JP2008209948A - Negative radiation-sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative radiation-sensitive resin composition superior in sensitivity and resolution, showing small optical proximity effect, capable of accurately and stably forming a fine pattern, even in the case of an isolated line pattern, capable of ensuring sufficient focus margin for an isolated line pattern, and useful as a chemically amplified resist. <P>SOLUTION: The negative radiation-sensitive resin composition comprises (A) a low-molecular compound obtained by substituting at least one hydrogen atom of a compound, having an amino group in which the hydrogen atom bonds to a nitrogen atom by a t-butoxycarbonyl group; (B) a radiation-sensitive acid generator; (D) an alkali-soluble resin comprising a p-hydroxystyrene/styrene copolymer; and (E) a crosslinking agent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a negative radiation-sensitive resin composition useful as a resist suitable for ultrafine processing using various types of radiation such as ultraviolet rays, far ultraviolet rays, X-rays or charged particle beams.

In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration, the process size in lithography has been miniaturized. In recent years, microfabrication of 0.5 μm or less is reproducible. There is a need for techniques that can be performed well. Therefore, it is necessary to accurately form a pattern of 0.5 μm or less even in a resist used for microfabrication, but a conventional method using visible light (wavelength 800 to 400 nm) or near ultraviolet light (wavelength 400 to 300 nm). Then, it is very difficult to form a fine pattern of 0.5 μm or less with high accuracy. Therefore, the use of radiation having a shorter wavelength (wavelength of 300 nm or less) has been intensively studied.
Examples of such short wavelength radiation include X-rays such as far ultraviolet rays, synchrotron radiation and the like represented by mercury lamp emission line spectrum (wavelength 254 nm), KrF excimer laser (wavelength 248 nm) or ArF excimer laser (wavelength 193 nm). Examples thereof include charged particle beams such as a beam and an electron beam. Among these, lithography using an excimer laser is particularly attracting attention because of its high output and high efficiency characteristics. Therefore, it is necessary for a resist used in lithography to be able to form a fine pattern of 0.5 μm or less with high sensitivity, high resolution and good reproducibility by using an excimer laser.
As a resist suitable for far ultraviolet rays such as an excimer laser, a radiation sensitive acid generator that generates an acid upon irradiation with radiation (hereinafter referred to as “exposure”) is used, and the sensitivity of the resist by the catalytic action of the acid. A “chemically amplified resist” with improved resistance has been proposed.
As such a chemically amplified resist, for example, Patent Document 1 discloses a combination of a resin protected with a t-butyl group or a t-butoxycarbonyl group and a radiation-sensitive acid generator. A combination of a silyl group protected resin and a radiation sensitive acid generator is disclosed. In addition, many reports have been made on chemically amplified resists such as a resist (Patent Document 3) containing a resin having an acetal group and a radiation-sensitive acid generator.
JP 59-45439 A JP-A-60-52845 JP-A-2-25850

However, it has been pointed out that conventional chemically amplified resists have their own problems, and that various difficulties are involved in the practical application to fine processing of 0.25 μm or less. As a first problem, it has been pointed out that a so-called optical proximity effect is large and a dimensional difference due to pattern density or a rounding or receding phenomenon at a pattern end is likely to occur. If there is a large dimensional difference due to pattern density, an isolated line pattern cannot produce a pattern that matches the design dimension when exposed at the optimal exposure for a line-and-space pattern. It is not possible to satisfy the needs for chip production. The second problem is that a sufficient focus margin cannot be secured especially for an isolated line pattern, and the need for a logic circuit having high speciality and commerciality cannot be satisfied.
For this reason, not only is it excellent in sensitivity and resolution, but also the optical proximity effect is small, and even in isolated line patterns, a fine pattern can be formed with high precision and stability, and sufficient for the isolated line pattern. There is a demand for a resist that can ensure a sufficient focus margin.

  The problem of the present invention is that it effectively responds to various types of radiation, has excellent sensitivity and resolution, has a small optical proximity effect, and can form a fine pattern with high accuracy and stability even in an isolated line pattern, In addition, an object of the present invention is to provide a negative radiation-sensitive composition useful as a chemically amplified resist that can secure a sufficient focus margin for an isolated line pattern.

According to the present invention, the problem is
(A) a low molecular compound in which at least one hydrogen atom bonded to the nitrogen atom of the compound having at least one amino group in which at least one hydrogen atom is bonded to the nitrogen atom is substituted with a t-butoxycarbonyl group;
(B) a radiation sensitive acid generator,
A negative radiation-sensitive resin composition comprising (D) an alkali-soluble resin containing a p-hydroxystyrene / styrene copolymer and (E) a compound capable of crosslinking the alkali-soluble resin in the presence of an acid. object,
Achieved by:

Hereinafter, the present invention will be described in detail.
Component (A) present component (A) in the invention, at least one compound having an amino group one or more hydrogen atom is bonded to a nitrogen atom (hereinafter, referred to as "amino compound (a)".) The nitrogen atom of the It consists of a compound (hereinafter referred to as “compound (A)”) in which one or more of the hydrogen atoms bonded to is substituted with a t-butoxycarbonyl group.
The “amino group” in the amino compound (a) includes an amino group bonded to a carbonyl group. In the compound (A), when the amino compound (a) has two or more amino groups in which at least one hydrogen atom is bonded to a nitrogen atom and two or more t-butoxycarbonyl groups, The t-butoxycarbonyl groups can be bonded to the same or different nitrogen atoms.

In the radiation sensitive resin composition used as a chemically amplified resist, the diffusion phenomenon of the acid generated from the radiation sensitive acid generator in the resist film is controlled to suppress undesirable chemical reactions in non-exposed areas. By adding an acid diffusion control agent having an action, the storage stability of the resin composition is improved, the resolution is improved as a resist, and the resist pattern is caused by fluctuations in the holding time (PED) from exposure to development processing. It is known that the change in the line width can be suppressed and the process stability is also improved.
As a result of intensive studies on the acid diffusion controller in the radiation-sensitive resin composition containing the radiation-sensitive acid generator, the present inventors have found that a basic amino group is protected with an acid-dissociable t-butoxycarbonyl group. It has been found that various performances as a resist are remarkably improved by using a molecular compound, and the present invention has been achieved.
As the amino compound (a), for example, the following formula (1)

[In the formula (1), R ¹ and R ² each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group or an aralkyl group, and these alkyl group, aryl group and aralkyl group Each may be substituted. ] (Hereinafter referred to as “nitrogen-containing compound (I)”), a compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (II)”), a nitrogen atom A compound having three or more compounds (hereinafter referred to as “nitrogen-containing compound (III)”), an amide group-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, and the like can be given.

  Examples of the nitrogen-containing compound (I) include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine; di-n-butylamine, di- -Dialkylamines such as n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine Aniline, N-methylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, 1-naphthylamine, 2- (4-aminophenyl) -2- (3-hydroxy Phenyl) propane, 2- (4-aminophenyl) -2- ( - aromatic amines such as hydroxyphenyl) propane; ethanolamine, and alkanolamines diethanolamine, 1-adamantyl amine, mention may be made of N- methyl-1-adamantyl amines.

Examples of the nitrogen-containing compound (II) include ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1, 12-diaminododecane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) 2- (4-aminophenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1- Methylethyl] benzene and the like.
Examples of the nitrogen-containing compound (III) include 4,4′-diaminodiphenylamine, polyallylamine, polymethallylamine, N- (2-aminoethyl) acrylamide polymer, and the like.

Examples of the amide group-containing compound include formamide, N-methylformamide, acetamide, N-methylacetamide, propionamide, benzamide, pyrrolidone and the like.
Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,3-diphenylurea, tri-n-butylthiourea and the like.
Examples of the nitrogen-containing heterocyclic compound include imidazole, benzimidazole, 2-methylimidazole, 4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-methyl-4. In addition to imidazoles such as -phenylimidazole, 2-methylbenzimidazole and 2-phenylbenzimidazole, indole, pyrrole, pyrazole, adenine, guanine, purine, pyrrolidine, piperidine, morpholine, piperazine and the like can be mentioned.

Of these amino compounds (a), nitrogen-containing compounds (I), nitrogen-containing compounds (II), and nitrogen-containing heterocyclic compounds are preferred. Among the nitrogen-containing compounds (I), dialkylamines and 1-adamantylamines are more preferable, and in particular, di-n-octylamine, di-n-nonylamine, di-n-decylamine, dicyclohexylamine, 1 -Adamantylamine, N-methyl-1-adamantylamine and the like are preferable, and among nitrogen-containing compounds (II), hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, 4,4′-diaminodiphenylmethane and the like are more preferable. Among nitrogen-containing heterocyclic compounds, imidazoles are more preferable, and benzimidazole, 2-methylimidazole are particularly preferable. 2-phenylbenzimidazole and the like are preferable.
The amino compound (a) preferably has a pKa (measurement temperature of 25 ° C., the same applies hereinafter) of the conjugate acid of 0 or more. In this case, when a compound having a pKa of a conjugate acid of less than 0, such as an imide compound, is used instead of the amino compound (a), the resolution and pattern shape of the resulting resist may be impaired.

Specific examples of the particularly preferred compound (A) in the present invention include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n. -Decylamine, Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, N, N-di-t-butoxycarbonyl -1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′-diaminodiphenylmethane, N, N′-di-t- Butoxycarbonylhexamethylenediamine, N, N, N′N′-tetra-t-butoxycarbonyl Hexamethylenediamine, N, N′-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t -Butoxycarbonyl-1,9-diaminononane, N, N'-di-t-butoxycarbonyl-1,10-diaminodecane, N, N'-di-t-butoxycarbonyl-1,12-diaminododecane, N, N'-di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenyl Benzimidazole etc. can be mentioned.
The molecular weight of the compound (A) is usually 100 to 3,000, preferably 200 to 2,000, particularly preferably 250 to 1,000.
In this invention, a compound (A) can be used individually or in mixture of 2 or more types.

(B) Component (B) component in this invention consists of a radiation sensitive acid generator (henceforth "acid generator (B)") which generate | occur | produces an acid by exposure.
Examples of the acid generator (B) include onium salt compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, diazomethane compounds, and disulfonylmethane compounds.
Examples of these acid generators (B) are shown below.

Onium salt compounds:
Examples of the onium salt compounds include iodonium salts, sulfonium salts (including tetrahydrothiophenium salts), phosphonium salts, diazonium salts, ammonium salts, pyridinium salts, and the like.
As a specific example of the onium salt compound,
Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium pyrenesulfonate, bis (4-t -Butylphenyl) iodonium n-dodecylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium p-toluenesulfonate, bis (4-tert-butylphenyl) iodoniumbenzenesulfonate, bis (4-tert-butylphenyl) iodonium 10 -Camphorsulfonate, bis (4-t-butylphenyl) iodonium n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, bis (4-t-butyl) Butylphenyl) iodonium 4-trifluoromethyl benzenesulfonate, bis (4-t- butylphenyl) iodonium 2,4-difluoro benzenesulfonate,
Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium n-dodecylbenzenesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodoniumbenzenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium n-octane sulfonate, diphenyliodonium 2-trifluoromethylbenzenesulfonate, diphenyliodonium4-trifluoromethylbenzenesulfonate, diphenyliodonium 2,4-difluorobenzenesulfonate,

Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium pyrenesulfonate, triphenylsulfonium n-dodecylbenzenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium n-octanesulfonate, triphenylsulfonium 2-trifluoromethylbenzenesulfonate, triphenylsulfonium 4-trifluorobenzenesulfonate, triphenylsulfonium 2,4-difluorobenzenesulfonate, triphenylsulfonium hexafluoro Antimonate Triphenylsulfonium 1-naphthalenesulfonate, 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium nonafluoro-n-butanesulfonate, 4-t-butylphenyl diphenylsulfonium pyrenesulfonate, 4-t-butylphenyl diphenylsulfonium n-dodecylbenzene sulfonate, 4-t-butylphenyl diphenylsulfonium p-toluenesulfonate, 4-t-butylphenyl diphenylsulfonium benzene sulfonate, 4-t-butylphenyl diphenylsulfonium 10-camphorsulfonate, 4-t-butylphenyl diphenylsulfonium n-octanesulfonate, 4-t-butylphenyl Nyl diphenylsulfonium 2-trifluoromethylbenzene sulfonate, 4-t-butylphenyl diphenylsulfonium 4-trifluoromethylbenzene sulfonate, 4-t-butylphenyl diphenylsulfonium 2,4-difluorobenzene sulfonate, 4-t- Examples include butoxyphenyl diphenylsulfonium nonafluoro-n-butanesulfonate, 4-hydroxyphenyl benzyl methylsulfonium p-toluenesulfonate, and the like.

Sulfone compounds:
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 compounds:
Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.
Specific examples of the sulfonate compound include benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), pyrogallol tris (nonafluoro-n-butanesulfonate), pyrogallol tris (methanesulfonate), nitrobenzyl-9,10-diethoxyanthracene. -2-Sulfonate, α-methylol benzoin tosylate, α-methylol benzoin n-octane sulfonate, α-methylol benzoin trifluoromethane sulfonate, α-methylol benzoin n-dodecane sulfonate and the like.
Sulfonimide compounds:
As a sulfonimide compound, for example, the following formula (2)

〔式（１）において、Ｖはアルキレン基、アリーレン基、アルコキシレン基等の２価の基を示し、Ｒ³ はアルキル基、アリール基、ハロゲン置換アルキル基、ハロゲン置換アリール基等の１価の基を示す。〕
で表される化合物を挙げることができる。

[In the formula (1), V represents a divalent group such as an alkylene group, an arylene group or an alkoxylene group, and R ³ represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group. Indicates a group. ]
The compound represented by these can be mentioned.

As a specific example of the sulfonimide compound,
N- (trifluoromethanesulfonyloxy) succinimide, N- (trifluoromethanesulfonyloxy) phthalimide, N- (trifluoromethanesulfonyloxy) diphenylmaleimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethane Sulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) 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- (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-trifluoro Methylbenzenesulfonyloxy) 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) naphthylimi ,

N- (4-trifluoromethylbenzenesulfonyloxy) succinimide, N- (4-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (4-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N- (4-trifluoro Methylbenzenesulfonyloxy) 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- (nonafluoro-n-butanesulfonyloxy) 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- (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- (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-{(5-methyl-5- Carboxymethyl methane [2.2.1] hept-2-yl) can be mentioned sulfonyloxy} succinimide, and the like.
Diazomethane compounds:
As a diazomethane compound, for example, the following formula (3)

〔式（３）において、Ｒ⁴ およびＲ⁵ は相互に独立にアルキル基、アリール基、ハロゲン置換アルキル基、ハロゲン置換アリール基等の１価の基を示す。〕
で表される化合物を挙げることができる。

[In Formula (3), R ⁴ and R ⁵ each independently represent a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group. ]
The compound represented by these can be mentioned.

Specific examples of diazomethane compounds include bis (trifluoromethanesulfonyl) diazomethane, bis (cyclohexanesulfonyl) diazomethane, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, methanesulfonyl-p-toluenesulfonyldiazomethane, cyclohexanesulfonyl -1,1-dimethylethylsulfonyldiazomethane, bis (1,1-dimethylethanesulfonyl) diazomethane, 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 compounds:
As the disulfonylmethane compound, for example, the following formula (4)

[In the formula (4), R ⁶ and R ⁷ are each independently a linear or branched monovalent aliphatic hydrocarbon group, a cycloalkyl group, an aryl group, an aralkyl group, or a monovalent 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 connected to each other to form a monocyclic or polycyclic ring having at least one unsaturated bond, or X and Y are Connected to each other

(However, X ′ and Y ′ each independently represent a hydrogen atom, a halogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, or the same or different carbon atoms. The bonded X ′ and Y ′ are connected to each other to form a carbon monocyclic structure, and a plurality of X ′ and Y ′ may be the same or different from each other, and n is an integer of 2 to 10. is there.)
The group represented by these is formed. ]
The compound represented by these can be mentioned.

  As the acid generator (B), an onium salt compound and a sulfonimide compound are preferable. In particular, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n- Butanesulfonate, bis (4-tert-butylphenyl) iodonium p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium 10-camphorsulfonate, bis (4-tert-butylphenyl) iodonium 2-trifluoromethylbenzenesulfonate Bis (4-tert-butylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium 2,4-difluorobenzenesulfonate, triphenylsulfonium trifluoro Methanesulfonate, triphenylsulfonium perfluoro-n-butanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium 2-trifluoromethylbenzenesulfonate, triphenylsulfonium 4-trifluorobenzenesulfonate , Triphenylsulfonium 2,4-difluoromethylbenzenesulfonate, N- (trifluoromethanesulfonyloxy) succinimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-di Carboximide, N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) bicyclo [2. .1] From the group of hept-5-ene-2,3-dicarboximide and N-{(5-methyl-5-carboxymethanebicyclo [2.2.1] hept-2-yl) sulfonyloxy} succinimide It is preferable to use at least one selected.

Alkali-soluble resin The alkali-soluble resin used in the present invention is soluble in an alkali developer having at least one functional group having affinity with an alkali developer, for example, an acidic functional group such as a phenolic hydroxyl group or a carboxyl group. It is a good resin.
Examples of such alkali-soluble resins include addition polymerization resins having at least one repeating unit represented by the following formulas (7) to (9), and one repeating unit represented by the following formula (10). Examples thereof include the polycondensation resins described above.

〔式（７）において、Ｒ⁸ は水素原子またはメチル基を示し、Ｒ⁹ は水酸基、カルボキシル基、−Ｒ¹⁰ＣＯＯＨ、−ＯＲ¹⁰ＣＯＯＨ、−ＯＣＯＲ¹⁰ＣＯＯＨまたは
−ＣＯＯＲ¹⁰ＣＯＯＨ（但し、Ｒ¹⁰は−（ＣＨ₂)g −を示し、ｇは１〜４の整数である。）を示す。〕

[In the formula (7), R ⁸ represents a hydrogen atom or a methyl group, R ⁹ represents a hydroxyl group, a carboxyl group, —R ¹⁰ COOH, —OR ¹⁰ COOH, —OCOR ¹⁰ COOH or —COOR ¹⁰ COOH (where R ¹⁰ is - (CH ₂₎ g - indicates, g represents an an integer of 1 to 4).. ]

〔式（８）において、Ｒ¹¹は水素原子またはメチル基を示す。〕

[In Formula (8), R < ¹¹ > shows a hydrogen atom or a methyl group. ]

〔式（１０）において、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵およびＲ¹⁶は相互に独立に水素原子または炭素数１〜４のアルキル基を示す。〕

[In Formula (10), R < ¹² >, R <^13> , R <^14> , R <^15> and R < ¹⁶ > show a hydrogen atom or a C1-C4 alkyl group mutually independently. ]

When the alkali-soluble resin is an addition polymerization resin, it may be composed only of the repeating units represented by the above formulas (7) to (9), but as long as the produced resin is soluble in an alkali developer. It may further have one or more other repeating units.
Examples of such other repeating units include styrene, α-methylstyrene, maleic anhydride, (meth) acrylonitrile, crotonnitrile, maleinonitrile, fumaronitrile, mesacononitrile, citracononitrile, itaconnitrile, (meth) acrylamide. , Crotonamide, maleinamide, fumaramide, mesaconamide, citraconic amide, itaconic amide, vinyl aniline, vinyl pyridine, vinyl-ε-caprolactam, vinyl pyrrolidone, vinyl imidazole, etc. .

The addition polymerization resin (co) polymerizes, for example, a monomer corresponding to the repeating unit represented by the formulas (7) to (9) together with a monomer that forms the other repeating unit. Can be manufactured.
These (co) polymerizations are carried out by appropriately using a polymerization initiator such as a radical polymerization initiator, an anionic polymerization catalyst, a coordination anionic polymerization catalyst, a cationic polymerization catalyst or a polymerization catalyst depending on the type of monomer and reaction medium. It can be selected and carried out by an appropriate polymerization method such as bulk polymerization, solution polymerization, precipitation polymerization, emulsion polymerization, suspension polymerization, bulk-suspension polymerization.

Further, when the alkali-soluble resin is a polycondensation resin, it may be composed only of the repeating unit represented by the formula (10), but as long as the produced resin is soluble in an alkali developer, 1 It can also have other repeating units of species or more. Such a polycondensation resin is obtained by mixing phenols and aldehydes corresponding to the repeating unit represented by the formula (10) with a polycondensation component capable of forming other repeating units in the presence of an acidic catalyst. It can be produced by (co) polycondensation in an aqueous medium or in a mixed medium of water and a hydrophilic solvent.
Examples of the phenols include o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol and the like can be mentioned. Examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde and the like. Can be mentioned.

The content of the repeating unit represented by the formulas (7) to (10) in the alkali-soluble resin cannot be defined unconditionally depending on the type of the other repeating unit contained in some cases, but preferably 10 to 100 mol%. More preferably, it is 20-100 mol%.
When the alkali-soluble resin has a repeating unit containing a carbon-carbon unsaturated bond represented by the formula (7), the formula (10) or the like, it can also be used as a hydrogenated product. In this case, the hydrogenation rate is usually 70% or less, preferably 50% or less, more preferably 50% or less, of the carbon-carbon unsaturated bond contained in the repeating unit represented by formula (7), formula (10) or the like. Is 40% or less. In this case, if the hydrogenation rate exceeds 70%, the developability of the alkali-soluble resin with an alkali developer may be lowered.

In the present invention, the alkali-soluble resin can be used alone or in admixture of two or more, but it is necessary to contain a p-hydroxystyrene / styrene copolymer as an essential component.
Examples of the alkali-soluble resin other than the p-hydroxystyrene / styrene copolymer in the present invention include poly (p-hydroxystyrene) and p-hydroxystyrene / p-hydroxy-α-methylstyrene copolymer. .
The polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography of the alkali-soluble resin varies depending on the desired properties of the radiation-sensitive resin composition, but preferably 1,000 to 150. 1,000, more preferably 3,000-100,000.

Crosslinking agent As a compound capable of crosslinking an alkali-soluble resin in the presence of an acid (for example, an acid generated by exposure) used in the present invention (hereinafter referred to as “crosslinking agent”), for example, crosslinking with an alkali-soluble resin. Examples thereof include compounds having one or more reactive functional groups (hereinafter referred to as “crosslinkable functional groups”).
Examples of the crosslinkable functional group include groups represented by the following formulas (18) to (22).

〔式（１８）において、ｋは１または２であり、Ｑ¹ は、ｋ＝１のとき、単結合、−Ｏ−、−Ｓ−、−ＣＯＯ−または−ＮＨ−を示し、ｋ＝２のとき、３価の窒素原子を示し、
Ｑ² は−Ｏ−または−Ｓ−を示し、i は０〜３の整数、j は１〜３の整数で、i ＋ j＝１〜４を満たす。〕

[In the formula (18), k is 1 or 2, and Q ¹ represents a single bond, —O—, —S—, —COO— or —NH— when k = 1, and k = 2 Sometimes showing a trivalent nitrogen atom,
Q ² represents —O— or —S—, i is an integer of 0 to 3, j is an integer of 1 to 3, and i + j = 1 to 4 is satisfied. ]

〔式（１９）において、Ｑ³ は−Ｏ−、−ＣＯ−または−ＣＯＯ−を示し、Ｒ²²および
Ｒ²³は相互に独立に水素原子または炭素数１〜４のアルキル基を示し、
Ｒ²⁴は炭素数１〜５のアルキル基、炭素数６〜１２のアリール基または炭素数７〜１４のアラルキル基を示し、y は１以上の整数である。〕

[In the formula (19), Q ³ represents —O—, —CO— or —COO—, R ²² and R ²³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ²⁴ represents an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 14 carbon atoms, and y is an integer of 1 or more. ]

〔式（２０）において、Ｒ²⁵、Ｒ²⁶およびＲ²⁷は相互に独立に水素原子または炭素数１〜４のアルキル基を示す。〕

[In Formula (20), R ²⁵ , R ²⁶ and R ²⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

〔式（２１）において、Ｒ²²およびＲ²³は式（１９）と同義であり、Ｒ²⁸およびＲ²⁹は相互に独立に炭素数１〜５のアルキル基または炭素数１〜５のアルキロール基を示し、y は１以上の整数である。〕

[In the formula (21), R ²² and R ²³ are as defined in the formula (19), and R ²⁸ and R ²⁹ are each independently an alkyl group having 1 to 5 carbon atoms or an alkylol group having 1 to 5 carbon atoms. Y is an integer of 1 or more. ]

〔式（２２）において、Ｒ²²およびＲ²³は式（１９）と同義であり、Ｒ³⁰は酸素原子、硫黄原子または窒素原子のいずれかのヘテロ原子を有し、３〜８員環を形成する２価の有機基を示し、y は１以上の整数である。〕

[In the formula (22), R ²² and R ²³ have the same meanings as those in the formula (19), and R ³⁰ has a hetero atom of any one of an oxygen atom, a sulfur atom and a nitrogen atom to form a 3- to 8-membered ring. And y is an integer of 1 or more. ]

  Specific examples of such crosslinkable functional groups include glycidyl ether groups, glycidyl ester groups, glycidyl amino groups, methoxymethyl groups, ethoxymethyl groups, benzyloxymethyl groups, acetoxymethyl groups, benzoyloxymethyl groups, formyl groups. Acetyl group, vinyl group, isopropenyl group, dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, diethylolaminomethyl group, morpholinomethyl group and the like.

  Examples of the compound having a crosslinkable functional group include a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, a novolac resin epoxy compound, a resole resin epoxy compound, and a poly (hydroxystyrene) epoxy. Compound, methylol group-containing melamine compound, methylol group-containing benzoguanamine compound, methylol group-containing urea compound, methylol group-containing phenol compound, alkoxyalkyl group-containing melamine compound, alkoxyalkyl group-containing benzoguanamine compound, alkoxyalkyl group-containing urea compound, alkoxyalkyl group -Containing phenol compound, carboxymethyl group-containing melamine resin, carboxymethyl group-containing benzoguanamine resin, carboxymethyl group-containing urea resin Carboxymethyl group-containing phenol resin, carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compounds, mention may be made of carboxymethyl group-containing phenol compounds and the like.

  Among these compounds having a crosslinkable functional group, a methylol group-containing phenol compound, a methoxymethyl group-containing melamine compound, a methoxymethyl group-containing phenol compound, a methoxymethyl group-containing glycoluril compound, a methoxymethyl group-containing urea compound, and an acetoxymethyl group Containing phenol compounds are preferred, and more preferred are methoxymethyl group-containing melamine compounds (for example, hexamethoxymethyl melamine), methoxymethyl group-containing glycoluril compounds, methoxymethyl group-containing urea compounds, and the like. The methoxymethyl group-containing melamine compound is a trade name such as CYMEL300, CYMEL301, CYMEL303, CYMEL305 (manufactured by Mitsui Cyanamid Co., Ltd.), and the methoxymethyl group-containing glycoluril compound is a trade name such as CYMEL1174 (manufactured by Mitsui Cyanamid Co., Ltd.). The methoxymethyl group-containing urea compounds are commercially available under trade names such as MX290 (manufactured by Sanwa Chemical Co., Ltd.).

  As the cross-linking agent, a compound having a property as a cross-linking agent obtained by substituting the hydrogen atom of the acidic functional group in the alkali-soluble resin with the cross-linkable functional group can also be suitably used. In this case, the rate of introduction of the crosslinkable functional group cannot be unconditionally defined by the type of the crosslinkable functional group or the alkali-soluble resin into which the group is introduced. 5 to 60 mol%, preferably 10 to 50 mol%, more preferably 15 to 40 mol%. In this case, if the introduction ratio of the crosslinkable functional group is less than 5 mol%, the remaining film ratio tends to decrease, the pattern meanders or swells easily, and if it exceeds 60 mol%, the development of the exposed area tends to occur. Tend to decrease.

As the crosslinking agent in the present invention, a methoxymethyl group-containing compound such as dimethoxymethylurea, tetramethoxymethylglycoluril and the like are particularly preferable.
In this invention, a crosslinking agent can be used individually or in mixture of 2 or more types.

Although the blending ratio of each component constituting the negative radiation-sensitive resin composition of the present invention varies depending on the desired properties of the resist, preferred blending ratios are as follows.
The amount of compound (A) is preferably 0.001 to 15 parts by weight, more preferably 0.005 to 10 parts by weight, and particularly preferably 0.01 to 3 parts by weight per 100 parts by weight of the alkali-soluble resin. . In this case, if the compounding amount of the compound (A) is less than 0.001 part by weight, the resolution and pattern shape tend to be deteriorated. On the other hand, if it exceeds 15 parts by weight, the sensitivity and development of the exposed part tend to occur. Tend to decrease.
The amount of the acid generator (B) is preferably 0.01 to 70 parts by weight, more preferably 0.1 to 50 parts by weight, particularly preferably 0.5 to 20 parts per 100 parts by weight of the alkali-soluble resin. Parts by weight. In this case, if the blending amount of the acid generator (B) is less than 0.01 parts by weight, the sensitivity and resolution tend to decrease. On the other hand, if it exceeds 70 parts by weight, the resist coatability and pattern shape deteriorate. It tends to be easy to do.
Moreover, the compounding quantity of a crosslinking agent becomes like this. Preferably it is 5-95 weight part per 100 weight part of alkali-soluble resin, More preferably, it is 15-85 weight part, Most preferably, it is 20-75 weight part. In this case, if the blending amount of the cross-linking agent is less than 5 parts by weight, the remaining film ratio tends to decrease, the pattern meanders or swells easily, and if it exceeds 95 parts by weight, the developability of the exposed part is increased. There is a tendency to decrease.

More specifically showing the blending ratio of each component in the present invention,
Preferably,
[1] 0.001 to 15 parts by weight of the compound (A), 0.01 to 70 parts by weight of the acid generator (B), 100 parts by weight of the alkali-soluble resin and 5 to 95 parts by weight of the crosslinking agent,
More preferably,
[2] 0.005 to 10 parts by weight of the compound (A), 0.1 to 50 parts by weight of the acid generator (B), 100 parts by weight of the alkali-soluble resin and 15 to 85 parts by weight of the crosslinking agent,
Particularly preferably,
[3] 0.01 to 3 parts by weight of the compound (A), 0.5 to 20 parts by weight of the acid generator (B), 100 parts by weight of the alkali-soluble resin and 20 to 75 parts by weight of the crosslinking agent.

Additives In the negative radiation sensitive resin composition of the present invention, an acid diffusion control agent other than the compound (A) (hereinafter referred to as “other acid diffusion control agent”), a surfactant, Various additives such as a sensitizer can be blended.
Other acid diffusion control agents include, for example, the following formula (23)

[In the formula (23), R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group or an aralkyl group. And the aralkyl group may each be substituted. ] (Hereinafter referred to as “nitrogen-containing compound (I ′)”), a compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (II ′)”), nitrogen A compound having 3 or more atoms (hereinafter referred to as “nitrogen-containing compound (III ′)”), an amide group-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, and the like can be given.

  As the nitrogen-containing compound (I ′), in addition to the nitrogen-containing compound (I) exemplified as the amino compound (a), for example, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n— Trityl such as pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, methyldicyclohexylamine, tricyclohexylamine Alkylamines; alkanolamines such as ethanolamine, diethanolamine, and triethanolamine.

  As the nitrogen-containing compound (II ′), in addition to the nitrogen-containing compound (II) exemplified as the amino compound (a), for example, N, N, N ′, N′-tetramethylethylenediamine, N, N, N Examples include ', N'-tetrakis (2-hydroxyethyl) ethylenediamine, N, N, N', N'-tetrakis (2-hydroxypropyl) ethylenediamine, and the like. Examples of the nitrogen-containing compound (III ′) include, in addition to the nitrogen-containing compound (III) exemplified as the amino compound (a), polymers such as polyethyleneimine and N- (2-dimethylaminoethyl) acrylamide. be able to.

Examples of the amide group-containing compound include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like in addition to the amide group-containing compounds exemplified as the amino compound (a). it can.
Examples of the urea compound include 1,1,3,3-tetramethylurea, in addition to the urea compound exemplified as the amino compound (a).
Examples of the nitrogen-containing heterocyclic compound include, in addition to the nitrogen-containing heterocyclic compound exemplified as the amino compound (a), for example, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine. , 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, acridine and other pyridines, pyrazine, pyridazine, quinosaline, 4 -Methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane and the like can be mentioned.

Of these other acid diffusion control agents, nitrogen-containing compounds (I ′), nitrogen-containing compounds (II ′), nitrogen-containing heterocyclic compounds and the like are preferable.
The other acid diffusion control agents can be used alone or in admixture of two or more.
The blending amount of the other acid diffusion control agent is usually 90% by weight or less, preferably 70% by weight or less, particularly preferably 50% by weight or less, based on the total of the compound (A) and the other acid diffusion control agent. It is. In this case, if the blending amount of the other acid diffusion control agent exceeds 90% by weight, the intended effect in the present invention may be impaired.

Moreover, the said surfactant shows the effect | action which improves the applicability | paintability, striation, developability, etc. of a radiation sensitive resin composition. As such a surfactant, any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, polyethylene glycol higher fatty acid diesters, and the following trade names: KP (manufactured by Shin-Etsu Chemical) , Polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), F Top (manufactured by Tokemu Products), Mega Fuck (manufactured by Dainippon Ink & Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass) Can be mentioned.
The surfactants can be used alone or in admixture of two or more. The compounding 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 total resin components 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. The radiation-sensitive resin composition It has the effect of improving the apparent sensitivity.
Preferred sensitizers are acetophenones, benzophenones, naphthalenes, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines and the like. The said sensitizer can be used individually or in mixture of 2 or more types.
The blending amount of the sensitizer is usually 50 parts by weight or less, preferably 30 parts by weight or less per 100 parts by weight of the total resin components in the radiation-sensitive resin composition.
Also, by blending dyes and / or pigments, the latent image of the exposed area can be visualized, and the influence of halation during exposure can be mitigated. By blending an adhesion aid, adhesion to the substrate is improved. be able to.
Furthermore, examples of other additives include an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improving agent, and the like, specifically 4-hydroxy-4′-methylchalcone.

Solvent When using the negative radiation-sensitive resin composition of the present invention, dissolve it in a solvent so that the solid content concentration is, for example, 2 to 50% by weight, and then filter with a filter having a pore size of about 0.2 μm, for example. To prepare a composition solution.
Examples of the solvent include ethers, esters, ether esters, ketone esters, ketones, amides, amide esters, lactams, lactones, and (halogenated) hydrocarbons. More specifically, ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, acetate esters , Hydroxyacetic acid esters, alkoxyacetic acid esters, acetoacetic acid esters, propionic acid esters, lactic acid esters, alkoxypropionic acid esters, butyric acid esters Pyruvates, (non-) cyclic ketones, N, N-dialkylformamides, N, N-dialkylacetamides, N-alkylpyrrolidones, γ-lactones, (halogenated) aliphatic hydrocarbons, (Halogenated) aromatic hydrocarbons can be mentioned.

Specific examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n- Propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono- n-propyl ether ace , Ethyl acetate, n-propyl acetate, n-butyl acetate, isopropenyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl hydroxyacetate, ethyl ethoxyacetate, methyl acetoacetate, acetoacetic acid Ethyl, isopropenyl propionate, 3-methyl-3-methoxybutylpropionate, ethyl lactate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl butyrate, methyl 2-hydroxy-3-methylbutyrate, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, N, N-dimethyl Formamide, N, N- dimethylacetamide, N- methylpyrrolidone, toluene, xylene and the like.
Of these solvents, propylene glycol monoalkyl ether acetates, lactic acid esters, 3-alkoxypropionic acid esters, (non) cyclic ketones, and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

  Further, the solvent may be benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol as necessary. One or more high-boiling solvents such as benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate can be added.

Formation of resist pattern When forming a resist pattern from the negative radiation-sensitive resin composition of the present invention, the composition solution prepared as described above is applied by means such as spin coating, cast coating, roll coating, etc. Then, for example, a resist film is formed by coating on a substrate such as a silicon wafer or a wafer coated with aluminum, followed by heat treatment (hereinafter referred to as “PB”), and then a predetermined mask pattern is formed. To expose the resist film. The radiation that can be used in this case is preferably a far ultraviolet ray such as an emission line spectrum of a mercury lamp (wavelength 254 nm), a KrF excimer laser (wavelength 248 nm), or an ArF excimer laser (wavelength 193 nm), but the acid generator (B) Depending on the type, X-rays such as synchrotron radiation, charged particle beams such as electron beams, and the like can be used. In addition, exposure conditions such as radiation dose are appropriately selected according to the composition of the radiation-sensitive resin composition, the type of additive, and the like.
After the exposure, in order to improve the apparent sensitivity of the resist, it is preferable to perform a heat treatment (hereinafter referred to as “PEB”). The heating conditions vary depending on the composition of the radiation-sensitive resin composition, the type of additive, and the like, but are usually 30 to 200 ° C, preferably 50 to 150 ° C.

Then, a predetermined resist pattern is formed by developing with an alkaline developer.
Examples of the alkali developer include alkali metal hydroxides, aqueous ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo [5.4. .0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene and the like, usually 1 to 10% by weight, preferably 2 to 5% by weight. An alkaline aqueous solution dissolved so as to have a concentration is used. A particularly preferred alkaline developer is an aqueous solution of tetraalkylammonium hydroxides. In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the developer composed of the alkaline aqueous solution.
In addition, when using the developing solution which consists of alkaline aqueous solution in this way, generally it wash | cleans with water after image development.

The negative radiation sensitive resin composition of the present invention is excellent in sensitivity and resolution by using a specific compound (A) as an acid diffusion control agent, has a small optical proximity effect, and has a fine pattern even in an isolated line pattern. Can be formed with high accuracy and stability, a sufficient focus margin can be secured for the isolated line pattern, and storage stability is also excellent. Moreover, both radiation-sensitive resin compositions can effectively respond to various types of radiation such as deep ultraviolet rays, X-rays, and charged particle beams.
Therefore, the negative radiation-sensitive resin composition of the present invention is extremely useful as a resist for semiconductor device production, which is expected to become increasingly finer in the future.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
Here, each resist was evaluated in the following manner.
The exposure amount for forming a line-and-space pattern (1L1S) having a sensitivity design dimension of 0.20 μm in a one-to-one line width was defined as the optimum exposure amount, and the optimum exposure amount was evaluated.
Resolution (1L1S)
With respect to a line and space pattern (1L1S) having a design dimension of 0.20 μm, the minimum dimension (μm) resolved when exposed at the optimum exposure amount was defined as the resolution (1L1S).
Resolution (1L5S)
For an isolated line pattern (1L5S) having a line pattern design dimension of 0.20 μm, the line width of the line pattern resolved when exposed at the optimum exposure amount in the case of the line and space pattern (1L1S) is ( The minimum dimension (μm) that falls within the range of the design dimension ± 10% was defined as the resolution (1L5S). The difference between the resolution (1L5S) and the resolution (1L1S) represents the size difference due to pattern density, that is, the degree of influence of the optical proximity effect.
DOF (1L5S)
For an isolated line pattern (1L5S) having a line pattern design size of 0.20 μm, an exposure amount for forming the isolated line pattern (1L5S) in a line width of 1: 5 is set as an optimum exposure amount, and a depth of focus is set at the optimum exposure amount. The depth of focus (μm) within which the line width of the line pattern falls within the range of (design dimension ± 10%) was defined as the focus margin (DOF (1L5S)) of the isolated line pattern (1L5S). The wider the DOF, the higher the process margin and the higher the yield during device manufacturing, which is preferable.
Compare the resist evaluation results when using the composition solution stored at 23 ° C. for 6 months after preparation of storage stability with the resist evaluation results when using the composition solution immediately after preparation. When the change rate of the optimum exposure amount of the line and space pattern (1L1S) with a design dimension of 0.20 μm is less than ± 2%, “○”, and the change in resolution and pattern shape is recognized. If the change rate of the optimum exposure amount of a line and space pattern (1L1S) with a design dimension of 0.20 μm is ± (2 to 5%), “Δ”, either resolution or pattern shape The case where the above changes or the change rate of the optimum exposure amount of the line and space pattern (1L1S) having the design dimension of 0.20 μm exceeds ± 5% was evaluated as “×”.

Each component used in each example and comparative example is as follows.
Acid diffusion control agent
Compound (A)
A-1: Nt-butoxycarbonyldicyclohexylamine A-2: Nt-butoxycarbonyl-2-phenylbenzimidazole

Other compounds α-1: methyldicyclohexylamine
Acid generator (B)
B-1: Bis (cyclohexanesulfonyl) diazomethane
Alkali-soluble resin D-1: poly (p-hydroxystyrene) (Mw = 7,500)
D-2: p-hydroxystyrene / styrene copolymer (copolymerization molar ratio = 8: 2, Mw = 4,000)
Crosslinking agent E-1: Dimethoxymethylurea (trade name MX290, manufactured by Sanwa Chemical Co., Ltd.)
E-2: Tetramethoxymethyl glycoluril (trade name CYMEL1174, manufactured by Mitsui Cyanamid Co., Ltd.)
Solvent S-1: Ethyl lactate

Examples 1-2 and Comparative Example 1
Each component shown in Table 1 (where parts are based on weight) was mixed to obtain a uniform solution, and then filtered through a membrane filter having a pore size of 0.2 μm to prepare a composition solution. Then, after spin-coating each composition solution on the silicon wafer, PB was performed on the conditions shown in Table 2, and the resist film with a film thickness of 0.5 micrometer was formed.
Next, using a KrF excimer laser irradiation apparatus (trade name: NSR-2205 EX12B, numerical aperture: 0.55) manufactured by Nikon Corporation, an exposure amount of an excimer laser with a wavelength of 248 nm is changed through a mask pattern on each resist film. After the exposure, PEB was performed under the conditions shown in Table 2. Thereafter, a 2.38 wt% tetramethylammonium hydroxide aqueous solution was used and developed by the paddle method at 23 ° C. for 60 seconds, followed by washing with pure water for 30 seconds and drying to form a resist pattern. The evaluation results are shown in Table 3.

Claims (3)

(A) a low molecular compound in which at least one hydrogen atom bonded to the nitrogen atom of the compound having at least one amino group in which at least one hydrogen atom is bonded to the nitrogen atom is substituted with a t-butoxycarbonyl group;
(B) a radiation sensitive acid generator,
A negative radiation-sensitive resin composition comprising (D) an alkali-soluble resin containing a p-hydroxystyrene / styrene copolymer and (E) a compound capable of crosslinking the alkali-soluble resin in the presence of an acid. object.   The low molecular weight compound of component (A) is Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt -Butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′-diaminodiphenylmethane, N, N′-di-t-butoxycarbonylhexamethylenediamine, N, N, N′N′-tetra-t-butoxycarbonylhexamethylenediamine N, N′-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t-butoxycarbonyl- 1,9-diaminononane, N, N′-di-t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl-1,12-diaminododecane, N, N′-di -T-Butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole and Nt-butoxycarbonyl-2-phenylbenzimidazole group The negative radiation sensitive resin composition of Claim 1 selected from these.   The negative radiation-sensitive resin composition according to claim 2, wherein the low molecular compound of component (A) is selected from the group consisting of Nt-butoxycarbonyldicyclohexylamine and Nt-butoxycarbonyl-2-phenylbenzimidazole. object.