolution controlling agent has a property of controlling the alkali solubility of the radiation-sensitive resin composition, and controls the alkali-solubility of the radiation-sensitive resin composition by dissociating in the presence of an acid, for example, by hydrolysis. It is a compound having an effect of reducing or eliminating the effect, or an effect of promoting alkali solubility of the radiation-sensitive resin composition. Examples of such a dissolution controlling agent include compounds in which a hydrogen atom in an acidic functional group such as a phenolic hydroxyl group and a carboxyl group has been replaced with an acid dissociable group. The dissolution controlling agent is
Although a low molecular weight compound or a high molecular weight compound may be used, preferred dissolution controlling agents include bisphenol A, bisphenol F, bisphenol S and 1,1-bis (4′-hydroxyphenyl) -1- [4 ′-{1 ′ '-Methyl-1''-
Compounds in which a hydrogen atom in an acidic functional group of a polyhydric phenolic compound such as (4 ″ ′-hydroxyphenyl) ethyl @ phenyl] ethane or a carboxylic acid compound such as 4-hydroxyphenylacetic acid is substituted with an acid dissociable group And the like. Specific examples of preferred low molecular weight compound dissolution controlling agents include the following structural formulas (12) and (13).
The compound shown by these can be mentioned.

[0063]

Embedded image

[0064]

Embedded image

Further, as the polymer dissolution controlling agent, a resin containing an acid dissociable group other than the resin (A) (hereinafter referred to as “dissolution controlling resin”) can be used. Here, the acid-dissociable group means a substituent that dissociates in the presence of an acid to exhibit alkali solubility with respect to the dissolution controlling agent. Such acid dissociable groups include, for example, substituted methyl groups,
Examples thereof include a 1-substituted ethyl group, a 1-branched alkyl group, a silyl group, a germyl group, an alkoxycarbonyl group, an alkoxycarbonylalkyl group, an acyl group, and a cyclic acid dissociable group. Examples of the substituted methyl group include a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group, a 2-methoxyethoxymethyl group, a benzyloxymethyl group, a benzylthiomethyl group,
Cyclopropylmethyl group, benzyl group, p-bromobenzyl group, p-nitrobenzyl group, p-methoxybenzyl group, p-methylthiobenzyl group, p-ethoxybenzyl group, p-ethylthiobenzyl group, diphenylmethyl group,
Examples thereof include a triphenylmethyl group and a piperonyl group. As the 1-substituted ethyl group, for example, 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-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropylethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, α-methylphenacyl group, etc. be able to. Examples of the 1-branched alkyl group include an i-propyl group, a sec-butyl group, a t-butyl group, and a 1,1-
Examples thereof include a dimethylpropyl group, a 1-methylbutyl group, and a 1,1-dimethylbutyl group. Examples of the silyl group include a trimethylsilyl group, a dimethylethylsilyl group, a methyldiethylsilyl group, a triethylsilyl group, a dimethyli-propylsilyl group, and a methylsilyl group.
Di-i-propylsilyl group, tri-i-propylsilyl group, dimethyl t-butylsilyl group, methyl di-t-
Examples thereof include a butylsilyl group, a tri-t-butylsilyl group, a dimethylphenylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group. Examples of the germyl group include a trimethylgermyl group, a dimethylethylgermyl group, a methyldiethylgermyl group, a triethylgermyl group, a dimethyli-propylgermyl group, a methyldi-i-propylgermyl group, Tri-i-propylgermyl group, dimethyl-t-butylgermyl group, methyl-di-t-butylgermyl group, tri-t
-Butylgermyl group, dimethylphenylgermyl group,
Examples thereof include a methyl-diphenylgermyl group and a triphenylgermyl group.

Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group,
Examples thereof include an i-propoxycarbonyl group, a t-butoxycarbonyl group, and a t-pentyloxycarbonyl group. Examples of the alkoxycarbonylalkyl group include a t-butoxycarbonylmethyl group, 2-t
-Butoxycarbonylethyl group and the like. Examples of the acyl group include, for example, acetyl, propionyl, butyryl, heptanoyl, hexanoyl, valeryl, pivaloyl, isovaleryl, lauryloyl, myristoyl, palmitoyl, stearoyl, oxalyl, malonyl, Succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azeolaoyl group, sebacoil group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group,
Mesaconoyl, camphoroyl, benzoyl, phthaloyl, isophthaloyl, terephthaloyl, naphthoyl, toluoyl, hydroatropoyl, atropoyl, cinnamoyl, furoyl, tenoyl, nicotinoyl, isonicotinoyl, p- Examples thereof include a toluenesulfonyl group and a mesyl group. Examples of the cyclic acid dissociable group include, for example, cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, oxocyclohexenyl group, 4-methoxycyclohexyl group, tetrahydrofuranyl group, tetrahydropyranyl group, tetrahydrothiofuranyl Group, tetrahydrothiopyranyl group, 3-bromotetrahydropyranyl group, 4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, S, S-dioxide group, 2-1,3-dioxolanyl group, 2 -1,3-dithiolanyl group, benzo-2-1,3-dioxolanyl group,
A benzo-2-1,3-dithiolanyl group and the like can be mentioned.

Among these acid dissociable groups, t-butyl, benzyl, t-butoxycarbonyl, t-butoxycarbonylmethyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydrothiofuranyl,
A tetrahydrothiopyranyl group and the like are preferred.

The dissolution-controlling resin is prepared, for example, by introducing one or more acid-dissociable groups into an alkali-soluble resin having an acidic functional group. It can be produced by a method of (co) polymerization, a method of (co) condensing a polycondensation component having one or more kinds of the acid dissociable groups, or the like. The rate of introduction of the acid-dissociable group in the dissolution-controllable resin (the ratio of the number of acid-dissociable groups to the total number of acidic functional groups and acid-dissociable groups in the dissolution-controllable resin) is preferably 15 to 100%. More preferably, 20 to 100
%, Particularly preferably 20 to 80%. Mw of the dissolution controlling resin is preferably 1,000 to 150,000,
More preferably, it is 3,000 to 100,000.
The dissolution controlling agent can be used alone or in combination of two or more of the low molecular compound and the high molecular compound (that is, the dissolution controlling resin), and the low molecular compound and the high molecular compound are used in combination. You can also. The amount of the dissolution controlling agent is 10 parts by weight per 100 parts by weight of the resin (a).
0 parts by weight or less is preferred. In this case, if the amount of the dissolution controlling agent is more than 100 parts by weight, the film forming property and the film strength of the resin composition tend to be reduced.

Other Additives The radiation-sensitive resin composition of the present invention may further contain other additives such as a surfactant and a sensitizer, if necessary. The surfactant has an effect of improving the applicability and striation of the radiation-sensitive resin composition solution, the developability of the resist, and the like. Examples of such surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene glycol dilaurate,
In addition to polyoxyethylene glycol distearate,
KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Polyflow No. 75, No95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK), F-Top EF301, EF303, EF
352 (manufactured by Tochem Products Co., Ltd.), Megafac F171, F172, F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Florado FC430, FC431 (manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S- 382, SC-101, SC-102, SC
-103, SC-104, SC-105, SC-106
(Made by Asahi Glass Co., Ltd.). These surfactants can be used alone or in combination of two or more. The amount of the surfactant is usually 2 parts by weight or less per 100 parts by weight of the total solids in the radiation-sensitive resin composition. The sensitizer absorbs radiation energy and transmits the energy to the acid generator (b), thereby increasing the amount of acid produced. This has the effect of improving the sensitivity of the resist obtained using the resin composition. Preferred specific examples of the sensitizer include acetone, benzene, acetophenones, benzophenones, naphthalenes, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines and the like. These sensitizers can be used alone or in combination of two or more. The compounding amount of the sensitizer is usually 50 parts by weight or less, preferably 30 parts by weight or less, based on 100 parts by weight of the total solids in the radiation-sensitive resin composition. Further, by adding a dye or a pigment, the effect of halation at the time of exposure can be reduced, and by adding an adhesion aid, the adhesion to the substrate can be improved. further,
Other additives include antihalation agents such as azo compounds and amine compounds, storage stabilizers, defoamers, shape improvers and the like.

Solvent The radiation-sensitive resin composition of the present invention may be used,
After being dissolved in a solvent so that the solid content concentration is, for example, 0.5 to 50% by weight, preferably 0.5 to 40% by weight,
For example, a resist solution is prepared by filtering with a filter having a pore size of about 0.2 μm. As the solvent used for preparing the resist solution, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-
Ethylene glycol monoalkyl ethers such as propyl ether and ethylene glycol mono-n-butyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate Ethylene glycol monoalkyl ether acetates such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether and the like; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Recall mono -n- propyl ether, propylene glycol monoalkyl ethers such as propylene glycol monobutyl -n- butyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di -n
Propylene glycol dialkyl ethers such as propyl ether and propylene glycol di-n-butyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate Propylene glycol monoalkyl ether acetates;

Lactic esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate and isobutyl lactate; methyl formate, ethyl formate, n-propyl formate, i-propyl formate, n-butyl formate I-butyl formate, n-amyl formate, i-amyl formate, methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-acetate Amyl, n-hexyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, i-propyl propionate, n-butyl propionate, i-butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, Aliphatic carboxylic acid esters such as i-propyl butyrate, n-butyl butyrate, i-butyl butyrate; Le, 2-hydroxy-2-methylpropionic acid ethyl, 2-hydroxy-3-methyl-butyric acid methyl, ethyl methoxy acetate, ethoxyethyl acetate,
Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-
Ethyl ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate,
3-methyl-3-methoxybutyl propionate, 3-
Other esters such as methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, 2-heptanone, 3- Ketones such as heptanone, 4-heptanone and cyclohexanone; N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N
Amides such as -dimethylacetamide and N-methylpyrrolidone; lactones such as γ-butyrolactone;

These solvents can be used alone or in combination of two or more. The amount of the solvent used in preparing the resist solution is usually 100 to 20,000 parts by weight, preferably 150 to 15,000 parts by weight, and more preferably 100 parts by weight of the total solids of the radiation-sensitive resin composition. Is from 200 to 10,000 parts by weight.

Formation of Resist Pattern When a resist pattern is formed from the radiation-sensitive resin composition of the present invention, a resist solution is applied to a silicon wafer, aluminum, or the like by means of spin coating, casting coating, roll coating, or the like. After coating on a substrate such as a coated wafer, pre-baking (PB)
After forming a resist film, the resist film is exposed so as to form a desired pattern. The radiation used at that time depends on the type of the acid generator (b) used, i.
Ultraviolet rays such as rays, far ultraviolet rays such as excimer laser, X-rays such as synchrotron radiation, and charged particle beams such as electron beams are appropriately selected and used, and far ultraviolet rays, X-rays and charged particle beams are particularly preferable. Exposure conditions such as the amount of exposure are appropriately selected according to the composition of the radiation-sensitive resin composition, types of additives, and the like. When a resist pattern is formed using the radiation-sensitive resin composition of the present invention, a protective film may be provided on the resist film in order to prevent the influence of basic impurities and the like contained in the working atmosphere. it can. In the present invention, in order to improve the apparent sensitivity of the resist film, it is preferable to perform baking (PEB) after exposure. The heating conditions vary depending on the composition of the radiation-sensitive resin composition, types of additives, and the like, but are usually 50 to 20.
0 ° C., preferably 80 to 160 ° C. Next, a predetermined resist pattern is formed by developing with an alkali developing solution. Examples of the alkali developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyl Diethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-
Alkaline compounds such as [5,4,0] -7-undecene and 1,5-diazabicyclo- [4.3.0] -5-nonene are usually added in an amount of 1 to 10% by weight, preferably 2 to 5% by weight.
An alkaline aqueous solution dissolved so as to have a concentration of is used. Further, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the developer. When a developer composed of an alkaline aqueous solution is used, the developer is generally washed with water after the development.

[0074]

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to these embodiments. Each resist in Examples and Comparative Examples was evaluated in the following manner. The resist film formed on the silicon wafer was exposed to light at a different exposure amount, immediately subjected to PEB, and then alkali-developed, washed with water and dried to form a resist pattern. The exposure amount for forming the line-and-space pattern (1L1S) to have a line width of 1: 1 is defined as an optimum exposure amount, and the optimum exposure amount is
Sensitivity. Resolution The minimum dimension (μm) of the resist pattern that was resolved when exposed at the optimal exposure amount was taken as the resolution. Pattern Size The lower side dimension La and the upper side dimension Lb of a rectangular cross section of a line and space pattern (1L1S) having a line width of 0.26 μm formed on a silicon wafer are measured using a scanning electron microscope. 0.85 ≦ Lb / La ≦ 1 and having no “gouge” near the base of the pattern or “eave” in the upper layer portion, the pattern shape is regarded as “good”, and at least one of these conditions is satisfied. Those that did not satisfy one were determined to have a pattern shape of “impossible”. For the line-and-space pattern (1L1S) having a designed line width of 0.26 μm, the cross-sectional dimension of the line pattern was measured by a scanning electron microscope, and as shown in FIG.
Of the cross-sectional dimensions of the line pattern, the minimum dimension is Lin,
The maximum dimension was defined as Lout, and (Lout−Lin) was defined as ΔL. FIG.
Are more exaggerated than they actually are. ΔL is less than 0.01 μm: good ΔL is 0.01 μm or more: improper

[0075]

Examples 1 to 21 and Comparative Examples 1 to 3 Resin (a), acid generator (b), basic compound (c) or another compound as acid diffusion controller, dissolution inhibitor and solvent After mixing at a ratio shown in Table 1 or Table 2 to obtain a uniform solution, the solution was filtered through a membrane filter having a pore diameter of 0.2 μm to prepare a resist solution. Next, after applying each resist solution on a silicon wafer by a spin coater, PB was performed at the temperature and time shown in Table 3 or Table 4 to form a 0.7 μm-thick resist film. Then, after exposure with radiation shown in Table 3 or Table 4, PEB was performed at the temperature and time shown in Table 3 or Table 4. Thereafter, the resist film was developed by an immersion method at 23 ° C. for 1 minute using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, and then washed with water for 30 seconds. Table 5 shows the evaluation results of the respective resists.

[0076]

[Table 1]

[0077]

[Table 2]

The components in Tables 1 and 2 are as follows. Resin (a) A1: Resin in which 32 mol% of hydrogen atoms of phenolic hydroxyl groups in poly (4-hydroxystyrene) have been substituted with 1-ethoxyethyl groups (Mw = 15,000) A2: Poly (4-hydroxystyrene) Resin (Mw = 16,000) wherein 25 mol% of hydrogen atoms of phenolic hydroxyl groups in styrene) are substituted with 1-ethoxyethyl groups and 8 mol% of the hydrogen atoms are substituted with t-butoxycarbonyl groups.
0) Acid generator (b) B1: bis (cyclohexylsulfonyl) diazomethane B2: bis (1,4-dioxaspiro [4.5] decane-7-sulfonyl) diazomethane B3: bis (t-butylsulfonyl) diazomethane B4: tri Phenylsulfonium nonafluoro-
n-butanesulfonate B5: bis (4-t-butylphenyl) iodonium 10-camphorsulfonate B6: 4-t-butoxyphenyl / diphenylsulfonium p-toluenesulfonate

Acid diffusion controller Basic compound (c) C1: 1,3-bis (dimethylamino) -2-propanol C2: N, N'-bis (2-hydroxyethyl) piperazine C3: 1,2-bis [4 ′-{N- (2 ″ -hydroxyethyl) piperidinyl}] propane C4: N, N, N ′, N′-tetrakis (2-hydroxyethyl) ethylenediamine C5: N, N, N ′, N ′ -Tetrakis (2-hydroxypropyl) ethylenediamine C6: N, N, N ', N ", N" -pentakis (2
-Hydroxypropyl) diethylenetriamine C7: 2,4,6-tris (dimethylaminomethyl) phenol C8: 2,4,6-tris [{bis (2'-hydroxyethyl) amino} methyl] phenol C9: 4-hydroxypyridine

Other compounds c1: tri-n-butylamine c2: N, N-dimethylaniline c3: N- (2-hydroxyethyl) piperidine

Dissolution controlling agent D1: Compound represented by the above structural formula (12) D2: 25 mol% of hydrogen atoms of phenolic hydroxyl groups in poly (4-hydroxystyrene) were substituted with t-butoxycarbonyl groups. Resin (Mw = 15,000) D3: Resin (Mw = 15,000) in which 25 mol% of hydrogen atoms of phenolic hydroxyl groups in poly (4-hydroxystyrene) are substituted by t-butoxycarbonylmethyl group.
0) D4: Copolymer of 4-hydroxystyrene, t-butyl acrylate and styrene (copolymer molar ratio = 6: 2:
2, Mw = 13,000) Solvent EL: Ethyl lactate EEP: Ethyl 3-ethoxypropionate MMP: Methyl 3-methoxypropionate PGMEA: Propylene glycol monomethyl ether acetate MAK: 2-Heptanone

[0082]

[Table 3]

[0083]

[Table 4]

[0084]

[Table 5]

[0085]

The radiation-sensitive resin composition of the present invention is excellent in sensitivity, resolution and pattern shape, and is particularly subjected to fine processing near the design dimension of 0.20 μm with a small film thickness (for example, 0.7 μm or less). Even at this time, "nano edge roughness" or "film surface roughness" does not occur, and a highly accurate and fine resist pattern can be stably formed. Moreover, the radiation-sensitive resin composition of the present invention can effectively respond to various radiations such as far ultraviolet rays, X-rays, and charged particle beams. Therefore, the radiation-sensitive resin composition of the present invention can be very suitably used as a chemically amplified resist for manufacturing semiconductor devices, which is expected to be further miniaturized in the future.

[Brief description of the drawings]

FIG. 1 is a side sectional view of a resist pattern for explaining a procedure for evaluating film surface roughness.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/027 H01L 21/30 502R (72) Inventor Shinichiro Iwanaga 2-11-24 Tsukiji 2-chome, Chuo-ku, Tokyo JSR Co., Ltd. F term (reference) 2H025 AA00 AA01 AA02 AA03 AC06 AC08 AD03 BE00 BE10 BG00 CC20 FA12 FA17 4J002 BC121 EN036 EN046 EU046 EU086 EU136 FD200 FD206 FD310 GQ04 4J100 AB02Q AB03Q AB07P A07Q03 A01Q03 A01 AM15Q AQ06Q AQ08Q AQ12Q BA02Q BA04H BA04Q BA05H BA05Q BA06H BA10H BA15Q BA16Q BA20Q BB01Q BC03P BC03Q BC04Q BC08Q BC09Q BC12Q BC43Q BC53H BC53Q CA01 CA04 CA31 HA61 JA38 JA46

Claims (1)

[Claims] 1. (A) (I) a resin having, as essential units, a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2); A radiation-sensitive resin composition, comprising: (c) at least one basic compound selected from the group of compounds represented by the following general formulas (3) to (8): . Embedded image [In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Show. [Chemical formula 2] [In the general formula (2), R ⁴ represents a hydrogen atom or a methyl group. [Chemical formula 3] [In the general formula (3), X ¹ represents a polymethylene chain having a main chain carbon number of 2 to 8, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a linear chain having 1 to 12 carbon atoms. Or a branched or cyclic alkyl group, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, or R ⁵ and R ⁶ are bonded, or R ⁷ and R ⁸ are bonded. Each of which forms a 5- to 8-membered heterocyclic structure together with one nitrogen atom in the general formula (3), and the rest of R ^{5 to} R ⁸ are each independently a straight-chain having 1 to 12 carbon atoms; A branched or cyclic alkyl group, an aryl group having 6 to 12 carbon atoms, or 7 to 1 carbon atoms
2 represents an aralkyl group, and at least one of the polymethylene chain, alkyl group, aryl group, aralkyl group and heterocyclic structure has at least one hydroxyl group bonded to a carbon atom. However, the polymethylene chain, the alkyl group, the aryl group, the aralkyl group and the heterocyclic structure may have an oxygen atom, a sulfur atom or a carbonyl group between any of their carbon-carbon bonds. A hydrogen atom bonded to an atom may be substituted with one or more substituents other than a hydroxyl group such as an alkoxyl group and a phenoxy group. [Formula 4] [In the general formula (4), R ⁹ and R ¹⁰ are each independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a C ^{7 to} C
12 represents an aralkyl group, and has at least one of the alkyl group, the aryl group, the aralkyl group, and at least one hydroxyl group bonded to a carbon atom in the general formula (4). However, the alkyl group, aryl group and aralkyl group may have an oxygen atom, a sulfur atom or a carbonyl group between any of their carbon-carbon bonds, and a hydrogen atom bonded to any of those carbon atoms It may be substituted with one or more substituents other than a hydroxyl group such as an alkoxyl group and a phenoxy group. [Chemical formula 5] [In the general formula (5), X ² represents a polymethylene chain having a main chain carbon number of 2 to 8, and R ¹¹ and R ¹² independently of each other have a linear, branched or cyclic shape having 1 to 12 carbon atoms. Alkyl group, aryl group having 6 to 12 carbon atoms or 7 to 7 carbon atoms
12 aralkyl groups, and said polymethylene chain,
An alkyl group, an aryl group, an aralkyl group, and at least one hydroxyl group in which at least one of one or two piperidine rings in formula (5) is bonded to a carbon atom. However, the polymethylene chain, the alkyl group, the aryl group and the aralkyl group can have an oxygen atom, a sulfur atom or a carbonyl group between any of their carbon-carbon bonds, and are bonded to any of those carbon atoms. A hydrogen atom may be substituted with one or more substituents other than a hydroxyl group such as an alkoxyl group and a phenoxy group. [Formula 6] [In the general formula (6), X ³ and X ⁴ independently represent a polymethylene chain having a main chain carbon number of 2 to 8, and R ¹³ ,
R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ independently of one another have 1 to 1 carbon atoms
12 linear, branched or cyclic alkyl group, or an aryl group or an aralkyl group having 7 to 12 carbon atoms of 6 to 12 carbon atoms, or R ¹³ and R ¹⁴ are bonded to each other or R ^16, And R ¹⁷ are mutually bonded to form a 5- to 8-membered heterocyclic structure together with one nitrogen atom in the general formula (6), and the rest of R ^{13 to} R ¹⁷ are each independently a carbon atom. Number 1
A linear, branched or cyclic alkyl group, an aryl group having 6-12 carbon atoms or an aralkyl group having 7-12 carbon atoms, and the polymethylene chain, alkyl group, aryl group, aralkyl group and At least one of the ring structures has at least one hydroxyl group bonded to a carbon atom. However, the polymethylene chain, the alkyl group, the aryl group, the aralkyl group and the heterocyclic structure may have an oxygen atom, a sulfur atom or a carbonyl group between any of their carbon-carbon bonds. A hydrogen atom bonded to an atom may be substituted with one or more substituents other than a hydroxyl group such as an alkoxyl group and a phenoxy group. [Formula 7] [In the general formula (7), R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R
²² and R ²³ are each independently a linear group having 1 to 12 carbon atoms;
A branched or cyclic alkyl group, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, or R ¹⁸ and R ¹⁹ are mutually bonded, or R ²⁰ and R ²¹ are mutually R ²² and R ²³ are bonded to each other to form a 5- to 8-membered heterocyclic structure together with one nitrogen atom in the general formula (7), and the remaining R ^{18 to} R ²³ Each independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. However, the alkyl group, the aryl group, the aralkyl group and the heterocyclic structure may have at least one hydroxyl group having at least one of them bonded to a carbon atom, and an oxygen atom between any of the carbon-carbon bonds. , A sulfur atom or a carbonyl group, and a hydrogen atom bonded to any carbon atom thereof may be substituted with one or more substituents other than a hydroxyl group such as an alkoxyl group and a phenoxy group. Embedded image [In the general formula (8), R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ each independently represent a hydrogen atom, a hydroxyl group, a carbon number of 1 to 1
2 linear, branched or cyclic alkyl group, or an aryl group or an aralkyl group having 7 to 12 carbon atoms of 6 to 12 carbon atoms, or R ²⁴ and R ²⁵ are bonded to each other or R ^25, And R ²⁶ are mutually bonded, or R ²⁶ and R ²⁷ are mutually bonded, or R ²⁷ and R ²⁸ are mutually bonded,
Each of the two carbon atoms in the general formula (8) forms a 6-membered aromatic ring structure together with the two carbon atoms, and the rest of R ^{24 to} R ²⁸ are independently a hydrogen atom, a hydroxyl group, a straight chain having 1 to 12 carbon atoms. , A branched or cyclic alkyl group, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms;
Or that at least one hydroxyl group of ²⁴ to R ^28, or having the alkyl group, an aryl group, at least one aralkyl group and aromatic ring structures wherein one or more hydroxyl groups bonded to a carbon atom. However, when at least one of R ^{24 to} R ²⁸ is a hydroxyl group, at least one of the remaining alkyl groups, aryl groups, aralkyl groups and aromatic ring structures of R ^{24 to} R ²⁸ can have one or more hydroxyl groups. The alkyl group, the aryl group, the aralkyl group and the aromatic ring structure may have an oxygen atom, a sulfur atom or a carbonyl group between any of their carbon-carbon bonds, and may be bonded to any of those carbon atoms. A hydrogen atom other than a hydroxyl group such as an alkoxyl group, a phenoxy group or a pyridyl group;
It may be substituted with one or more substituents. ]