JP2001114825A - Base polymer for resist composition, resist material and method for forming pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a chemical amplification negative type resist material having a high cross-linking efficiency and a high sensitivity. SOLUTION: This base polymer for a chemical amplification negative type resist comprises a recurring unit represented by general formula (1) (wherein R1 is a 1-10C linear, branched or cyclic alkyl group in which the carbon atom directly bonded to the oxygen atom is primary or secondary; R2 is hydrogen atom or a 1-10C linear, branched or cyclic alkyl group; m and n are each 0<m<5; and 0<n<5).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel base polymer for a chemically amplified negative resist material suitable for fine processing technology, a resist material using the same, and a pattern forming method.

[0002]

2. Description of the Related Art LSI
With the demand for finer pattern rules in accordance with higher integration and higher speed, far-ultraviolet lithography is regarded as promising as a next-generation fine processing technology. Deep-UV lithography can process 0.3 μm or less, and when a resist material having low light absorption is used, a pattern having side walls nearly perpendicular to the substrate can be formed. In recent years, attention has been paid to a technique utilizing a high-brightness KrF excimer laser as a light source of far ultraviolet rays. In order to use this technique as a mass production technique, a resist material having low light absorption and high sensitivity is demanded. .

From such a viewpoint, a chemically amplified resist material using an acid catalyst recently developed (Japanese Patent Publication No. 2-276)
No. 60, described in JP-A-63-27829, etc.)
It has high sensitivity, high resolution, and excellent characteristics, and is a particularly promising resist material for deep ultraviolet lithography.
These are known to exhibit excellent characteristics even in exposure using an electron beam or X-ray as a light source.

[0004] Generally, chemically amplified resist materials are used in a resist composition of 0.1.
It has begun to be used in the 3 micron process, has passed the 0.25 micron rule, is now applying the 0.18 micron rule to mass production, and has begun studying the 0.15 micron rule, and has been working on the miniaturization of KrF excimer laser lithography. The momentum is accelerating. At the same time, realistic studies using EB or X-rays as a light source for the next generation of miniaturization have begun, and further improvement in resolution of resist materials is required along with miniaturization of design rules.

Heretofore, a positive resist process using a positive resist material has been widely used, but a negative process has been found to be more advantageous in optical images. For example, in combination with a super-resolution technique such as the Shibuya-Levenson phase shift method or the edge shifter method, in a process using a positive resist, exposure is performed twice to prevent connection between line ends, and the phase is set to π → 1. Although there is a method of changing in a multi-step manner such as / 2π → 0, the process becomes complicated, the throughput is reduced, or the mask production becomes more difficult. In a wiring using a CMP process or a blocking separation step, a negative process in which a narrow slit can be opened is advantageous, and there is an advantage that a negative mask has a smaller dimensional variation between an isolated pattern and a repeated group pattern than a positive mask.

Although the negative process has many advantages in terms of optical images, the positive resist material is still superior in the performance of the resist material. Problems of the negative resist material include stringing (microbridge) between patterns, collapse and fall of patterns, and the like. These are thought to be due to the low crosslink density, increase the crosslink density,
It is considered that increasing the contrast between crosslinked and uncrosslinked leads to improved performance.

[0007] Transfer of Cr pattern in mask production,
Also, in the transfer of the phase shifter, the demand for increasing the accuracy is becoming stricter.
The high acceleration electron beam exposure apparatus described above has come to be used. One way to increase the throughput in direct drawing is to reduce the drawing area.
For this purpose, a negative resist material is more advantageous for the isolated pattern. Here, as the EB is accelerated, the influence of forward scattering is reduced, and the energy of the beam passes through the resist, so that the sensitivity of the resist has been reduced. In particular, in the case of EB direct drawing,
Since the sensitivity of the resist is directly linked to the throughput, there is an increasing demand for improving the sensitivity.

[0008] The present invention has been made in view of the above circumstances,
It is an object of the present invention to provide a chemically amplified negative resist base polymer capable of forming a highly sensitive resist film with high crosslinking efficiency, a chemically amplified negative resist material containing the polymer, and a pattern forming method using the resist material. .

[0009]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies to achieve the above object, and considered to increase the electron density of the hydroxyl group of phenol in order to increase the efficiency of the crosslinking reaction. As a result, it was found that crosslinking efficiency can be increased by introducing an alkoxy group as an electron donating group, particularly by introducing an alkoxy group as an electron donating group ortho to the hydroxyl group at the para position of the benzene ring. did. In addition, they have found that the incorporation of a branch in the polymer structure further increases the cross-linking efficiency, leading to the present invention.

Accordingly, the present invention provides the following base polymer, chemically amplified negative resist material, and pattern forming method.

[0011] Claim 1: A base polymer for a chemically amplified negative resist comprising a repeating unit represented by the following general formula (1):

[0012]

Embedded image (Wherein, R ¹ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a carbon atom directly connected to an oxygen atom is primary or secondary, and R ² is a hydrogen atom, or It is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. M and n are 0 <m <5 and 0 <n <5.)

(2) A chemically amplified negative resist base polymer comprising a repeating unit represented by the following general formula (2):

Embedded image (Wherein, R ¹ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a carbon atom directly connected to an oxygen atom is primary or secondary, and R ² is a hydrogen atom, or A linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, in the range of 0 ≦ a ≦ 1, 0 ≦ b ≦ 1, and 0 <a + b ≦ 1.)

(3) A chemically amplified negative resist base polymer comprising a repeating unit represented by the following general formula (3):

Embedded image (Wherein, R ¹ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a carbon atom directly connected to an oxygen atom is primary or secondary, and R ² is a hydrogen atom, or A linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, R ³ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may contain a hetero atom; ≦ a ≦
1, 0 ≦ b ≦ 1, 0 ≦ c <1, 0 ≦ d <1, and a + b + c + d = 1. )

(4) The base polymer for a chemically amplified negative resist according to the above (1), (2) or (3), which contains a unit represented by the following general formula (4).

Embedded image (In the formula, R ⁴ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, which may contain an ether bond or an ester bond.)

(5) The base polymer for a chemically amplified negative resist according to the above (4), which is a den polymer or a hyperbranched polymer represented by the following general formula (5).

Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁴ , a, b, c, and d are the same as above. E is 1 ≦ e ≦ 1,000.)

(6) The base polymer for a chemically amplified negative resist according to any one of (1) to (5), obtained by living anionic polymerization.

Claim 7: (A) The alkali-soluble base polymer according to any one of claims 1 to 6, which becomes alkali-insoluble or hardly soluble when the crosslinking agent is crosslinked, (B) an organic solvent, (C) A) a chemically amplified negative resist composition comprising: () an acid generator; and (D) a crosslinking agent.

(8) The chemically amplified negative resist material according to the above (7), which contains (E) a basic compound.

Claim 9: (1) a step of applying the chemically amplified negative resist material according to claim 7 or 8 onto a substrate;
A pattern forming method, comprising: a step of exposing with a high-energy beam or an electron beam of 500 nm or less through a photomask, and (3) a step of performing a heat treatment as necessary and then developing with a developer.

Hereinafter, the present invention will be described in more detail.
The base polymer for a chemically amplified negative resist of the present invention,
It has a repeating unit represented by the following general formula (1), preferably the following general formula (2), and more preferably the following general formula (3).

[0022]

Embedded image (Wherein, R ¹ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a carbon atom directly connected to an oxygen atom is primary or secondary, and R ² is a hydrogen atom, or It is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. M and n are 0 <m <5 and 0 <n <5.)

[0023]

Embedded image (Wherein, R ¹ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a carbon atom directly connected to an oxygen atom is primary or secondary, and R ² is a hydrogen atom, or A linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, in the range of 0 ≦ a ≦ 1, 0 ≦ b ≦ 1, and 0 <a + b ≦ 1.)

[0024]

Embedded image (Wherein, R ¹ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a carbon atom directly connected to an oxygen atom is primary or secondary, and R ² is a hydrogen atom, or A linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, R ³ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may contain a hetero atom; ≦ a ≦
1, 0 ≦ b ≦ 1, 0 ≦ c <1, 0 ≦ d <1, and a + b + c + d = 1. )

Here, the alkyl group for R ¹ includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl and the like. Is mentioned. Examples of the alkyl group for R ² include the same as described above, and may be a tertiary alkyl group such as a tert-butyl group. R ³ may be the same as R ² , but may contain a hetero atom such as a carbonyl group. Specific examples of such an alkyl group containing a hetero atom include an acetoxy group, a pivaloyl group,
Examples thereof include a tert-butoxycarbonyl group and an isopropoxycarbonyl group.

A, b, c, and d are 0 ≦ a ≦ 1, 0 ≦ b ≦
1, 0 <a + b ≦ 1, 0 ≦ c <1, 0 ≦ d <1,
a + b + c + d = 1, but preferably 0.2 <a +
b ≦ 1, 0 ≦ c <0.8, and 0 ≦ d <0.2.

It is preferable that the base polymer further has preferably 1 to 1,000 units of the following general formula (4).

[0028]

Embedded image (In the formula, R ⁴ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, which may contain an ether bond or an ester bond.)

Here, examples of the alkylene group include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, cyclopentylene, hexylene, cyclohexylene, octylene and the like. The arylene group includes a phenylene group. Further, these alkylene groups and arylene groups may have an ether bond (-O-) or an ester bond (-CO-O-).

In the present invention, the base polymer is preferably a den polymer or a hyperbranched polymer represented by the following general formula (5).

[0031]

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ , a, b, c, d are the same as above. E is 1 ≦ e ≦ 1,000, preferably 1 ≦ e ≦ 1
00. )

The denpolymer and the hyperbranched polymer of the present invention are specifically represented by the following general formulas (5a) to (5e):
And those having a repeating unit represented by

[0033]

Embedded image

[0034]

Embedded image

As a method for producing a den polymer having a phenol residue and a hyperbranched polymer according to the present invention, during living anion polymerization, a polymerization component is reacted with a compound having a termination component, and the polymerization is further advanced.
Polymerization is performed while repeating the progress of the reaction and the stopping operation.

For example, living anionic polymerization is started using the monomers represented by the general formulas (6a) to (6d), and after a predetermined amount is polymerized, the compound represented by the general formula (7) is reacted. If this operation is repeated many times, a predetermined denpolymer can be obtained.

[0037]

Embedded image

Here, in the above formula, R ⁵ has 1 carbon atom.
6 straight, branched or cyclic primary, secondary or tertiary alkyl group, or a trialkylsilyl group, R ⁶
Is an alkylene group having 1 to 20 carbon atoms, and X is a halogen, hydrogen, aldehyde group, hydroxyl group, carboxyl group or the like.

When performing living anionic polymerization, the reaction solvent is preferably a solvent such as toluene, benzene, tetrahydrofuran, dioxane or ethyl ether.
In particular, polar solvents such as tetrahydrofuran, dioxane, and ethyl ether are preferred, and they may be used alone or as a mixture of two or more.

As an initiator, sec-butyl lithium,
Preference is given to n-butyllithium, sodium naphthalene and cumyl potassium, the amount of which is used is proportional to the design molecular weight.

The reaction temperature is -80 to 100 ° C, preferably -70 to 0 ° C, and the reaction time is 0.1 to 100 ° C.
It is 50 hours, preferably 0.5 to 5 hours.

An example of a reaction formula when sec-butyllithium is used as an initiator is as follows. The following reaction is optionally repeated to change the degree of branching.

[0043]

Embedded image

The base polymer used in the present invention has a weight average molecular weight of 1,000 to 10,000,000.
0, more preferably 1,000 to 1,000,000,
More preferably, it is 1,000 to 100,000. Also, Mw / Mn is 1.0 to 3.0,
More preferably, it is 1.0 to 2.0.

The chemically amplified negative resist material of the present invention comprises:
It contains the above polymer, specifically,
(A) a base polymer which is alkali-insoluble or hardly soluble when the cross-linking agent is cross-linked by the above-mentioned alkali-soluble, (B)
It contains an organic solvent, (C) an acid generator, and (D) a crosslinking agent.

Here, the organic solvent of the component (B) used in the present invention is an organic solvent in which an acid generator, a base resin (the polymer compound of the present invention), a dissolution inhibitor and the like can be dissolved. Either may be used. Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, and 3-methyl-
Alcohols such as 3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether , Ethers such as diethylene glycol dimethyl ether,
Propylene glycol monomethyl ether acetate,
Propylene glycol monoethyl ether acetate,
Ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-propionate
Esters such as butyl and propylene glycol-mono-tert-butyl ether acetate can be mentioned, and one of these can be used alone or as a mixture of two or more, but is not limited thereto. In the present invention, among these organic solvents, in addition to diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, and ethyl lactate, which have the highest solubility of the acid generator in the resist component, propylene glycol monomethyl ether acetate, which is a safe solvent, is used. And mixed solvents thereof are preferably used.

The amount of the organic solvent used is based on the base resin 1
200 to 5,000 parts by weight, especially 4 parts by weight
It is 00 to 3,000 parts by weight.

Examples of the acid generator (C) include onium salts of the following general formula (11), diazomethane derivatives of the formula (12), glyoxime derivatives of the formula (13), β-ketosulfone derivatives, disulfone derivatives, nitrobenzyl Sulfonate derivatives, sulfonic acid ester derivatives, imido-yl sulfonate derivatives, and the like. (R ³⁰ ) _b M ⁺ K ⁻ (11) (where R ³⁰ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or 7 to 12 carbon atoms) Wherein M ⁺ represents iodonium or sulfonium, K ⁻ represents a non-nucleophilic counter ion, and b is 2 or 3.)

Examples of the alkyl group for R ³⁰ include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group,
An oxocyclohexyl group, a norbornyl group, an adamantyl group and the like can be mentioned. As the aryl group, a phenyl group,
p-methoxyphenyl group, m-methoxyphenyl group, o
-Methoxyphenyl group, ethoxyphenyl group, p-te
an alkoxyphenyl group such as an rt-butoxyphenyl group, an m-tert-butoxyphenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group,
Ethylphenyl group, 4-tert-butylphenyl group,
Examples thereof include an alkylphenyl group such as a 4-butylphenyl group and a dimethylphenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. K ^- a non-nucleophilic counter chloride ions as the ion, halide ions such as bromide ion, triflate, 1,1,1-trifluoroethane sulfonate, fluoroalkyl sulfonate such as nonafluorobutanesulfonate, tosylate, benzenesulfonate , 4-fluorobenzenesulfonate, arylsulfonates such as 1,2,3,4,5-pentafluorobenzenesulfonate, and alkylsulfonates such as mesylate and butanesulfonate.

[0050]

Embedded image (However, R ³¹ and R ³² are a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogenated aryl group or 7 carbon atoms. ~ 12 aralkyl groups.)

Examples of the alkyl group for R ³¹ and R ³² include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, a nonafluorobutyl group, and the like. Examples of the aryl group include phenyl, p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, and m-tert.
An alkoxyphenyl group such as -butoxyphenyl group, 2-
Examples thereof include an alkylphenyl group such as a methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, and a dimethylphenyl group. Examples of the halogenated aryl group include a fluorobenzene group, a chlorobenzene group, a 1,2,3,4,5-pentafluorobenzene group, and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0052]

Embedded image (However, R ³³ , R ³⁴ and R ³⁵ are linear having 1 to 12 carbon atoms,
It represents a branched or cyclic alkyl group or a halogenated alkyl group, an aryl group having 6 to 12 carbon atoms, an aryl halide group or an aralkyl group having 7 to 12 carbon atoms. Also,
R ³⁴ and R ³⁵ may combine with each other to form a cyclic structure, and when forming a cyclic structure, R ³⁴ and R ³⁵ each represent a linear or branched alkylene group having 1 to 6 carbon atoms. . )

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group of R ³³ , R ³⁴ , and R ³⁵ include the same groups as those described for R ³¹ and R ³² . The alkylene group for R ³⁴ and R ³⁵ includes a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and the like.

Specifically, for example, diphenyliodonium trifluoromethanesulfonate, phenyliodonium trifluoromethanesulfonate (p-tert-butoxyphenyl), diphenyliodonium p-toluenesulfonate, p-toluenesulfonic acid (p-tert-sulfonic acid)
(Butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris trifluoromethanesulfonate (P-tert-butoxyphenyl) sulfonium,
triphenylsulfonium p-toluenesulfonate, p
-(P-tert-butoxyphenyl) diphenylsulfonium toluenesulfonate, bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, tris (p-tert-toluenesulfonate)
(t-butoxyphenyl) sulfonium, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) Sulfonium, cyclohexylmethyl p-toluenesulfonate (2-oxocyclohexyl) sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate Onium salts such as bis (benze) Sulfonyl) diazomethane, bis (p- toluenesulfonyl) diazomethane, bis (xylene sulfonyl) diazomethane, bis (cyclohexyl sulfonyl) diazomethane, bis (cyclopentyl sulfonyl) diazomethane, bis (n- butylsulfonyl)
Diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (t
tert-butylsulfonyl) diazomethane, bis (n-
Amylsulfonyl) diazomethane, bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1
-(Tert-butylsulfonyl) diazomethane, 1-
Diazomethane derivatives such as cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane and 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane; bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime , Bis-o-
(P-toluenesulfonyl) -α-diphenylglyoxime, bis-o- (p-toluenesulfonyl) -α-dicyclohexylglyoxime, bis-o- (p-toluenesulfonyl) -2,3-pentanedione glyoxime, Bis-o- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-o-
(N-butanesulfonyl) -α-dimethylglyoxime, bis-o- (n-butanesulfonyl) -α-diphenylglyoxime, bis-o- (n-butanesulfonyl) -α-dicyclohexylglyoxime, bis-o −
(N-butanesulfonyl) -2,3-pentanedione glyoxime, bis-o- (n-butanesulfonyl) -2
-Methyl-3,4-pentanedione glyoxime, bis-o- (methanesulfonyl) -α-dimethylglyoxime, bis-o- (trifluoromethanesulfonyl) -α
-Dimethylglyoxime, bis-o- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o- (tert-butanesulfonyl) -α
-Dimethylglyoxime, bis-o- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis-o- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-o- (benzenesulfonyl) -α-
Dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-
o- (p-tert-butylbenzenesulfonyl) -α
Glyoxime derivatives such as -dimethylglyoxime, bis-o- (xylenesulfonyl) -α-dimethylglyoxime, bis-o- (camphorsulfonyl) -α-dimethylglyoxime, 2-cyclohexylcarbonyl-2
Β-ketosulfone derivatives such as-(p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane; disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone; 2,6-dinitro p-toluenesulfonate Nitrobenzylsulfonate derivatives such as benzyl and 2,4-dinitrobenzyl p-toluenesulfonate;
Tris (methanesulfonyloxy) benzene, 1,2,2
Sulfonate derivatives such as 3-tris (trifluoromethanesulfonyloxy) benzene and 1,2,3-tris (p-toluenesulfonyloxy) benzene, phthalimido-yl-triflate, phthalimido-yl-
Tosylate, 5-norbornene-2,3-dicarboximido-yl-triflate, 5-norbornene-2,
Imido-yl-sulfonate derivatives such as 3-dicarboximido-yl-tosylate and 5-norbornene-2,3-dicarboximido-yl-n-butylsulfonate; and triphenylsulfonium trifluoromethanesulfonate; Triphenylmethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid tris (p-
Onium such as tert-butoxyphenyl) sulfonium, triphenylsulfonium p-toluenesulfonate, diphenylsulfonium p-toluenesulfonate (p-tert-butoxyphenyl), and tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate Salt, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, Bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl)
Diazomethane derivatives such as diazomethane and bis (tert-butylsulfonyl) diazomethane; bis-o- (p-
Glyoxime derivatives such as toluenesulfonyl) -α-dimethylglyoxime and bis-o- (n-butanesulfonyl) -α-dimethylglyoxime are preferably used. In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types. The onium salt is excellent in the effect of improving the rectangularity, and the diazomethane derivative and the glyoxime derivative are excellent in the standing wave reducing effect. However, by combining the two, fine adjustment of the profile can be performed.

The compounding amount of the acid generator is 100 base resin.
The amount is preferably from 0.2 to 15 parts by weight, particularly preferably from 0.5 to 8 parts by weight with respect to parts by weight. If the amount is less than 0.2 parts by weight, the amount of acid generated upon exposure is small, and the sensitivity and resolution are poor. In some cases, when the amount exceeds 15 parts by weight, the transmittance of the resist is reduced, and the resolution may be poor.

As the basic compound as the component (E), a compound capable of suppressing the rate of diffusion of the acid generated from the acid generator into the resist film is suitable. By the compounding, the diffusion rate of the acid in the resist film is suppressed, the resolution is improved, the sensitivity change after exposure is suppressed, the dependency on the substrate and the environment is reduced, and the exposure margin and the pattern profile are improved. (JP-A-5-232706, JP-A-5-249683 and JP-A-5-249683).
No. 158239, No. 5-249662, No. 5-25
No. 7282, No. 5-289322, No. 5-28934
No. 0 publication).

Such basic compounds include primary, secondary and tertiary aliphatic amines, hybrid amines,
Aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group,
Examples of the compound include a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, and an imide derivative, and an aliphatic amine is particularly preferably used.

Specifically, the primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tertiary aliphatic amines.
t-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine,
Nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like are exemplified. As secondary aliphatic amines, dimethylamine, diethylamine, di-n
-Propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine,
Dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N
-Dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine, and the like. Examples of the tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, and triisopropylamine. , Tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine,
Triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-tetra Examples include methylethylenediamine, N, N, N ', N'-tetramethyltetraethylenepentamine and the like.

Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine and benzyldimethylamine. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (for example, aniline,
N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline , 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-
Dimethyl toluidine, etc.), diphenyl (p-tolyl) amine, methyl diphenylamine, triphenylamine,
Phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole,
2,5-dimethylpyrrole, N-methylpyrrole, etc.),
Oxazole derivatives (eg, oxazole, isoxazole, etc.), thiazole derivatives (eg, thiazole, isothiazole, etc.), imidazole derivatives (eg, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, Pyrroline derivatives (eg, pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (eg, pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg, pyridine, methyl) Pyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridyl , 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl- 4-phenylpyridine, 2- (1-ethylpropyl) pyridine,
Aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (Eg, quinoline, 3-quinolinecarbonitrile), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,1
Examples thereof include 0-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

Further, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (eg, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine,
Histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine) and the like, and 3-pyridinesulfonic acid as a nitrogen-containing compound having a sulfonyl group; Pyridinium p-toluenesulfonate and the like are exemplified. Examples of the nitrogen-containing compound having a hydroxy group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, and 2,4-quinolinediol. , 3-indolemethanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-imino Diethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1
-Butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2
-Hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine,
1- (2-hydroxyethyl) -2-pyrrolidinone, 3
-Piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyurolidine, 3-quinuclidinol, 3-tropanol,
Examples thereof include 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, and N- (2-hydroxyethyl) isonicotinamide. Examples of the amide derivative include formamide, N-methylformamide, N, N-dimethylformamide, acetamido, N-methylacetamido,
N-dimethylacetamide, propionamide, benzamide and the like are exemplified. Examples of the imide derivative include phthalimide, succinimide, and maleimide.

Further, basic compounds represented by the following general formulas (14) and (15) can be blended.

[0062]

Embedded image(Where R⁴¹, R⁴², R⁴³, R⁴⁷, R⁴⁸Are independent
Linear, branched or cyclic C 1-20 alkyl
Kylene group, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁹, R⁵⁰Is a hydrogen atom,
An alkyl group or an amino group having 1 to 20 carbon atoms;⁴⁴
And R⁴⁵, R⁴⁵And R ⁴⁶, R⁴⁴And R⁴⁶, R⁴⁴And R⁴⁵And R⁴⁶,
R⁴⁹And R⁵⁰May combine with each other to form a ring.
S, T, and U each represent an integer of 0 to 20. However,
When S, T, U = 0, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁹, R⁵⁰
Does not contain a hydrogen atom. )

Here, the alkylene group represented by R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁷ and R ⁴⁸ has 1 to 20 carbon atoms, preferably 1 carbon atom.
-10, more preferably 1-8, and specifically, methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-
Examples include a pentylene group, an isopentylene group, a hexylene group, a nonylene group, a decylene group, a cyclopentylene group, and a cyclohexylene group.

The alkyl group of R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ⁵⁰ has 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
8, more preferably 1 to 6, which may be linear, branched, or cyclic. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, hexyl, nonyl, decyl, dodecyl Group, tridecyl group, cyclopentyl group, cyclohexyl group and the like.

Further, R ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁴⁴ and R ^46
46, if R ⁴⁴ and R ⁴⁵ and R ^46, R ⁴⁹ and R ⁵⁰ form rings, the number of carbon atoms in the ring is 1 to 20, more preferably 1 to
8, more preferably 1 to 6, and in these rings, an alkyl group having 1 to 6, particularly 1 to 4 carbon atoms may be branched.

S, T and U are each an integer of 0 to 20, more preferably 1 to 10, and further preferably an integer of 1 to 8.

Specific examples of the compounds of the above (14) and (15) include tris {2- (methoxymethoxy) ethyl}
Amine, tris {2- (methoxyethoxy) ethyl} amine, tris [2-{(2-methoxyethoxy) methoxy} ethyl] amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- ( 1-methoxyethoxy) ethyl @ amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2-{(2-
Hydroxyethoxy) ethoxydiethyl] amine, 4,
7,13,16,21,24-hexaoxa-1,10
-Diazabicyclo [8.8.8] hexacosan, 4,
7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosan, 1,4,10,13-
Tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-
Crown-5, 1-aza-18-crown-6 and the like. In particular, tertiary amines, aniline derivatives, pyrrolidine derivatives, pyridine derivatives, quinoline derivatives, amino acid derivatives, nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, Tris ｛2-
(Methoxymethoxy) ethyl {amine, tris} (2-
(2-methoxyethoxy) ethyldiamine, tris [2
-{(2-methoxyethoxy) methyl} ethyl] amine, 1-aza-15-crown-5 and the like are preferred.

The above basic compounds can be used alone or in combination of two or more. The compounding amount is 0.01 to 2 parts by weight, particularly 0 to 2 parts by weight, based on 100 parts by weight of the total base resin. 0.01 to 1 part by weight is preferred. When the amount is less than 0.01 part by weight, the effect of the compounding is not obtained.

Further, (D) in the negative resist material
Examples of the acid crosslinking agent that forms a crosslinked structure by the action of an acid of a component include a compound having two or more hydroxymethyl groups, alkoxymethyl groups, epoxy groups or vinyl ether groups in a molecule, a substituted glycouril derivative, a urea derivative, Hexa (methoxymethyl) melamine or the like is suitably used as an acid crosslinking agent for a chemically amplified negative resist material.
For example, tetraalkoxymethyl-substituted glycolurils such as N, N, N ', N'-tetramethoxymethylurea and hexamethoxymethylmelamine, tetrahydroxymethyl-substituted glycolurils and tetramethoxymethylglycoluril, substituted and unsubstituted Phenolic compounds such as bis-hydroxymethylphenols and bisphenol A and condensates such as epichlorohydrin are exemplified. Particularly suitable crosslinking agents are 1,3,5,7-tetraalkoxymethylglycoluril or 1,3,5,7-tetramethoxymethylglycoluril or 1,3,5,7-tetramethoxymethylglycoluril.
5,7-tetrahydroxymethylglycoluril,
2,6-dihydroxymethyl p-cresol, 2,6-
Dihydroxymethylphenol, 2,2 ', 6,6'-
Tetrahydroxymethyl-bisphenol A and 1,4
-Bis- [2- (2-hydroxypropyl)]-benzene, N, N, N ', N'-tetramethoxymethylurea and hexamethoxymethylmelamine. The addition amount is optional, but is 1 to 1 with respect to the total solid content in the resist material.
It is 25 parts by weight, preferably 5 to 15 parts by weight. These may be used alone or in combination of two or more.

The resist composition of the present invention may contain, as an optional component, other than the above components, a surfactant which is commonly used to improve coating properties. In addition, the addition amount of the optional component can be a normal amount as long as the effect of the present invention is not impaired.

The surfactant is preferably a nonionic surfactant, and examples thereof include perfluoroalkylpolyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, and fluorine-containing organosiloxane compounds. For example, Florard "F
C-430 "," FC-431 "(all manufactured by Sumitomo 3M Limited), Surflon" S-141 "," S-1 "
45, S-381, S-383 (all manufactured by Asahi Glass Co., Ltd.), Unidyne DS-401, DS
-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), MegaFac" F-8151 "," F-1
71 "," F-172 "," F-173 "," F-17 "
7 "(all manufactured by Dainippon Ink and Chemicals, Inc.)," X-7
0-092 "and" X-70-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.). Preferably, Florard "FC-430" (manufactured by Sumitomo 3M Limited) and "X-70-093" (manufactured by Shin-Etsu Chemical Co., Ltd.) are exemplified.

A pattern can be formed using the resist material of the present invention by employing a known lithography technique. For example, a film having a thickness of 0 is formed on a substrate such as a silicon wafer by a method such as spin coating. .1 to 1.0 μ
m on a hot plate.
~ 200 ° C, 10 seconds ~ 10 minutes, preferably 80 ~ 15
Prebake at 0 ° C. for 30 seconds to 5 minutes. Next, a mask for forming a target pattern is held over the resist film, and a deep ultraviolet ray having a wavelength of 300 nm or less, an excimer laser, a high energy ray such as an X-ray or an electron beam is exposed at a dose of about 1 to 200 mJ / cm ² , Preferably 10 to 100
After irradiating to about mJ / cm ^2, post-exposure bake (PEB) is performed on a hot plate at 60 to 150 ° C. for 10 seconds to 5 minutes, preferably at 80 to 130 ° C. for 30 seconds to 3 minutes. Further, using a developer of an aqueous alkali solution such as 0.1 to 5%, preferably 2 to 3% tetramethylammonium hydroxide (TMAH),
Immersion (di) for 0 seconds to 3 minutes, preferably 30 seconds to 2 minutes
p) method, paddle method, spray method (spr)
The target pattern is formed on the substrate by developing using a conventional method such as the ay) method. In addition, the material of the present invention is preferably a deep ultraviolet ray or excimer laser having a wavelength of 254 to 120 nm, especially an ArF, 15
7 nm F2, 146 nm Kr2, 134 nm Kr
Excimer laser such as Ar, 126 nm Ar2, X
Most suitable for fine patterning by electron beam and electron beam.
In addition, when the above range is out of the upper limit and the lower limit, a desired pattern may not be obtained.

[0073]

The chemically amplified negative resist composition of the present invention has high crosslinking efficiency and high sensitivity.

[0074]

EXAMPLES The present invention will be specifically described below with reference to Synthesis Examples and Examples, but the present invention is not limited to the following Examples.

[Synthesis Example 1] Poly-2-methoxy-4-
Synthesis of hydroxyphenol Tetrahydrofuran 500 as a solvent in a 1 L flask
ml, sec-butyl lithium 0.01 m as initiator
ol. P-ter at −78 ° C.
30 g of t-butoxystyrene was added, and the mixture was polymerized with stirring for 30 minutes. The reaction solution turned red. next,
Further, 2-methoxy-4-tert-butoxystyrene 1
0 g was added, and the mixture was polymerized with stirring for 30 minutes. The polymerization termination reaction was performed by adding 0.1 mol of methanol to the reaction solution. Next, in order to purify the polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated, separated and dried, and 29 g of a white polymer poly-2-methoxy-4- was obtained. Tert-butoxystyrene was obtained. Further, in order to obtain poly-2-methoxy-4-hydroxystyrene, the above-mentioned 2-methoxy-4-tert.
29 g of t-butoxystyrene was dissolved in 300 ml of acetone, a small amount of concentrated hydrochloric acid was added at 60 ° C., and the mixture was stirred for 7 hours, poured into water to precipitate a polymer, and washed and dried.
18 g of polymer were obtained. The analysis by GPC revealed that no peak derived from a tert-butyl group was observed in ¹ H-NMR, and the presence of 170 ppm CＣO in ¹³ C-NMR resulted in poly-2 having a narrow molecular weight distribution. -Methoxy-4-hydroxystyrene was confirmed.

[Synthesis Example 2] Synthesis of poly-2,6-dimethoxy-4-hydroxyphenol In a 1 L flask, tetrahydrofuran 500 was used as a solvent.
ml, sec-butyl lithium 0.01 m as initiator
ol. P-ter at −78 ° C.
30 g of t-butoxystyrene was added, and the mixture was polymerized with stirring for 30 minutes. The reaction solution turned red. next,
Further, 10 g of 2,6-dimethoxy-4-tert-butoxystyrene was added, and the mixture was polymerized with stirring for 30 minutes.
The polymerization termination reaction was performed by adding 0.1 mol of methanol to the reaction solution. Further, poly-2,6-dimethoxy-4-
To obtain hydroxystyrene, 29 g of the above 2,6-dimethoxy-4-tert-butoxystyrene was dissolved in 300 ml of acetone, a small amount of concentrated hydrochloric acid was added at 60 ° C., the mixture was stirred for 7 hours, and then poured into water to precipitate the polymer. And wash
Upon drying, 18 g of polymer was obtained. Also,
Analysis by GPC, no peak derived from tert-butyl group was observed in ¹ H-NMR, and the presence of 170 ppm C ＝ O in ¹³ C-NMR resulted in poly-2,6 having a narrow molecular weight distribution. -Dimethoxy-4-hydroxystyrene.

[Synthesis Example 3] Synthesis of 3-branched (poly-2-methoxy-4-hydroxystyrene) Tetrahydrofuran 500 was used as a solvent in a 1 L flask.
ml, sec-butyl lithium 0.01 m as initiator
ol. P-ter at −78 ° C.
30 g of t-butoxystyrene was added, and the mixture was polymerized with stirring for 30 minutes. The reaction solution turned red. Furthermore,
To obtain a branched polymer, 0.005 mol of p-chloromethylstyrene was added and reacted for 5 minutes. The reaction solution was a red solution. Next, 10 g of 2-methoxy-4-tert-butoxystyrene was further added,
The polymerization was carried out with stirring for 30 minutes. The polymerization termination reaction was performed by adding 0.1 mol of methanol to the reaction solution. next,
To purify the polymer, the reaction mixture was poured into methanol, and the resulting polymer was precipitated, separated and dried to obtain 29 g of a white polymer (3-branched poly-2).
-Methoxy-4-tert-butoxystyrene) was obtained. Further, in order to make the mixture into 3-branched (p-hydroxystyrene), 29 g of the above-mentioned 3-branched poly-p-tert-butoxystyrene was dissolved in 300 ml of acetone, a small amount of concentrated hydrochloric acid was added at 60 ° C., and the mixture was stirred for 7 hours. The polymer was precipitated, washed and dried to obtain 18 g of a polymer. The obtained polymer was analyzed by GPC, the peak derived from the tert-butyl group was not observed in ¹ H-NMR, and the presence of 170 ppm of C ＝ O in ¹³ C-NMR caused the obtained polymer to have three branches having a narrow molecular weight distribution ( p-
(Hydroxystyrene).

Synthesis Example 4 9-branch (2-methoxy-4)
Synthesis of -Hydroxystyrene) In a 2 L flask, tetrahydrofuran 1,0
00 ml, sec-butyl lithium 0.0 as an initiator
6 mol was charged. To this mixed solution was added 60 g of 2-methoxy-4-tert-butoxystyrene at -78 ° C, and the mixture was polymerized with stirring for 30 minutes. The reaction solution turned red. Furthermore, in order to obtain a three-branched polymer, p-
0.03 mol of chloromethylstyrene was added and reacted for 5 minutes. To this reaction solution was added 2-methoxy-4-ter
30 g of t-butoxystyrene was added, and the mixture was polymerized with stirring for 30 minutes. The reaction solution turned red. next,
To obtain a five-branched polymer, 0.03 mol of p-chloromethylstyrene was added and reacted for 5 minutes. 30 g of 2-methoxy-4-tert-butoxystyrene was added to the reaction solution, and the mixture was polymerized with stirring for 30 minutes. The reaction solution turned red. Finally, to obtain a 9-branched polymer, 0.015 mol of p-chloromethylstyrene
1 was added and reacted for 5 minutes. 15 g of 2-methoxy-4-tert-butoxystyrene was added to the reaction solution, and the mixture was polymerized with stirring for 30 minutes. The reaction solution turned red. Further, 10 g of 2-methoxy-4-tert-butoxystyrene was added, and the mixture was polymerized with stirring for 30 minutes. For the polymerization termination reaction, 0.1 mol of carbon dioxide gas was added to the reaction solution.
Was performed. Next, to purify the polymer,
The reaction mixture was poured into methanol, and the resulting polymer was precipitated, separated and dried to obtain 99 g of a white polymer (9-branched 2-methoxy-4-hydroxystyrene). Further, in order to obtain 9 branches (p-hydroxystyrene), the above 9-branched poly-2-methoxy-
99 g of 4-hydroxystyrene was dissolved in 1,000 m of acetone.
After stirring for 7 hours, a polymer was precipitated, washed and dried to obtain 66 g of a polymer. GPC analysis,
A peak derived from the tert- butyl groups ¹ H-NMR is not observed, the 170ppm by ¹³ C-NMR C =
The presence of O confirmed that the obtained polymer was 9-branched (2-methoxy-4-hydroxystyrene) having a narrow molecular weight distribution.

[Examples and Comparative Examples] Polym shown below
er1 to 7 (Examples) and Polymers 8 to 10 (Comparative Examples), an acid generator represented by PAG1,
Crosslinkers 1 and 2 and a base were used in the amounts shown in Tables 1 and 2 and dissolved in propylene glycol monomethyl ether acetate (PGMEA) at 6 times the solid content to prepare a resist composition. 0.
By filtering through a 2 μm Teflon filter,
A resist solution was prepared.

The resulting resist solution was applied to a silicon wafer by forming a film of DUV-30 (manufactured by Nissan Chemical Industries, Ltd.) to a thickness of 55 nm and forming a Kr film.
The substrate is spin-coated on a substrate whose reflectance is suppressed to 1% or less with F light (248 nm), and is coated on a hot plate using a hot plate.
Bake at 00 ° C for 90 seconds to reduce resist thickness to 0.55
The thickness was set to μm. This was exposed using an excimer laser stepper (Nikon Corporation, S-202A, NA-0.6), and immediately after exposure, baked at 110 ° C. for 90 seconds.
When development was performed for 60 seconds with an aqueous solution of 38% by weight of tetramethylammonium hydroxide, a negative pattern was obtained.

The obtained resist pattern was evaluated as follows. The results are shown in Tables 1 and 2. Evaluation method: 0.30 μm line and space:
The exposure amount resolved in step 1 was measured by the S-7 Hitachi S-7
At 280, this was taken as the optimum exposure amount (Eop), and the minimum line width of the line and space separated at this exposure amount was taken as the resolution of the evaluation resist.

[0082]

Embedded image

[0083]

Embedded image

[0084]

Embedded image

[0085]

Embedded image

[0086]

Embedded image

[0087]

Embedded image

[0088]

Embedded image

[0089]

Embedded image

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

[0095]

[Table 1]

[0096]

[Table 2]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) G03F 7/039 601 G03F 7/039 601 H01L 21/027 H01L 21/30 502R (72) Inventor Osamu Watanabe Niigata 28-1 Nishifukushima, Nishifukushima, Nakakushiro-gun, Niigata Prefecture Shinsei Chemical Industry Co., Ltd. (72) Inventor Takanobu Takeda 28-1, Nishifukushima, Nishi-Fukushima, Niigata Pref.Shinetsu Chemical Industry Co., Ltd. (72) Inventor Yoichi Osawa 28-1, Nishifukushima, Oaza, Kushiro-mura, Nakakibijo-gun, Niigata Prefecture Inside the Synthetic Research Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inventor Tomohiro Kobayashi 28-1, Nishifukushima, Oaza-ku, Nishifukushima, Naka-Nakashiro-gun, Niigata Chemical Industry Co., Ltd. Synthetic Technology Laboratory F-term (reference) 2H025 AA01 AA02 AA03 AB16 AC06 AC08 AD01 BE00 BE10 BG00 BJ10 CB17 CB41 CB45 CC03 CC17 FA12 4J002 BC121 BN201 BP031 CH052 DF008 EJ067 EN028 EN038 EN048 EN068 EN108 EN118 EN127 EN128 EP018 ES008 ET017 EU018 EU028 EU038 EU048 EU058 EU078 EU108 EU118 EU128 EU138 EU148 EU187 EU208 EU218 EU228 EU238 EVEV EVEV 156 EV EV EV EV GP03 HA05 4J026 HA06 HA26 HA32 HA39 HA49 HB06 HB26 HB32 HB39 HB43 HE05 4J100 AB02R AB03R AB07P AB07Q AB07S BA03P BA03Q BA04P BA04Q BA04S BA05P BA05Q BA05S BA06P BA06Q BA06S BA76P BA07HC04 HC03 CA05 HC04 HC71 HC72 HG01 JA38

Claims (9)

[Claims] 1. A chemically amplified negative resist base polymer comprising a repeating unit represented by the following general formula (1). Embedded image (Wherein, R ¹ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a carbon atom directly connected to an oxygen atom is primary or secondary, and R ² is a hydrogen atom, or It is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. M and n are 0 <m <5 and 0 <n <5.) 2. A chemically amplified negative resist base polymer comprising a repeating unit represented by the following general formula (2). Embedded image (Wherein, R ¹ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a carbon atom directly connected to an oxygen atom is primary or secondary, and R ² is a hydrogen atom, or A linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, in the range of 0 ≦ a ≦ 1, 0 ≦ b ≦ 1, and 0 <a + b ≦ 1.) 3. A base polymer for a chemically amplified negative resist comprising a repeating unit represented by the following general formula (3). Embedded image (Wherein, R ¹ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a carbon atom directly connected to an oxygen atom is primary or secondary, and R ² is a hydrogen atom, or A linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, R ³ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may contain a hetero atom; ≦ a ≦
1, 0 ≦ b ≦ 1, 0 ≦ c <1, 0 ≦ d <1, and a + b + c + d = 1. ) 4. The base polymer for a chemically amplified negative resist according to claim 1, comprising a unit represented by the following general formula (4). Embedded image (In the formula, R ⁴ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, which may contain an ether bond or an ester bond.) 5. The base polymer for a chemically amplified negative resist according to claim 4, which is a den polymer or a hyperbranched polymer represented by the following general formula (5). Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁴ , a, b, c, and d are the same as above. E is 1 ≦ e ≦ 1,000.) 6. The chemically amplified negative resist base polymer according to claim 1, which is obtained by living anionic polymerization. 7. The base polymer according to claim 1, wherein the base polymer is alkali-insoluble or hardly soluble when the crosslinking agent is crosslinked, (B) an organic solvent,
A chemically amplified negative resist composition comprising (C) an acid generator and (D) a crosslinking agent. 8. The method according to claim 7, which further comprises (E) a basic compound.
The chemically amplified negative resist material according to the above. 9. A step of applying the chemically amplified negative resist material according to claim 7 on a substrate, and (2) a high-energy ray of 500 nm or less or an electron through a photomask after a heat treatment. Exposing with a line, (3)
A pattern forming method, comprising a step of performing a heat treatment as needed and then developing with a developer.