JP2001324811A - Negative type radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative type radiation sensitive resin composition suitable for use as a chemical amplification type negative type resist developable with an alkali developing solution having the conventional concentration, capable of forming a high resolution rectangular resist pattern in an ordinary line-and- space pattern (1L1S) and excellent also in focus latitude. SOLUTION: The negative type radiation sensitive resin composition contains (A) an alkali-soluble resin having a phenolic hydroxyl group, (B) a radiation sensitive acid generating agent and (C) a compound having an α- hydroxyisopropyl group and/or an acid dissociable derivative of an α- hydroxyisopropyl group. The component (C) is typified by 1,3-bis(α- hydroxyisopropyl)benzene, 4,4'-bis(α-hydroxyisopropyl)biphenyl or 2,6-bis(α- hydroxyisopropyl)naphthalene, and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art In the field of fine processing typified by the manufacture of integrated circuit elements, the processing size in lithography has been rapidly reduced in order to obtain a higher degree of integration. There is a need for a technique capable of stably performing fine processing of 0.25 μm or less. Therefore, the resist used is also 0.2
It is required that a fine resist pattern of 5 μm or less can be formed with high precision. From that viewpoint, lithography using radiation having a shorter wavelength is being studied. Such short-wavelength radiation includes far ultraviolet rays typified by KrF excimer laser (wavelength 248 nm) and ArF excimer laser (wavelength 193 nm), charged particles typified by X-ray typified by synchrotron radiation, and electron beams. Lines and the like are used, and various resists that can cope with these radiations have been studied in recent years. Among such resists, those which are particularly noticed use a reaction in which an acid is generated by irradiation with radiation (hereinafter, referred to as "exposure"), and the solubility of the resist in a developer is changed by the catalytic action of the acid. There is a “chemically amplified resist”.

When an integrated circuit is actually manufactured using a resist, usually, resist components such as a radiation-sensitive component and a film-forming component are dissolved in a solvent to prepare a resist solution. A solution is applied on a substrate to be processed, a resist film is formed, and then the resist film is exposed through a predetermined mask and developed to form a resist pattern suitable for fine processing. are doing. At that time, the cross-sectional shape of the pattern has a significant effect on the precision of the fine processing, and a rectangular shape is preferred.
In a chemically amplified negative resist, a resist pattern is formed by, for example, causing a cross-linking reaction in an exposed portion to reduce a dissolution rate in a developer, and a conventional chemically amplified negative resist is used. Since the contrast of the dissolution rate between the exposed part and the non-exposed part with respect to the developing solution is not sufficient, there are disadvantages that the resolution is low and the head shape of the pattern is not rectangular but round. Further, the dissolution rate of the exposed portion in the developing solution is not sufficiently reduced, and the resist pattern is disadvantageously swollen or meandered by the developing solution.

To solve the above-mentioned problem of the conventional chemically amplified negative resist, Japanese Patent Laid-Open Publication No.
339 and JP-A-2-15270,
A chemically amplified negative resist composition using an amino resin such as a glycoluril resin as a crosslinking agent is disclosed in JP-A-5-3492.
JP-A-6-3 discloses a chemically amplified negative resist composition containing a partially hydrogenated phenolic resin and a glycoluril resin crosslinking agent having a defined mononuclear ratio.
No. 01200 discloses a chemically amplified negative resist composition using a crosslinking agent comprising an N- (alkoxymethyl) glycoluril compound. However, these resist compositions have a line width of 0.2
It was difficult to form a fine resist pattern of 5 μm or less at a satisfactory level. More recently, as a chemically amplified negative resist composition with particularly improved resolution, a composition in which the degree of dispersion of an alkali-soluble resin, the amount of a low molecular weight component, and the like are specified is disclosed in JP-A-7-120924,
JP-A-7-31463, JP-A-8-44061
And JP-A-8-292559. However, these resist compositions are still unsatisfactory in terms of resolution, pattern shape, and focus margin, which are important characteristics of ordinary negative resists.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to apply an alkaline developing solution having a normal concentration and to form a high-resolution rectangular resist pattern in a normal line-and-space pattern (1L1S). It is an object of the present invention to provide a negative-type radiation-sensitive resin composition which can be formed and is excellent in a focus margin and suitable as a chemically amplified negative-type resist.

[0006]

According to the present invention, the above object is achieved by (A) a polymerizable unsaturated compound having a phenolic hydroxyl group in which a polymerizable unsaturated bond is cleaved, and an unsubstituted or substituted recurring unit. (B) a radiation-sensitive acid generator, and (C) a α-hydroxyisopropyl group and / or an α-hydroxyisopropyl group. This is achieved by a negative radiation-sensitive resin composition comprising a compound having an acid dissociable derivative.

Hereinafter, the present invention will be described in detail. (A) Component The component (A) in the present invention comprises a repeating unit in which a polymerizable unsaturated bond of a polymerizable unsaturated compound having a phenolic hydroxyl group (hereinafter referred to as “phenolic unsaturated compound”) is cleaved, An alkali-soluble resin (hereinafter referred to as “resin (A)”) having a substituted or substituted styrene-based compound (hereinafter simply referred to as “other styrene-based compound”) and a repeating unit in which a polymerizable unsaturated bond is cleaved. )). In the resin (A), examples of the phenolic unsaturated compound include o-vinylphenol, m-vinylphenol, p-vinylphenol, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol and the like. Can be mentioned. These phenolic unsaturated compounds can be used alone or in combination of two or more.

[0008] Examples of the substituent in other styrene compounds include a methyl group, an ethyl group, an n-propyl group,
i-propyl group, n-butyl group, i-butyl group, sec
A butyl group, a linear or branched alkyl group having 1 to 4 carbon atoms such as a t-butyl group; a methoxy group, an ethoxy group,
a linear or branched alkoxyl group having 1 to 4 carbon atoms such as an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a sec-butoxy group, a t-butoxy group; a fluorine atom, Examples include a halogen atom such as a chlorine atom, a bromine atom and an iodine atom.

Specific examples of other styrene compounds include:
In addition to styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methylstyrene
Styrene derivatives substituted with an alkyl group such as t-butylstyrene; p-methoxystyrene, p-ethoxystyrene, p-n-propoxystyrene, p-i-propoxystyrene, p-n-butoxystyrene, p-t Styrene derivatives substituted with an alkoxyl group such as butoxystyrene; and styrene derivatives substituted with a halogen atom such as p-fluorostyrene, p-chlorostyrene and p-bromostyrene. These other styrene compounds can be used alone or in combination of two or more.

The resin (A) further comprises a polymerizable unsaturated compound other than a phenolic unsaturated compound and another styrene compound (hereinafter, simply referred to as “other unsaturated compound”).
May have a repeating unit in which the polymerizable unsaturated bond is cleaved. As other unsaturated compounds, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate,
i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate,
Alkyl (meth) acrylates such as 2-ethylexyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate Kind;
Other (meth) acrylates such as cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and isobornyl (meth) acrylate;

Unsaturated nitrile compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile and vinylidene cyanide; (meth)
Unsaturated amide compounds such as acrylamide, N, N-dimethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide; (meth) acrylic acid;
Unsaturated carboxylic acids (anhydrides) such as cinnamic acid, maleic acid, maleic anhydride and fumaric acid; maleimides such as maleimide, N-cyclohexylmaleimide and N-phenylmaleimide; N-vinylpyrrolidone and N-vinylcaprolactam And heteroatom-containing alicyclic vinyl compounds. These other unsaturated compounds can be used alone or in combination of two or more.

Specific examples of the resin (A) include, for example, p
-Vinylphenol / styrene copolymer, p-vinylphenol / α-methylstyrene copolymer, p-vinylphenonol / p-methoxystyrene copolymer, p-vinylphenol / p-ethoxystyrene copolymer, p -Vinylphenol / other styrene compound copolymers such as vinylphenol / pn-propoxystyrene copolymer and p-vinylphenol / pn-butoxystyrene copolymer; p-isopropenylphenol / styrene Copolymer, isopropenylphenol such as p-isopropenylphenol / α-methylstyrene copolymer / other styrene compound copolymers; p-vinylphenol /
Styrene / methyl (meth) acrylate copolymer, p-
Vinylphenol / styrene / 2-hydroxyethyl (meth) acrylate copolymer, p-vinylphenol / styrene / 2-hydroxypropyl (meth) acrylate copolymer, p-vinylphenol / styrene / 3-
Vinylphenol / styrene / (meth) acrylate copolymers such as hydroxypropyl (meth) acrylate copolymer; p-vinylphenol / styrene /
Examples thereof include (meth) acrylonitrile copolymers, phenolic unsaturated compounds such as p-isopropenylphenol / styrene / (meth) acrylonitrile copolymer / styrene / unsaturated nitrile compound copolymers.

Among these resins (A), in particular, p-vinylphenol / styrene copolymer, p-vinylphenol / α-methylstyrene copolymer, p-vinylphenol / p-methoxystyrene copolymer, P-vinylphenol / p-ethoxystyrene copolymer and the like are preferred.

In the resin (A), the content of the repeating unit derived from the phenolic unsaturated compound is usually from 50 to 50.
It is 95 mol%, preferably 60 to 90 mol%, particularly preferably 70 to 85 mol%. In this case, when the content of the repeating unit derived from the phenolic unsaturated compound is less than 50 mol%, the dissolution rate in an alkali developing solution is reduced, and the developability and resolution of the resist tend to be impaired. If the amount exceeds mol%, swelling due to the alkali developing solution is likely to occur, and the pattern shape may be damaged or a pattern defect may occur. When the resin (A) has a repeating unit derived from another unsaturated compound, the content of the other repeating unit varies depending on the type of the repeating unit, but is usually 50 mol%.
Is less than.

The method for producing the resin (A) includes, for example, (i) monomers in which the phenolic hydroxyl group of a phenolic unsaturated compound is protected, such as pt-butoxycarbonyloxystyrene, pt-butoxystyrene, p
-Acetoxystyrene, p-tetrahydropyranyloxystyrene, etc., and another styrenic compound, optionally in the presence of another unsaturated compound, after addition polymerization,
A method in which a protecting group is eliminated by a hydrolysis reaction in the presence of an acid catalyst or a basic catalyst; (ii) a phenolic unsaturated compound and another styrenic compound are optionally added in the presence of another unsaturated compound. And the method of addition polymerization can be mentioned, but the method (i) is preferable.

The addition polymerization is, for example, radical polymerization,
The method can be carried out by an appropriate method such as anionic polymerization, cationic polymerization, thermal polymerization and the like, but a method using anionic polymerization or cationic polymerization is preferable in that the degree of dispersion of the obtained copolymer can be reduced. Examples of the acid catalyst used in the method (i) include, for example, inorganic acids such as hydrochloric acid and sulfuric acid. Examples of the basic catalyst include an organic base such as a trialkylamine and a hydroxylic acid. Examples include inorganic bases such as sodium.

The resin (A) has a weight average molecular weight in terms of polystyrene (hereinafter, referred to as “Mw”) of 2,000 to 2 by gel permeation chromatography (GPC).
000, preferably 3,000 to 10,000, and a ratio (Mw / Mn) of Mw to a number average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) (hereinafter, referred to as “Mn”). It is desirable that the defined degree of dispersion is 1.8 or less, preferably 1.3 or less. In this case, Mw of the resin (A) is 2,0
If it is less than 00, the film-forming properties of the composition, the sensitivity as a resist, and the like tend to decrease. If it exceeds 1.8, the resolution as a resist tends to decrease. In the present invention,
The resin (A) can be used alone or in combination of two or more.

Component (B) The component (B) in the present invention comprises a radiation-sensitive acid generator that generates an acid upon exposure (hereinafter, referred to as “acid generator (B)”). As the acid generator (B), for example,
Examples thereof include an onium salt compound, a sulfonimide compound, a diazomethane compound, a disulfonylmethane compound, a halogen-containing compound, a sulfone compound, and a sulfonate compound. Hereinafter, examples of these acid generators (B) will be described.

Onium salt: Examples of the onium salt include a sulfonium salt, an iodonium salt, a phosphonium salt, a diazonium salt, an ammonium salt, and a pyridinium salt. Of these, a sulfonium salt and an iodonium salt are preferable. Specific examples of the sulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumbenzene Sulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium n-dodecylbenzenesulfonate, triphenylsulfonium 2-trifluoromethylbenzenesulfonate, triphenylsulfonium 4
-Trifluoromethylbenzenesulfonate, triphenylsulfonium 2,4-difluorobenzenesulfonate, triphenylsulfonium pentafluorobenzenesulfonate, triphenylsulfonium 1-naphthalene sulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, diphenyl-4-methyl Phenylsulfonium nonafluoro-n
-Butanesulfonate, diphenyl-4-methylphenylperfluoro-n-octanesulfonate, diphenyl-4-methylphenylsulfonium p-toluenesulfonate, diphenyl-4-methylphenylsulfonium 10-camphorsulfonate,

Diphenyl-2,4-dimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-2,4-dimethylphenylsulfonium nonafluoro-n-butanesulfonate, diphenyl-2,4-dimethylphenylsulfonium perfluoro-n-octanesulfonate, Diphenyl-2,4-dimethylphenylsulfonium p-toluenesulfonate, diphenyl-2,4-dimethylphenylsulfonium 10-camphorsulfonate, diphenyl-2,4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-2,4,6 -Trimethylphenylsulfonium nonafluoro-n-butanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium perfluoro-n Octanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium 10-camphorsulfonate, diphenyl-4-t-butylphenylsulfonium trifluoromethanesulfonate, diphenyl- 4-t
-Butylphenylsulfonium nonafluoro-n-butanesulfonate, diphenyl-4-t-butylphenylsulfonium perfluoro-n-octanesulfonate, diphenyl-4-t-butylsulfonium p-toluenesulfonate, diphenyl-4-t-butylphenyl Sulfonium 10-camphorsulfonate,

Diphenyl-4-fluorophenylsulfonium trifluoromethanesulfonate, diphenyl-
4-fluorophenylsulfonium nonafluoro-n-
Butanesulfonate, diphenyl-4-fluorophenylsulfonium perfluoro-n-octanesulfonate, diphenyl-4-fluorophenylsulfonium p
-Toluenesulfonate, diphenyl-4-fluorophenylsulfonium 10-camphorsulfonate, diphenyl-4-hydroxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, diphenyl-4-hydroxyphenylsulfonium par Fluoro-n-octanesulfonate, diphenyl-4-hydroxyphenylsulfonium p-toluenesulfonate, diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate, diphenyl-4-methoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-methoxyphenylsulfonium nona Fluoro-n-butanesulfonate, diphenyl-4 Methoxyphenyl sulfonium perfluoro -n- octane sulfonate, diphenyl -
4-methoxyphenylsulfonium p-toluenesulfonate, diphenyl-4-methoxyphenylsulfonium 10-camphorsulfonate,

Diphenyl-4-t-butoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium nonafluoro-n-butanesulfonate, diphenyl-4-t-butoxyphenylsulfonium perfluoro-n-octanesulfonate, Diphenyl-4-t-butoxyphenylsulfonium p-toluenesulfonate, diphenyl-4-t-butoxyphenylsulfonium 10-camphorsulfonate, bis (4-fluorophenyl) -phenylsulfonium trifluoromethanesulfonate,
Bis (4-fluorophenyl) -4-hydroxyphenylsulfonium trifluoromethanesulfonate, bis (4-fluorophenyl) -4-methoxyphenylsulfonium trifluoromethanesulfonate, bis (4-
(Hydroxyphenyl) -phenylsulfonium trifluoromethanesulfonate, bis (4-hydroxyphenyl) -4-hydroxyphenylsulfonium trifluoromethanesulfonate, bis (4-hydroxyphenyl) -4-methoxyphenylsulfonium trifluoromethanesulfonate,

Bis (4-methoxyphenyl) phenylsulfonium trifluoromethanesulfonate, bis (4-methoxyphenyl) -4-hydroxyphenylsulfonium trifluoromethanesulfonate, bis (4
-Methoxyphenyl) -4-methoxyphenylsulfonium trifluoromethanesulfonate, tris (4-fluorophenyl) sulfonium trifluoromethanesulfonate, tris (4-hydroxyphenyl) sulfonium trifluoromethanesulfonate, tris (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, Tris (4-methoxyphenyl) sulfonium nonafluoro-n-butanesulfonate, tris (4
-Methoxyphenyl) perfluoro-n-octanesulfonate, tris (4-methoxyphenyl) sulfonium p-toluenesulfonate, tri (4-methoxyphenyl) sulfoniumbenzenesulfonate, tris (4
-Methoxyphenyl) sulfonium 10-camphorsulfonate.

Specific examples of the iodonium salt include bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate and bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate. t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-
t-butylphenyl) iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodoniumbenzenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, 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 pentafluorobenzenesulfonate,

Bis (3,4-dimethylphenyl) iodonium trifluoromethanesulfonate, bis (3,4
-Dimethylphenyl) iodonium nonafluoro-n-
Butanesulfonate, bis (3,4-dimethylphenyl) iodonium perfluoro-n-octanesulfonate, bis (3,4-dimethylphenyl) iodonium p-toluenesulfonate, bis (3,4-dimethylphenyl) iodoniumbenzenesulfonate, bis (3,4-dimethylphenyl) iodonium 10-camphorsulfonate, bis (3,4-dimethylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, bis (3,4-dimethylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, Bis (3,4-dimethylphenyl) iodonium 2,4-
Difluorobenzenesulfonate, bis (3,4-dimethylphenyl) iodonium hexafluorobenzenesulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium p-toluene Sulfonate, diphenyliodonium benzenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium 2-trifluoromethylbenzenesulfonate, diphenyliodonium 4-trifluoromethylbenzenesulfonate, diphenyliodonium 2,4-difluorobenzenesulfonate, diphenyliodonium pentafluoroben Nsuruhoneto,

4-nitrophenyl / phenyliodonium trifluoromethanesulfonate, 4-nitrophenyl / phenyliodonium nonafluoro-n-butanesulfonate, 4-nitrophenyl / phenyliodonium perfluoro-n-octanesulfonate, 4-nitrophenyl / phenyl Iodonium p-toluenesulfonate, 4-nitrophenyl / phenyliodonium benzenesulfonate, 4-nitrophenyl / phenyliodonium 10-camphorsulfonate, bis (3-
Nitrophenyl) iodonium trifluoromethanesulfonate, bis (3-nitrophenyl) iodonium nonafluoro-n-butanesulfonate, bis (3-nitrophenyl) iodonium perfluoro-n-octanesulfonate, bis (3-nitrophenyl) iodonium p- Toluenesulfonate, bis (3-nitrophenyl) iodoniumbenzenesulfonate, bis (3-nitrophenyl) iodonium 10-camphorsulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium nonafluoro-n- Butanesulfonate, 4-methoxyphenyl-phenyliodonium perfluoro-n-octanesulfonate, 4-methoxyphenyl Cycloalkenyl iodonium p- toluenesulfonate, 4-methoxyphenyl-phenyl iodonium benzenesulfonate, 4-methoxyphenyl-phenyl iodonium 10-camphorsulfonate,

Bis (4-chlorophenyl) iodonium trifluoromethanesulfonate, bis (4-chlorophenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-chlorophenyl) iodonium perfluoro-n-octanesulfonate, bis (4-chlorophenyl) Iodonium p-toluenesulfonate,
Bis (4-chlorophenyl) iodoniumbenzenesulfonate, bis (4-chlorophenyl) iodonium 1
0-camphorsulfonate, bis (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, bis (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-trifluoromethylphenyl) iodonium perfluoro- n-octanesulfonate, bis (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, bis (4-trifluoromethylphenyl) iodoniumbenzenesulfonate, bis (4-trifluoromethylphenyl) iodonium 10-camphorsulfonate, and the like. be able to.

Sulfonimide compound: Examples of the sulfonimide compound include compounds represented by the following formula (1).

[0029]

Embedded image [In the formula (1), V represents a divalent group such as an alkylene group, an arylene group, or an alkoxylene group, and R ¹ 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- (nonafluoro-n-butane Sulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) phthalimide, N- (nonafluoro-n-butanesulfonyloxy) diphenylmaleimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.
1] heptane-5,6-oxy-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide,

N- (perfluoro-n-octanesulfonyloxy) succinimide, N- (perfluoro-n
-Octanesulfonyloxy) phthalimide, N- (perfluoro-n-octanesulfonyloxy) diphenylmaleimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro- n-octanesulfonyloxy) bicyclo [2.2.1] heptane-5,6
-Oxy-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy)
Phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-
Dicarboximide, N- (10-camphorsulfonyloxy) naphthylimide,

N- (n-octanesulfonyloxy) succinimide, N- (n-octanesulfonyloxy)
Phthalimide, N- (n-octanesulfonyloxy)
Diphenylmaleimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (n-octanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-
(N-octanesulfonyloxy) bicyclo [2.2.
1] Heptane-5,6-oxy-2,3-dicarboximide, N- (n-octanesulfonyloxy) naphthylimide, N- (p-toluenesulfonyloxy) succinimide, N- (p-toluenesulfonyloxy) Phthalimide, N- (p-toluenesulfonyloxy) diphenylmaleimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,
3-dicarboximide, N- (p-toluenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-
Toluenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide,

N- (2-trifluoromethylbenzenesulfonyloxy) succinimide, N- (2-trifluoromethylbenzenesulfonyloxy) phthalimide,
N- (2-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N- (2-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (2 -Trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4-trifluoromethylbenzenesulfonyloxy) succinimide, N- (4-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (4-trifluoromethylbenzenesulfonyloxy) ) Diphenylmaleimide, N- (4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-
5,6-oxy-2,3-dicarboximide, N-
(4-trifluoromethylbenzenesulfonyloxy)
Naphthylimide,

N- (pentafluorobenzenesulfonyloxy) succinimide, N- (pentafluorobenzenesulfonyloxy) phthalimide, N- (pentafluorobenzenesulfonyloxy) diphenylmaleimide, N- (pentafluorobenzenesulfonyloxy)
Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (pentafluorobenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N-
(Pentafluorobenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (pentafluorobenzenesulfonyloxy) naphthylimide, N- (benzenesulfonyloxy) Succinimide, N- (benzenesulfonyloxy) phthalimide, N- (benzenesulfonyloxy) diphenylmaleimide, N- (benzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (benzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (benzenesulfonyloxy) bicyclo [ 2.2.1] Heptane-5,6-oxy-2,3-dicarboximide, N
-(Benzenesulfonyloxy) naphthylimide,

N- (1-naphthalenesulfonyloxy)
Succinimide, N- (1-naphthalenesulfonyloxy) phthalimide, N- (1-naphthalenesulfonyloxy) diphenylmaleimide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] hept-5
Ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) -7-oxabicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide , N- (1-naphthalenesulfonyloxy) naphthylimide and the like.

Diazomethane compound: Examples of the diazomethane compound include compounds represented by the following formula (2).

[0037]

Embedded image [In the formula (2), R ² and R ³ independently represent a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, and a halogen-substituted aryl group. ]

Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (1-methylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane,
Bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylbenzenesulfonyl) diazomethane, bis (4-t-
Butylphenylsulfonyl) diazomethane, bis (4-
(Chlorophenylsulfonyl) diazomethane, methylsulfonyl / p-toluenesulfonyldiazomethane, cyclohexylsulfonyl / 1,1-dimethylethylsulfonyldiazomethane, cyclohexylsulfonyl / p-toluenesulfonyldiazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5 .5] dodecane-8-sulfonyl) diazomethane, bis (1,4-dioxaspiro [4.5] decane-7-sulfonyl) diazomethane and the like.

Disulfonylmethane compound: Examples of the disulfonylmethane compound include compounds represented by the following formula (3).

[0040]

Embedded image [In the formula (3), R ⁴ and R ⁵ are each independently a linear or branched monovalent aliphatic hydrocarbon group, a cycloalkyl group, an aryl group, an aralkyl group or another group having a hetero atom. X and Y each independently represent an aryl group, a hydrogen atom, a linear or branched monovalent aliphatic hydrocarbon group or another monovalent organic group having a hetero atom; And at least one of X and Y is an aryl group, or X and Y are interconnected to form a carbon monocyclic or polycyclic structure having at least one unsaturated bond, or X and Y are interconnected to form

[0041]

Embedded image

(Provided that X 'and Y' each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an aralkyl group, or X 'and Y' bonded to the same or different carbon atoms represent Are connected to each other to form a carbon monocyclic structure, and m is an integer of 2 to 10.)
To form a group represented by ]

Halogen-containing compound: Examples of the halogen compound include a haloalkyl group-containing hydrocarbon compound,
Examples thereof include a haloalkyl group-containing heterocyclic compound. Specific examples of the halogen-containing compound include tris (2,3-dibromopropyl) isocyanurate, α,
α, α-tribromomethylphenylsulfone, 2,2-
Dimethyl-3,3,3-tribromo-1-propanol, 2,2-bis (bromomethyl) -1,3-propanediol, 2- (bromomethyl) -2- (hydroxymethyl) -1,3-propanediol, Pentaerythritol tetrabromide, hexabromo-n-hexanes, hexabromo-n-heptane, hexabromocyclo-n-dodecane, tetrabromo-o-cresol, tetrabromobisphenol A bis (2-hydroxyethyl ether) s, Bromine compounds such as 4,4-dibromo-2,4-dimethyl-3-pentanone; pentaerythritol tetrachloride, phenylbis (trichloromethyl) -s-triazine, 4-methoxyphenyl.
(Trichloromethyl) -s-triazine derivatives such as bis (trichloromethyl) -s-triazine and 1-naphthylbis (trichloromethyl) -s-triazine;
Chlorine compounds such as 1-bis (4-chlorophenyl) -2,2,2-trichloroethane; iodine compounds such as hexaiodo-n-hexanes and 1,4-diiodobenzene;

Sulfone compound: Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof. Specific examples of the sulfone compound include phenacyl phenyl sulfone, mesityl phenacyl sulfone, bis (phenylsulfonyl) methane, and 4-trisphenacyl sulfone. 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 benzoin tosylate, pyroganol tris (trifluoromethanesulfonate), pyroganol tris (methanesulfonate), nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, α- Examples include methylol benzoin tosylate, α-methylol benzoin n-octane sulfonate, α-methylol benzoin trifluoromethanesulfonate, α-methylol benzoin n-dodecane sulfonate, and the like.

Of these acid generators (B), onium salt compounds and sulfonic acid imide compounds are preferred, and onium salt compounds are more preferred. In the present invention, the acid generator (B) can be used alone or in combination of two or more.

In the present invention, the acid generator (B) is used in an amount of usually 0.1 to 20 per 100 parts by weight of the resin (A).
Parts by weight, preferably 0.5 to 15 parts by weight, more preferably 1 to 12 parts by weight. In this case, the acid generator (B)
If the amount used is less than 0.1 part by weight, the resolution as a resist tends to decrease, while if it exceeds 20 parts by weight, the pattern cross-sectional shape as a resist tends to decrease.

Component (C) In the present invention, the component (C) is a compound having an α-hydroxyisopropyl group and / or an acid-dissociable derivative of an α-hydroxyisopropyl group (hereinafter, referred to as “compound (C)”). Become. Here, “acid-dissociable derivative of α-hydroxyisopropyl group” means a group in which a hydroxyl group in α-hydroxyisopropyl group is protected by an acid-dissociable group that dissociates by the action of an acid. Such a compound (C) causes, for example, a crosslinking reaction in the resin (A) in the presence of an acid (for example, an acid generated by exposure), thereby suppressing the solubility of the resin in an alkali developing solution. It is a component which shows. Hereinafter, a compound having only an α-hydroxyisopropyl group is referred to as a “tertiary alcohol compound (C1)”, and a compound having only an acid-dissociable derivative of an α-hydroxyisopropyl group is referred to as an “acid-dissociable compound (C2)”. And a compound having both an α-hydroxyisopropyl group and an acid-dissociable derivative of the α-hydroxyisopropyl group is referred to as “tertiary alcohol derivative (C3)”. Examples of the tertiary alcohol compound (C1) include a compound represented by the following general formula (4) (hereinafter, referred to as a “benzene compound (4)”) and a compound represented by the following general formula (5) ( Hereinafter, referred to as “diphenyl compound (5)”), a compound represented by the following general formula (6) (hereinafter referred to as “naphthalene compound (6)”), and represented by the following general formula (7). Compound (hereinafter, referred to as
It is referred to as "furan-based compound (7)". ) And the like.

[0048]

Embedded image [In the general formula (4), each A independently represents an α-hydroxyisopropyl group or a hydrogen atom, and at least one A is an α-hydroxyisopropyl group, and R ⁶ represents a hydrogen atom, a hydroxyl group, It represents a straight-chain or branched alkylcarbonyl group having 2 to 6 carbon atoms or a straight-chain or branched alkoxycarbonyl group having 2 to 6 carbon atoms. ]

[0049]

Embedded image [In the general formula (5), each A independently represents an α-hydroxyisopropyl group or a hydrogen atom, and at least one A is an α-hydroxyisopropyl group; R ⁷ is a single bond; To 5 linear or branched alkylene groups, -O-, -CO- or -COO-
Is shown. ]

[0050]

Embedded image [In the general formula (6), each A independently represents an α-hydroxyisopropyl group or a hydrogen atom, and at least one A is an α-hydroxyisopropyl group. ]

[0051]

Embedded image [In the general formula (7), each A independently represents an α-hydroxyisopropyl group or a hydrogen atom, and at least one A is an α-hydroxyisopropyl group, and R ⁸ and R ⁹ are mutually independent. Represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. ]

Among the tertiary alcohol compounds (C1), specific examples of the benzene compound (4) include α-hydroxyisopropylbenzene, 1,3-bis (α-hydroxyisopropyl) benzene, 1,4-bis ( α-hydroxyisopropyl) benzene, 1,2,4-tris (α
Α-hydroxypropyl) benzene, 1,3,5-tris (α-hydroxyisopropyl) benzene, etc.
Hydroxyisopropylbenzenes such as 3-α-hydroxyisopropylphenol, 4-α-hydroxyisopropylphenol, 3,5-bis (α-hydroxyisopropyl) phenol, and 2,4,6-tris (α-hydroxyisopropyl) phenol α-hydroxyisopropylphenols;

3-α-hydroxyisopropylphenyl methyl ketone, 4-α-hydroxyisopropylphenyl methyl ketone, 4-α-hydroxyisopropylphenyl ethyl ketone, 4-α-hydroxyisopropylphenyl n-propyl ketone, 4-α- Hydroxyisopropyl phenyl / isopropyl ketone, 4-α
-Hydroxyisopropylphenyl / n-butyl ketone, 4-α-hydroxyisopropylphenyl / t-butyl ketone, 4-α-hydroxyisopropylphenyl / n-pentyl ketone, 3,5-bis (α-hydroxyisopropyl) phenyl / methyl ketone, 3 Α-hydroxyisopropylphenyl alkyl ketones such as 2,5-bis (α-hydroxyisopropyl) phenyl ethyl ketone and 2,4,6-tris (α-hydroxyisopropyl) phenyl methyl ketone;

Methyl 3-α-hydroxyisopropylbenzoate, methyl 4-α-hydroxyisopropylbenzoate, ethyl 4-α-hydroxyisopropylbenzoate,
N-propyl 4-α-hydroxyisopropylbenzoate, isopropyl 4-α-hydroxyisopropylbenzoate, n-butyl 4-α-hydroxyisopropylbenzoate, t-butyl 4-α-hydroxyisopropylbenzoate, 4-α- N-pentyl hydroxyisopropyl benzoate, 3,5-bis (α-hydroxyisopropyl)
Examples of alkyl 4-α-hydroxyisopropyl benzoates such as methyl benzoate, ethyl 3,5-bis (α-hydroxyisopropyl) benzoate, and methyl 2,4,6-tris (α-hydroxyisopropyl) benzoate. be able to.

Specific examples of the diphenyl compound (5) include 3-α-hydroxyisopropylbiphenyl, 4-α-hydroxyisopropylbiphenyl,
5-bis (α-hydroxyisopropyl) biphenyl,
3,3′-bis (α-hydroxyisopropyl) biphenyl, 3,4′-bis (α-hydroxyisopropyl)
Biphenyl, 4,4′-bis (α-hydroxyisopropyl) biphenyl, 2,4,6-tris (α-hydroxyisopropyl) biphenyl, 3,3 ′, 5-tris (α-hydroxyisopropyl) biphenyl,
4 ′, 5-tris (α-hydroxyisopropyl) biphenyl, 2,3 ′, 4,6, -tetrakis (α-hydroxyisopropyl) biphenyl, 2,4,4 ′, 6,-
Tetrakis (α-hydroxyisopropyl) biphenyl, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) biphenyl, 2,3 ′, 4,5 ′, 6-
Pentakis (α-hydroxyisopropyl) biphenyl, 2,2 ′, 4,4 ′, 6,6′-hexakis (α-
Α-hydroxyisopropylbiphenyls such as (hydroxyisopropyl) biphenyl;

3-α-hydroxyisopropyldiphenylmethane, 4-α-hydroxyisopropyldiphenylmethane, 1- (4-α-hydroxyisopropylphenyl) -2-phenylethane, 1- (4-α-hydroxyisopropylphenyl) -2- Phenylpropane, 2-
(4-α-hydroxyisopropylphenyl) -2-phenylpropane, 1- (4-α-hydroxyisopropylphenyl) -3-phenylpropane, 1- (4-α-
(Hydroxyisopropylphenyl) -4-phenylbutane, 1- (4-α-hydroxyisopropylphenyl)
-5-phenylpentane, 3,5-bis (α-hydroxyisopropyldiphenylmethane, 3,3′-bis (α
-Hydroxyisopropyl) diphenylmethane, 3,
4′-bis (α-hydroxyisopropyl) diphenylmethane, 4,4′-bis (α-hydroxyisopropyl) diphenylmethane, 1,2-bis (4-α-hydroxyisopropylphenyl) ethane, 1,2-bis (4
-Α-hydroxypropylphenyl) propane, 2,2
-Bis (4-α-hydroxypropylphenyl) propane, 1,3-bis (4-α-hydroxypropylphenyl) propane, 2,4,6-tris (α-hydroxyisopropyl) diphenylmethane, 3,3 ′, 5 -Tris (α-hydroxyisopropyl) diphenylmethane,
3,4 ', 5-tris (α-hydroxyisopropyl)
Diphenylmethane, 2,3 ′, 4,6-tetrakis (α
-Hydroxyisopropyl) diphenylmethane, 2,
4,4 ′, 6-tetrakis (α-hydroxyisopropyl) diphenylmethane, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) diphenylmethane,
2,3 ′, 4,5 ′, 6-pentakis (α-hydroxyisopropyl) diphenylmethane, 2,2 ′, 4
Α-hydroxyisopropyldiphenylalkanes such as 4 ′, 6,6′-hexakis (α-hydroxyisopropyl) diphenylmethane;

3-α-hydroxyisopropyl diphenyl ether, 4-α-hydroxyisopropyl diphenyl ether, 3,5-bis (α-hydroxyisopropyl) diphenyl ether, 3,3′-bis (α-hydroxyisopropyl) diphenyl ether, 3, 4 ′ -Bis (α-hydroxyisopropyl) diphenyl ether, 4,4′-bis (α-hydroxyisopropyl) diphenyl ether, 2,4,6-tris (α-hydroxyisopropyl) diphenyl ether, 3,3 ′, 5-
Tris (α-hydroxyisopropyl) diphenyl ether, 3,4 ′, 5-tris (α-hydroxyisopropyl) diphenyl ether, 2,3′4,6-tetrakis (α-hydroxyisopropyl) diphenyl ether, 2,4,4 ′, 6-tetrakis (α-hydroxyisopropyl) diphenyl ether, 3,3 ′, 5,5 ′
-Tetrakis (α-hydroxyisopropyl) diphenyl ether, 2,3 ′, 4,5 ′, 6-pentakis (α
-Hydroxyisopropyl) diphenyl ether, 2,
Α-hydroxyisopropyl diphenyl ethers such as 2 ′, 4,4 ′, 6,6′-hexakis (α-hydroxyisopropyl) diphenyl ether;

3-α-hydroxyisopropyl diphenyl ketone, 4-α-hydroxyisopropyl diphenyl ketone, 3,5-bis (α-hydroxyisopropyl)
Diphenyl ketone, 3,3′-bis (α-hydroxyisopropyl) diphenyl ketone, 3,4′-bis (α-
(Hydroxyisopropyl) diphenyl ketone, 4,4 '
-Bis (α-hydroxyisopropyl) diphenyl ketone, 2,4,6-tris (α-hydroxyisopropyl) diphenyl ketone, 3,3 ′, 5-tris (α-hydroxyisopropyl) diphenyl ketone, 3,4 ′,
5-tris (α-hydroxyisopropyl) diphenyl ketone, 2,3 ′, 4,6-tetrakis (α-hydroxyisopropyl) diphenyl ketone, 2,4,4 ′, 6
-Tetrakis (α-hydroxyisopropyl) diphenyl ketone, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) diphenyl ketone, 2,3 ′,
4,5 ′, 6-pentakis (α-hydroxyisopropyl) diphenyl ketone, 2,2 ′, 4,4 ′, 6,6 ′
Α-hydroxyisopropyl diphenyl ketones such as hexakis (α-hydroxyisopropyl) diphenyl ketone;

Phenyl 3-α-hydroxyisopropylbenzoate, phenyl 4-α-hydroxyisopropylbenzoate, 3-α-hydroxyisopropylphenyl benzoate, 4-α-hydroxyisopropylphenyl benzoate, 3,5-bis (α -Hydroxyisopropyl) phenyl benzoate, 3-α-hydroxyisopropylphenyl 3-α-hydroxyisopropylbenzoate, 3-α-
4-α-hydroxyisopropylphenyl hydroxyisopropylbenzoate, 3-α-hydroxyisopropylphenyl 4-α-hydroxyisopropylbenzoate,
-Α-hydroxyisopropylbenzoic acid 4-α-hydroxyisopropylphenyl, benzoic acid 3,5-bis (α
-Hydroxyisopropyl) phenyl, 2,4,6-tris (α-hydroxyisopropyl) benzoic acid phenyl, 3,5-bis (α-hydroxyisopropyl) benzoic acid 3-α-hydroxyisopropylphenyl, 3,5
-Bis (α-hydroxyisopropyl) benzoic acid 4-α
-Hydroxyisopropylphenyl, 3,5-bis (α-hydroxyisopropyl) phenyl 3-α-hydroxyisopropylbenzoate, 3,5-bis (α-hydroxyisopropyl) phenyl 4-α-hydroxyisopropylbenzoate, benzoic acid 2 , 4,6-tris (α-hydroxyisopropyl) phenyl,

3-α-hydroxyisopropylphenyl 2,4,6-tris (α-hydroxyisopropyl) benzoate, 4-α-hydroxyisopropylphenyl 2,4,6-tris (α-hydroxyisopropyl) benzoate 3,5-bis (α-hydroxyisopropyl) benzoic acid 3,5-bis (α-hydroxyisopropyl) phenyl, 3-α-hydroxyisopropylbenzoic acid 2,
4,6-tris (α-hydroxyisopropyl) phenyl, 4-α-hydroxyisopropylbenzoic acid
6-tris (α-hydroxyisopropyl) phenyl,
3,5-bis (α-hydroxyisopropyl) phenyl 2,4,6-tris (α-hydroxyisopropyl) benzoate, 3,5-bis (α-hydroxyisopropyl)
Α- such as 2,4,6-tris (α-hydroxyisopropyl) phenyl benzoate and 2,4,6-tris (α-hydroxyisopropyl) phenyl benzoate; And phenyl hydroxyisopropylbenzoate.

Specific examples of the naphthalene compound (6) include 1- (α-hydroxyisopropyl) naphthalene, 2- (α-hydroxyisopropyl) naphthalene, 1,3-bis (α-hydroxyisopropyl) naphthalene, 1,4-bis (α-hydroxyisopropyl)
Naphthalene, 1,5-bis (α-hydroxyisopropyl) naphthalene, 1,6-bis (α-hydroxyisopropyl) naphthalene, 1,7-bis (α-hydroxyisopropyl) naphthalene, 2,6-bis (α-hydroxy Isopropyl) naphthalene, 2,7-bis (α-hydroxyisopropyl) naphthalene, 1,3,5-tris (α-hydroxyisopropyl) naphthalene, 1,3
6-tris (α-hydroxyisopropyl) naphthalene, 1,3,7-tris (α-hydroxyisopropyl) naphthalene, 1,4,6-tris (α-hydroxyisopropyl) naphthalene, 1,4,7-tris (α −
(Hydroxyisopropyl) naphthalene, 1,3,5,7
-Tetrakis (α-hydroxyisopropyl) naphthalene and the like.

Further, specific examples of the furan compound (7) include 3- (α-hydroxyisopropyl) furan,
2-methyl-3- (α-hydroxyisopropyl) furan, 2-methyl-4- (α-hydroxyisopropyl)
Furan, 2-ethyl-4- (α-hydroxyisopropyl) furan, 2-n-propyl-4- (α-hydroxyisopropyl) furan, 2-isopropyl-4- (α-
(Hydroxyisopropyl) furan, 2-n-butyl-4
-(Α-hydroxyisopropyl) furan, 2-t-butyl-4- (α-hydroxyisopropyl) furan, 2
-N-pentyl-4- (α-hydroxyisopropyl)
Furan, 2,5-dimethyl-3- (α-hydroxyisopropyl) furan, 2,5-diethyl-3- (α-hydroxyisopropyl) furan, 3,4-bis (α-hydroxyisopropyl) furan, 2,5 -Dimethyl-3,
4-bis (α-hydroxyisopropyl) furan, 2,
5-diethyl-3,4-bis (α-hydroxyisopropyl) furan and the like can be mentioned.

The tertiary alcohol compound (C1) is usually
It can be synthesized by the following methods. A method in which an acetyl group-containing compound such as 1,3-diacetylbenzene is reacted with a Grignard reagent such as CH ₃ MgBr, methylated, and then hydrolyzed. A method in which an isopropyl group-containing compound such as 1,3-diisopropylbenzene is oxidized with oxygen or the like to generate a peroxide, and then reduced.

Next, as the acid dissociable compound (C2),
For example, a compound in which the hydrogen atom of the hydroxyl group in all the α-hydroxyisopropyl groups in each of the compounds exemplified as the tertiary alcohol compound (C1) is replaced with one or more acid dissociable groups, and the like. Can be.
The acid dissociable compound (C2) generates an α-hydroxyisopropyl group by dissociating at least a part of the acid dissociable group in the presence of an acid (eg, an acid generated by exposure), thereby forming a resin. In (A), for example, a crosslinking reaction is caused, and as a result, an effect of suppressing the solubility of the resin in an alkali developing solution is exhibited.

Next, as the tertiary alcohol derivative (C3), for example, the hydrogen atom of the hydroxyl group in some α-hydroxyisopropyl groups in each of the compounds mentioned as specific examples of the tertiary alcohol compound (C1) And the like, in which is substituted by an acid dissociable group. In this case, the substitution of the hydrogen atom in the hydroxyl group by the acid dissociable group may be carried out at any position and any position in the tertiary alcohol compound (C1) as long as one or more free α-hydroxyisopropyl groups remain after the substitution. Α-
This can be done for a hydroxyisopropyl group.
The tertiary alcohol derivative (C3) has a free α-hydroxyisopropyl group, and its acid dissociable group dissociates in the presence of an acid (eg, an acid generated by exposure) to form an α-hydroxyisopropyl group. In the presence of an acid (eg, an acid generated by exposure), the resin (A) has, for example, a crosslinking reaction, and as a result, has an action of suppressing the solubility of the resin in an alkali developing solution. is there.

The acid dissociable group in the acid dissociable compound (C2) and the tertiary alcohol derivative (C3) is, for example, an acetal group together with an oxygen atom in the α-hydroxyisopropyl group in the tertiary alcohol compound (C1). (Hereinafter, referred to as an “acetal acid dissociable group”), an acyl group, a 1-branched alkoxycarbonyl group, and the like. Examples of the acetal acid dissociable group include, for example, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-i-propoxyethyl group, 1-n-butoxyethyl group, 1-phenyl Examples thereof include an oxyethyl group, a 1-benzyloxyethyl group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, and the like. Further, as the acyl group,
For example, an acetyl group, a propionyl group, a butyryl group and the like can be mentioned. Examples of the 1-branched alkoxycarbonyl group include an isopropoxycarbonyl group, a sec-butoxycarbonyl group, a t-butoxycarbonyl group, and a 1,1-dimethylpropoxycarbonyl group. Examples of the acid dissociable group other than those described above include, for example, a substituted methyl group such as a methoxymethyl group and an ethoxymethyl group; a 1-substituted ethyl group such as a 1-methoxyethyl group and a 1-ethoxyethyl group; 1-substituted propyl group such as 1-ethoxypropyl group; silyl group such as trimethylsilyl group and triethylsilyl group; germyl group such as trimethylgermyl group and triethylgermyl group; cyclic acid such as cyclopentyl group and cyclohexyl group Dissociable groups and the like can be mentioned.

The compound (C) is preferably a compound having two or more free α-hydroxyisopropyl groups, more preferably a tertiary alcohol compound (C1)
Benzene compound (4) having two or more α-hydroxyisopropyl groups, diphenyl compound (5)
Among them, α-hydroxyisopropyl biphenyls having two or more α-hydroxyisopropyl groups, naphthalene compounds (6) having two or more α-hydroxyisopropyl groups, and benzene-based compounds as tertiary alcohol derivatives (C3) Compound (4), α-hydroxyisopropylbiphenyls or naphthalene-based compound (6)
A compound in which the α-hydroxyl group of some of the α-hydroxyisopropyl groups in the compound is protected with an acid-dissociable group, and is a compound having two or more free α-hydroxyisopropyl groups, particularly preferably α-hydroxyisopropyl group. Of the benzene compound (4) and the diphenyl compound (5) having two or more
Α-hydroxyisopropyl biphenyls having at least two α-hydroxyisopropyl groups and naphthalene compounds (6) having at least two α-hydroxyisopropyl groups. In the present invention, the compound (C) can be used alone or in combination of two or more.

In the present invention, another crosslinking agent can be used in combination with the compound (C). As the other cross-linking agent, any one having an action of cross-linking the resin (A) in the presence of an acid (for example, an acid generated by exposure) to reduce the solubility of the resin in an alkali developing solution is used. It is not particularly limited, and examples thereof include an N- (alkoxymethyl) glycoluril compound represented by the following general formula (8), and an N- (alkoxymethyl) glycoluril compound represented by the following general formula (9).
(Alkoxymethyl) urea compound represented by the following general formula (1)
N- (alkoxymethyl) melamine compounds represented by formula (0) and N- (alkoxymethyl) amino compounds such as N- (alkoxymethyl) ethyleneurea compounds represented by the following general formula (11).

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

[In the general formulas (8) to (11), R ¹⁰
To R ²⁵ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms. ]

Specific examples of the N- (alkoxymethyl) glycoluril compound include N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N,
N-tetra (ethoxymethyl) glycoluril, N,
N, N, N-tetra (n-propoxymethyl) glycoluril, N, N, N, N-tetra (i-propoxymethyl) glycoluril, N, N, N, N-tetra (n
-Butoxymethyl) glycoluril, N, N, N, N
-Tetra (t-butoxymethyl) glycoluril and the like. Specific examples of the N- (alkoxymethyl) urea compound include N, N′-di (methoxymethyl) urea, N, N′-di (ethoxymethyl) urea, and N, N ′.
-Di (n-propoxymethyl) urea, N, N'-di (i-propoxymethyl) urea, N, N'-di (n-
Butoxymethyl) urea, N, N′-di (t-butoxymethyl) urea and the like.

Specific examples of the N- (alkoxymethyl) melamine compound include N, N, N, N, N, N
-Hexa (methoxymethyl) melamine, N, N, N,
N, N, N-hexa (ethoxymethyl) melamine, N,
N, N, N, N, N-hexa (n-propoxymethyl)
Melamine, N, N, N, N, N, N-hexa (i-propoxymethyl) melamine, N, N, N, N, N, N-hexa (n-butoxymethyl) melamine, N, N, N,
N, N, N-hexa (t-butoxymethyl) melamine and the like can be mentioned. Specific examples of the N- (alkoxymethyl) ethylene urea compound include N, N
-Di (methoxymethyl) -4,5-di (methoxymethyl) ethyleneurea, N, N-di (ethoxymethyl)-
4,5-di (ethoxymethyl) ethyleneurea, N, N
-Di (n-propoxymethyl) -4,5-di (n-propoxymethyl) ethyleneurea, N, N-di (i-propoxymethyl) -4,5-di (i-propoxymethyl)
Ethylene urea, N, N-di (n-butoxymethyl)-
4,5-di (n-butoxymethyl) ethylene urea,
N, N-di (t-butoxymethyl) -4,5-di (t-
Butoxymethyl) ethylene urea.

Among these other crosslinking agents, N- (alkoxymethyl) glycoluril compounds are preferred, and N, N, N, N-tetra (methoxymethyl) glycoluril is particularly preferred. The other crosslinking agents may be used alone or in combination of two or more.

In the present invention, the total amount of the compound (C) and the other crosslinking agent is usually 0.5 to 50 parts by weight, preferably 1 to 40 parts by weight, per 100 parts by weight of the resin (A).
More preferably, it is 2 to 30 parts by weight. In this case, if the total amount used is less than 0.5 part by weight, the effect of suppressing the solubility of the resin (A) in the alkali developing solution is reduced, and as a resist, the residual film ratio is reduced, and the swelling and meandering of the pattern are caused. On the other hand, if it exceeds 50 parts by weight, the heat resistance as a resist tends to decrease.
In addition, the use ratio of the other cross-linking agent varies depending on the type of the substrate used when forming the resist pattern and the like,
Usually, 9 relative to the sum of the compound (C) and the other crosslinking agent.
5% by weight or less.

<Other Components> Acid Diffusion Control Agent In the present invention, the diffusion phenomenon of the acid generated from the acid generator (B) by exposure to light in the resist film is controlled to prevent an undesired chemical reaction in the unexposed area. It is preferable to add an acid diffusion controller having a controlling action or the like. By using such an acid diffusion controlling agent, the storage stability of the composition is improved, the resolution as a resist is further improved, and the post-exposure delay time (PED) is further improved.
The line width of the resist pattern can be suppressed from changing due to the fluctuation of the resist pattern, and the process stability becomes extremely excellent. Examples of the acid diffusion controller include a nitrogen-containing organic compound and a basic compound that decomposes upon exposure. As the nitrogen-containing organic compound, for example, the following general formula (12)

[0079]

Embedded image [In the general formula (12), R ²⁶ , R ²⁷ and R ²⁸ each independently represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and these groups are substituted with a functional group such as a hydroxyl group. Is also good. ]

(Hereinafter, referred to as "nitrogen-containing compound (I)"), a diamino compound having two nitrogen atoms in the same molecule (hereinafter, referred to as "nitrogen-containing compound (II)"), Examples thereof include polyamino compounds and polymers having three or more nitrogen atoms (hereinafter collectively referred to as "nitrogen-containing compound (III)"), amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds. .

Examples of the nitrogen-containing compound (I) include, for example, n
Mono- (cyclo) alkylamines such as hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-dodecylamine and cyclohexylamine; di-n-butylamine, di-n
-Pentylamine, di-n-hexylamine, di-n-
Di (cyclo) alkylamines such as heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, methyl-n-dodecylamine, di-n-dodecylmethyl, cyclohexylmethylamine and dicyclohexylamine , Triethylamine, tri-n-
Propylamine, tri-n-butylamine, tri-n-
Pentylamine, tri-n-hexylamine, tri-n
-Heptylamine, tri-n-octylamine, tri-
tri (cyclo) alkylamines such as n-nonylamine, tri-n-decylamine, dimethyl-n-dodecylamine, di-n-dodecylmethylamine, dicyclohexylmethylamine and tricyclohexylamine; monoethanolamine, diethanolamine, triethanol Alkanolamines such as amines; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline,
And aromatic amines such as -nitroaniline, diphenylamine, triphenylamine and 1-naphthylamine.

Examples of the nitrogen-containing compound (II) include, for example, ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetrakis (2-
(Hydroxypropyl) ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylether, 4,4′-diaminobenzophenone, 4,
4'-diaminodiphenylamine, 2,2-bis (4-
Aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4
-Aminophenyl) -2- (3-hydroxyphenyl)
Propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4
-Aminophenyl) -1-methylethyl] benzene,
1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene and the like can be mentioned. Examples of the nitrogen-containing compound (III) include polyethyleneimine, polyallylamine, and N- (2-dimethylaminoethyl) acrylamide polymer.

Examples of the amide group-containing compound include formamide, N-methylformamide, N, N-
Examples thereof include dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, and N-methylpyrrolidone. Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and tri-n
-Butylthiourea and the like. Examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, and 2-phenylbenzimidazole; pyridine, 2-methylpyridine, and 4-methyl Pyridine, 2-ethylpyridine, 4
-Ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, 2,
^2, 2 ^,, - Toripirijin, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, other pyridines acridine such as pyrazine, pyrazole, pyridazine, quinoxaline, purine, pyrrolidine, piperidine, morpholine, 4- Methyl morpholine, piperazine,
Examples include 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, and the like.

Examples of the basic compound decomposed by exposure include a sulfonium compound represented by the following general formula (13) and an iodonium compound represented by the following general formula (14).

[0085]

Embedded image [In the general formulas (13) and (14),
R ²⁹ , R ³⁰ and R ³¹ each independently represent a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group or a halogen atom; R ³² and R ³³ each independently represent a hydrogen atom;
An alkyl group, an alkoxyl group or a halogen atom; Z ⁻ is HO ⁻ , R—COO ⁻ (where R represents an alkyl group, an aryl group or an alkaryl group) or the following formula:

[0086]

Embedded image Represents an anion represented by ]

[0087]

Embedded image

Specific examples of the basic compound which is decomposed by exposure include triphenylsulfonium hydroxide, triphenylsulfonium acetate, triphenylsulfonium salicylate, diphenyl-4-hydroxyphenylsulfonium hydroxide, diphenyl-4-hydroxyphenyl Sulfonium acetate, diphenyl-4-hydroxyphenylsulfonium salicylate, bis (4-t-butylphenyl) iodonium hydroxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium hydro Oxide, bis (4
-T-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium salicylate, 4-t-butylphenyl-4-hydroxyphenyliodonium hydroxide, 4-t-butylphenyl-4-hydroxyphenyliodonium Acetate, 4-t-butylphenyl-4-hydroxyphenyliodonium salicylate and the like can be mentioned. These acid diffusion controllers can be used alone or in combination of two or more.

The compounding amount of the acid diffusion controlling agent is as follows.
Usually, 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, more preferably 0.00 parts by weight per 0 parts by weight.
1 to 3 parts by weight. In this case, if the compounding amount of the acid diffusion controller is less than 0.001 part by weight, the pattern shape and dimensional fidelity of the resist may be deteriorated depending on the process conditions, or if the PED is long, the pattern shape in the upper layer portion of the pattern may be reduced. If the content exceeds 10 parts by weight, sensitivity as a resist, developability of an unexposed portion, and the like tend to decrease.

Dissolution Control Agent When the solubility of the resin (A) in an alkali developing solution is too high, the dissolution controlling agent has a function of controlling the solubility and appropriately reducing the dissolution rate of the resin during alkali development. Control agents can be included. As such a dissolution controlling agent, a dissolution controlling agent which does not chemically change in steps such as heating, exposure, and development of the resist film is preferable. Examples of the dissolution controlling agent include aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; sulfones such as methylphenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone. And the like. These dissolution controlling agents can be used alone or in combination of two or more. The amount of the dissolution controlling agent is appropriately adjusted depending on the type of the resin (A) to be used, and is usually 50 per 100 parts by weight of the resin (A).
It is at most 30 parts by weight, preferably at most 30 parts by weight.

When the solubility of the resin (A) in an alkali developing solution is too low, the dissolving accelerator has a function of increasing the solubility and appropriately increasing the dissolution rate of the resin during alkali development. Accelerators can be included. As such a dissolution accelerator, one that does not chemically change in steps such as heating, exposure, and development of the resist film is preferable. Examples of the dissolution accelerator include low-molecular-weight phenolic compounds having about 2 to 6 benzene rings, and specific examples include bisphenols and tris (hydroxyphenyl) methanes. Can be. These dissolution promoters can be used alone or in combination of two or more. The amount of the dissolution promoter is appropriately adjusted according to the type of the resin (A) used.
It is usually at most 50 parts by weight, preferably at most 30 parts by weight, per 100 parts by weight.

The sensitizer also has the function of absorbing the energy of the exposed radiation and transmitting the energy to the acid generator (B), thereby increasing the amount of acid generated. A sensitizer having an effect of improving sensitivity can be added. Examples of such a sensitizer include benzophenones, biacetyls, pyrenes, phenothiazines, eosin, and rose bengara. These sensitizers can be used alone or in combination of two or more. The compounding amount of the sensitizer is 100 (A).
Usually 50 parts by weight or less, preferably 30 parts by weight,
Not more than parts by weight.

Surfactant A surfactant having an effect of improving the coating properties, striation, developability as a resist and the like of the composition can be added. As such a surfactant,
Any of anionic, cationic, nonionic and amphoteric surfactants can be used, but preferred surfactants are nonionic surfactants. Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyethylene glycol, and the like. ), Megafac (Dai Nippon Ink and Chemicals), Florard (Sumitomo 3M), Asahi Guard, Surflon (from Asahi Glass), Pepole (Toho Chemical), KP (Shin-Etsu Chemical) Company),
Each series such as Polyflow (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) can be mentioned. 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 as an active ingredient of the surfactant per 100 parts by weight of the resin (A).

Other additives In addition, by blending a dye or a pigment, the latent image in the exposed area can be visualized to reduce the influence of halation at the time of exposure. Can be improved.

Solvent The negative-type radiation-sensitive resin composition of the present invention is dissolved in a solvent so that the solid content concentration is usually 5 to 50% by weight. It is prepared as a composition solution by filtering through a filter. As the solvent used for preparing the composition solution, for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate and the like Glycol monoalkyl ether acetates; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-
propylene glycol monoalkyl ether acetates such as n-propyl ether acetate and propylene glycol mono-n-butyl ether acetate; lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate and n-amyl lactate; Methyl acetate,
Ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate,
Aliphatic carboxylic acid esters such as ethyl propionate;
Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-
Ethyl ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-
Other esters such as butyl methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; 2- Ketones such as heptanone, 3-heptanone, 4-heptanone and cyclohexanone; N, N-dimethylformamide, N-
Methylacetamide, N, N-dimethylacetamide,
Amides such as N-methylpyrrolidone; lactones such as γ-lactone; These solvents are
They can be used alone or in combination of two or more.

Formation of Resist Pattern When a resist pattern is formed from the negative-type radiation-sensitive resin composition of the present invention, the composition solution is spin-coated,
By a suitable coating means such as casting coating and roll coating, for example, by coating on a substrate such as a silicon wafer or a wafer coated with aluminum, a resist coating is formed, and then the resist coating is formed through a predetermined mask pattern. Expose the resist coating. The radiation that can be used at that time is, for example, ultraviolet rays such as g-rays or i-rays, a KrF excimer laser (wavelength 248 nm), or an ArF excimer laser (wavelength 193 nm), depending on the type of the acid generator (B). Radiation such as X-rays such as synchrotron radiation, charged particle beams such as electron beams, etc., of which deep UV is preferable. Exposure conditions such as the exposure amount are appropriately selected according to the composition of the negative-type radiation-sensitive resin composition. In the present invention, it is preferable to perform a post-exposure bake in order to make the cross-linking reaction in the exposed portion proceed more efficiently. The heating conditions vary depending on the composition of the negative radiation-sensitive resin composition and the like, but are usually 30 to 200 ° C, preferably 50 to 200 ° C.
150 ° C. Next, a predetermined resist pattern is formed by developing the exposed resist film with an alkaline developer. Examples of the alkali developing solution include alkaline compounds such as mono-, di- or tri-alkylamines, mono-, di- or tri-alkanolamines, heterocyclic amines, tetramethylammonium hydroxide, and choline. At least one of
Usually, an alkaline aqueous solution dissolved to a concentration of 1 to 10% by weight, preferably 1 to 5% by weight is used.
Further, an appropriate amount of an alcohol such as methanol or ethanol or a surfactant can be added to the alkali developer. In the case where such a developing solution composed of an alkaline aqueous solution is used, generally, it is washed with water after development.

[0097]

Embodiments of the present invention will now be described more specifically with reference to the following examples. However, the present invention is not limited to these embodiments.

EXAMPLES Synthesis Example 20 g of 1,3-bis (α-hydroxyisopropyl) benzene (trade name: m-DIOL, manufactured by Mitsui Chemicals, Inc .; the same applies hereinafter) was dissolved in anhydrous tetrahydrofuran to give 10 g.
0.3 g of pyridinium p-toluenesulfonate was added to and dissolved in a weight% solution. After confirming that the water content of this solution was 500 ppm or less by the Karl Fischer method, 15 g of ethyl vinyl ether was slowly added while stirring at room temperature, and the mixture was reacted at room temperature for 8 hours. Thereafter, the reaction solution was purified by reprecipitation with a large amount of water, the precipitate was filtered under reduced pressure, and then dried under vacuum to reduce the hydroxyl groups of 1,3-bis (α-hydroxyisopropyl) benzene to one.
28 g of a compound protected with an -ethoxyethyl group were obtained. This compound is referred to as compound (C-5).

Examples 1 to 21 and Comparative Examples 1 to 6 The components shown in Tables 1 to 3 (parts are based on weight) are mixed to form a uniform solution, and then Teflon having a pore size of 0.2 μm ( Foreign substances were removed by filtration through a membrane filter made of (registered trademark) to prepare a composition solution. Each of the obtained composition solutions was spin-coated on a silicon wafer having a diameter of 8 inches, and then heated to 90 ° C. to form a film having a thickness of 0.3 μm.
m of the resist film was formed. Thereafter, each resist film was exposed to a KrF excimer laser (wavelength: 248 μm) via a mask pattern. In Examples 19 and 20, instead of the KrF excimer laser,
The electron beam was exposed using a simple electron beam direct writing apparatus (output: 50 keV). After exposure, the film was heated at 110 ° C. for 1 minute, and then developed at 23 ° C. for 60 seconds by a paddle method using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide. Thereafter, the substrate was washed with water for 30 seconds and dried to form a negative resist pattern. Tables 4 and 5 show the evaluation results of each resist.

Each measurement and evaluation in the examples and comparative examples was carried out by the following methods. Mw and Mw / Mn Tosoh Corporation's high-speed GPC apparatus HLC-8120 was equipped with a Tosoh Corporation GPC column (G2000H ^XL : 2 pieces, G
3000H ^XL : 1, G4000H ^XL : 1)
The measurement was performed by gel permeation chromatography using monodisperse polystyrene as a standard under the analysis conditions of a flow rate of 1.0 ml / min, an elution solvent of tetrahydrofuran, and a column temperature of 40 ° C. The exposure amount for forming a line-and-space pattern (1L1S) having a sensitivity design dimension of 0.18 μm with a line width of 1: 1 was defined as an optimum exposure amount, and evaluation was performed based on the optimum exposure amount. Resolution The dimension of the smallest resist pattern that was resolved when exposed at the optimum exposure was measured and defined as the resolution. Focus margin For a line-and-space pattern (1L1S) with a design dimension of 0.18 μm, the depth of focus is varied at the optimum exposure amount of each resist film, and the line width of the line pattern falls within the range of (design dimension ± 15%). The depth of focus
Focus margin was set. A resist having a wider focus margin is preferable because the process margin becomes higher and the yield in manufacturing an actual device becomes higher.

Pattern Cross Section Shape 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 0.18 μm formed on a silicon wafer were measured using a scanning electron microscope. The pattern shape satisfying 0.90 ≦ Lb / La ≦ 1.10, and not having a round pattern head, and having no “gougling” and “hem pull” in the pattern near the substrate, It was evaluated as "rectangular" according to the following criteria. ：: 0.90 ≦ Lb / La ≦ 1.10 is satisfied, and the pattern shape is rectangular. Δ: 0.90 ≦ Lb / La ≦ 1.10.
The head of the pattern is round, or the pattern near the substrate has "gougling" or "hemming". ×: Lb / La <0.90 or Lb / La> 1.1
0 or no pattern can be formed.

Each component used in each Example and Comparative Example was
It is as follows. Resin (A) A-1: p-vinylphenol / styrene copolymer (copolymerization molar ratio = 85/15, Mw = 5,100, Mw / M
A-2: p-vinylphenol / styrene copolymer (copolymer molar ratio = 75/25, Mw = 5,000, Mw / M)
A-3: p-vinylphenol / styrene copolymer (copolymer molar ratio = 85/15, Mw = 3,200, Mw / M)
A-4: p-vinylphenol / styrene copolymer (copolymer molar ratio = 75/25, Mw = 3,000, Mw / M)
A-5: p-vinylphenol / p-methoxystyrene copolymer (copolymer molar ratio = 75/25, Mw = 3,10)
0, Mw / Mn = 1.15) a-1: poly (p-vinylphenol) (Mw = 5.2)
00, Mw / Mn = 1.14)

Acid generator (B) B-1: Triphenylsulfonium trifluoromethanesulfonate B-2: Diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate B-3: Diphenyl-4-hydroxyphenylsulfonium trifluoromethanesulfonate B-4 : N- (trifluoromethylsulfonyloxy)
Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide

Compound (C) C-1: 1,3-bis (α-hydroxyisopropyl)
Benzene C-2: 1,3,5-tris (α-hydroxyisopropyl) benzene C-3: 2,6-bis (α-hydroxyisopropyl)
Naphthalene C-4: 4,4'-bis (α-hydroxyisopropyl) biphenyl C-5: Compound obtained in Synthesis Example Other crosslinking agent D-1: N, N, N, N-tetra (methoxymethyl) glycol Uril

Acid diffusion controller E-1: dimethyl-n-dodecylamine E-2: triphenylsulfonium salicylate E-3: 2-phenylbenzimidazole E-4: diphenyl-4-hydroxyphenylsulfonium salicylate Solvent F-1: ethyl lactate (ethyl 2-hydroxypropionate) F-2: ethyl 3-ethoxypropionate, F-3: propylene glycol monomethyl ether acetate

[0105]

[Table 1]

[0106]

[Table 2]

[0107]

[Table 3]

[0108]

[Table 4]

[0109]

[Table 5]

[0110]

The negative-working radiation-sensitive resin composition of the present invention can be applied to an alkali developing solution having a normal concentration when used as a chemically amplified negative-working resist, and can be used in a normal line-and-space pattern (1L1S). It is capable of forming a rectangular resist pattern with high resolution and has excellent focus margin, and is also suitable for charged particles such as deep ultraviolet rays such as excimer lasers, X-rays such as synchrotron radiation, and electron beams. , Which can cope with short-wavelength radiation of far ultraviolet rays or less. Therefore, the negative-type radiation-sensitive resin composition of the present invention can be extremely suitably used for the production of semiconductor devices in which miniaturization is expected to progress further in the future.

──────────────────────────────────────────────────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 Daigo Ichinohe 2-11-24 Tsukiji 2-chome, Chuo-ku, Tokyo JSR Co., Ltd. F-term (reference) 2H025 AA02 AA03 AA04 AB16 AC04 AC05 AC06 AC07 AC08 AD01 BC14 BE00 BE07 BE08 BE10 BF14 BF15 CB45 CC17 CC20 FA17 4J100 AB04Q AB07P AB07Q AB08Q AB09Q AB10Q AJ02R AJRAL08R AM03R AM08R AM15R AM19R AM21R AM43R AM47R AM48R AQ07R AQ08R BA03P BA03R BA04Q BA05Q BA06Q BB01R BC04R BC08R BC43R BC68R CA04 CA05 DA04 GC22 HA53 HC09 HC10 HC25 HC38 HC43 HC45 HC63 HC71 JA38

Claims (3)

[Claims] (A) a repeating unit in which a polymerizable unsaturated bond of a polymerizable unsaturated compound having a phenolic hydroxyl group is cleaved, and a polymerizable unsaturated bond of an unsubstituted or substituted other styrene compound are cleaved. An alkali-soluble resin having a repeating unit, (B) a radiation-sensitive acid generator, and (C)
A negative radiation-sensitive resin composition comprising a compound having an α-hydroxyisopropyl group and / or an acid-dissociable derivative of an α-hydroxyisopropyl group. 2. The method according to claim 1, wherein (A) the alkali-soluble resin is a polymerizable unsaturated compound having a phenolic hydroxyl group, wherein the polymerizable unsaturated bond is cleaved, and styrene and carbon number 1
Linear or branched alkyl group having 1 to 4 carbon atoms
(4) a resin having a repeating unit in which a polymerizable unsaturated bond of another styrene compound selected from the group of styrene derivatives substituted with a linear or branched alkoxyl group or a halogen atom has been cleaved. The negative-type radiation-sensitive resin composition according to claim 1, wherein 3. The method according to claim 1, further comprising (C) a crosslinking agent other than a compound having an α-hydroxyisopropyl group and / or an acid-dissociable derivative of the α-hydroxyisopropyl group. 3. The negative radiation-sensitive resin composition according to item 2.