JP2001272785A - Chemical amplification type resist material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chemical amplification type resist material having enhanced resolution by the narrow dispersing effect of a polymer as compared with a conventional base resin having a wide dispersity, giving a good resist pattern shape because the low molecular weight part of a polymer is removed, having enhanced shelf stability as a resist and therefore having higher resolution, a better pattern shape and better shelf stability as compared with a conventional resist material. SOLUTION: The chemical amplification type resist material contains a high molecular compound comprising repeating units of formula (1) (where R1 is alkyl, alkoxyalkyl, acetyl or carbonylalkoxy and 0<p/(p+q)<=1) and repeating units of formula (2) (where R2 is H or methyl and R3 is a 4-30C tertiary hydrocarbon) or repeating units of the formula (2) and having a molecular weight distribution of 1.0-1.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a chemically amplified resist material.

[0002]

2. Description of the Related Art In recent years,
As the integration and speed of LSIs are increasing and the pattern rules are required to be finer, lithography is considered to be a promising microfabrication technology. Deep ultraviolet, EB, and X-ray lithography can also perform processing of 0.2 μm or less.

Recently, a chemically amplified positive resist material using an acid as a catalyst (described in Japanese Patent Publication No. 2-27660 and Japanese Patent Application Laid-Open No. 63-27829) is known as a high-intensity KrF excimer as a light source for far ultraviolet rays. Using a laser, sensitivity,
It is expected to be a particularly promising resist material for deep-ultraviolet lithography having high resolution and dry etching resistance and excellent characteristics. For example, hydroxystyrene,
Methacrylate ester copolymer (Japanese Patent Publication 6-2)
No. 66112, JP-A-8-101509) have been proposed. Further, a device utilizing a high-brightness ArF excimer laser is also expected.

However, these resist materials have problems, such as the inability to form the required fine line pattern and the unsatisfactory sensitivity and resolution, when further fine processing is required. At present, some improvement is required.

[0005] The present invention has been made in view of the above circumstances,
To provide a chemically amplified resist material that has higher sensitivity and resolution, exposure latitude, process adaptability, and reproducibility than conventional resist materials, has excellent plasma etching resistance, and also has excellent heat resistance of resist patterns. The purpose is to:

[0006]

Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies in order to achieve the above-mentioned object, and as a result, a chemical using a narrowly dispersed base resin obtained by a method described later. Amplified resist material has high resolution,
It has been found that it is excellent in exposure latitude and process adaptability, is highly practical, is advantageous for precise fine processing, and is very effective as a resist material for VLSI.

That is, the degree of dispersion of the developed base polymer for a resist is wide due to its non-living polymerization technique (particularly radical polymerization), and it still contains low molecular weight components. The present inventor has focused on the degree of dispersion of the polymer compound, and blended the resist compound as a base resin with a narrowly dispersed polymer compound, particularly a polymer compound from which low molecular weight components have been removed by fractionation. It has been found that a chemically amplified resist material having a significantly high alkali dissolution rate contrast, high sensitivity and high resolution, and particularly suitable as a fine pattern forming material for VLSI manufacturing can be obtained.

That is, the present invention provides the following chemically amplified resist material. Claim 1: A polymer compound comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), a polymer compound comprising a repeating unit represented by the following formula (2), A polymer compound comprising a repeating unit represented by the following formula (4), a polymer compound comprising a repeating unit represented by the following formula (3), and a polymer compound represented by the following formula (4) Selected from high molecular compounds consisting of repeating units having a molecular weight distribution of 1.0 to 1.0
A chemically amplified resist material comprising the high molecular compound of 1.5.

[0009]

Embedded image (Wherein, R ¹ represents an alkyl group, an alkoxyalkyl group, an acetyl group or a carbonylalkoxy group,
Each unit may be composed of one type or two or more types. p is a positive number, q is 0 or a positive number, and is a number satisfying 0 <p / (p + q) ≦ 1. )

[0010]

Embedded image (In the formula, R ² represents a hydrogen atom or a methyl group, and R ³ represents a tertiary hydrocarbon group having 4 to 30 carbon atoms.)

[0011]

Embedded image (Wherein, R ⁴ represents a tertiary hydrocarbon group having 4 to 30 carbon atoms, and R ^{5 to} R ⁸ each independently represent a hydrogen atom, an ester group, an alkoxycarbonylalkyl group, a lactone group, a carboxyl group, or a cyclic group. Represents an acid anhydride group;
Any two of ^{5 to} R ⁸ may combine to form a cyclic lactone group or an acid anhydride group. r is a positive number, s is 0 or a positive number, and is a number satisfying 0 <r / (r + s) ≦ 1. )

[0012]

Embedded image (In the formula, R ⁹ represents a tertiary hydrocarbon group having 4 to 30 carbon atoms, and n is 0 or 1.)

In another preferred embodiment, the resist composition comprises a polymer having a molecular weight distribution of 1.0 to 1.4.

In another preferred embodiment, the high molecular compound is dissolved in a good solvent for the high molecular compound, and the solution is poured into a poor solvent for the high molecular compound to fractionate and remove low molecular weight components in the high molecular compound. The resist material according to claim 1, further comprising a polymer compound having a molecular weight distribution of 1.0 to 1.5.

In a preferred embodiment, the poor solvent and the good solvent are water,
Acetone, ethyl acetate, methyl acetate, diethyl ether, tetrahydrofuran, cyclohexanone, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, propylene glycol monomethyl ether acetate, ethyl lactate, methanol, ethanol, isopropyl alcohol, pentane, hexane, toluene, benzene, 4. The resist material according to claim 3, which is selected from xylene and is selected according to a polymer compound to be fractionated.

When the above polymer compound is blended in a resist material as a base resin, the performance is improved as compared with the conventional base resin having a wide degree of dispersion due to the narrow dispersibility effect of the polymer. For example, in a hydroxystyrene / methacrylic acid ester copolymer, the resolution is more improved with a base resin whose dispersity is narrowed to about 1.4 as compared with a base resin obtained by ordinary radical polymerization. I do. Also,
Since the low molecular weight portion of the polymer is removed, the resist pattern shape becomes good, and the stability as a resist is also improved.

Hereinafter, the present invention will be described in more detail.
The chemically amplified resist material of the present invention comprises a polymer compound comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (2) A polymer compound comprising a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (4); a polymer compound comprising a repeating unit represented by the following formula (3); Equation (4)
And a polymer compound selected from polymer compounds comprising a repeating unit represented by

[0018]

Embedded image (Wherein, R ¹ represents an alkyl group, an alkoxyalkyl group, an acetyl group or a carbonylalkoxy group,
Each unit may be composed of one type or two or more types. p is a positive number, q is 0 or a positive number, and is a number satisfying 0 <p / (p + q) ≦ 1. )

Embedded image (In the formula, R ² represents a hydrogen atom or a methyl group, and R ³ represents a tertiary hydrocarbon group having 4 to 30 carbon atoms.)

Embedded image (Wherein, R ⁴ represents a tertiary hydrocarbon group having 4 to 30 carbon atoms, and R ^{5 to} R ⁸ each independently represent a hydrogen atom, an ester group, an alkoxycarbonylalkyl group, a lactone group, a carboxyl group, or a cyclic group. Represents an acid anhydride group;
Any two of ^{5 to} R ⁸ may combine to form a cyclic lactone group or an acid anhydride group. r is a positive number, s is 0 or a positive number, and is a number satisfying 0 <r / (r + s) ≦ 1. )

Embedded image (In the formula, R ⁹ represents a tertiary hydrocarbon group having 4 to 30 carbon atoms, and n is 0 or 1.)

Here, the alkyl group for R ¹ is preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms, such as methyl, ethyl, propyl and isopropyl. Group, n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-
Examples include a pentyl group, an n-hexyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group. As the alkoxyalkyl group for R ^1, a linear, branched, or cyclic group having 2 to 20 carbon atoms, particularly 2 to 10 carbon atoms, is preferable. Specifically, a 1-methoxyethyl group, a 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-se
c-butoxyethyl group, 1-tert-butoxyethyl group, 1-tert-amyloxyethyl group, 1-ethoxy-n-propyl group, 1-cyclohexyloxyethyl group,
Linear or branched acetal groups such as methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methyl-ethyl group, tetrahydrofuranyl group, and tetrahydropyranyl group; Examples include a cyclic acetal group and the like, preferably an ethoxyethyl group, a butoxyethyl group, and an ethoxypropyl group.

As the carbonylalkoxy group for R ¹ ,
Those having 2 to 20 carbon atoms, particularly 2 to 10 carbon atoms, are preferred, and specific examples include a tert-butoxycarbonyl group and a tert-butoxycarbonylmethyl group.

The tertiary hydrocarbon group of R ³ , R ⁴ and R ⁹ is a tertiary alkyl group having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms. Alkenyl group such as group, aryl group such as phenyl group, cyano group, 1-substituted cycloalkyl group substituted with acyl group such as acetyl group and the like are preferable.
rt-butyl, 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-isopropylcyclopentyl, 1
-Vinylcyclopentyl, 1-acetylcyclopentyl, 1-phenylcyclopentyl, 1-cyanocyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-isopropylcyclohexyl, 1-vinylcyclohexyl, 1-acetylcyclohexyl, 1-
Phenylcyclohexyl, 1-cyanocyclohexyl and the like.

Further, examples of the ester group of R ^{5 to} R ⁸ include a methyl ester and an ethyl ester. The alkoxycarbonylalkyl group has 3 to 10 carbon atoms, particularly 3 to 6 carbon atoms, such as methoxycarbonylmethyl group,
and a t-butoxycarbonylmethyl group. As the lactone group, 5-membered lactone, 6-membered lactone, 7
Membered lactones can be exemplified. Examples of the cyclic acid anhydride group include a succinic anhydride group and a glutaric anhydride group.

Here, p is a positive number, q is 0 or a positive number,
p / (p + q) is 0 <p / (p + q) ≦ 1, preferably 0.1 ≦ p / (p + q) ≦ 0.95, and more preferably 0.6 ≦ p / (p + q) ≦ 0.8. And r is a positive number, s is 0 or a positive number, and r / (r + s) is 0 <r /
(R + s) ≦ 1, preferably 0.1 ≦ r / (r + s) ≦
0.9, more preferably 0.4 ≦ r / (r + s) ≦ 0.
6.

The polymer compound used in the present invention has a weight average molecular weight of 500 to 10,000,000, especially 5,000.
0 to 20,000 is preferred.

In the present invention, the high molecular compound has a molecular weight distribution (Mw / Mn = weight average molecular weight / number average molecular weight) of 1.0 to 1.5, preferably 1.0 to 1.4, and more preferably. 1.0 to 1.35.

In order to obtain a high molecular compound having a molecular weight distribution as described above, a high molecular compound having a molecular weight distribution exceeding 1.5 is used, and the solubility of the high molecular compound in a good solvent and a poor solvent according to the molecular weight is utilized. Then, a method of performing fractionation by removing low molecular weight components can be adopted.

In this case, good and poor solvents used for removing low molecular weight components are water, acetone, ethyl acetate, methyl acetate, diethyl ether, tetrahydrofuran, cyclohexanone, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, propylene. Glycol monomethyl acetate, ethyl lactate, methanol, ethanol, isopropyl alcohol, pentane,
From among hexane, toluene, benzene and xylene,
It can be selected and used according to the polymer compound to be fractionated.

Specifically, a good solvent of a polymer compound containing a relatively large amount of a low molecular weight component and having a molecular weight distribution of more than 1.5 is used, and the polymer compound is charged into the good solvent to obtain the polymer. The compound is dissolved in a good solvent, and then the good solvent solution is added to a poor solvent for the polymer compound. This allows
Since the low molecular weight component in the polymer compound is dissolved in the poor solvent and separated into two layers, it can be separated from the high molecular weight component. Next, the layer in which the high molecular weight component is dissolved is again put into the poor solvent, and the low molecular weight component is fractionated and removed by a method such as crystallization filtration or concentration and crystallization filtration. A high molecular compound having a molecular weight distribution of 1.0 to 1.5, particularly 1.0 to 1.4 is obtained. In the present invention, the high molecular compound having a narrow molecular weight distribution obtained by the fractionation method is used. It is preferred to use

The chemically amplified resist material of the present invention is particularly preferably used as a positive resist composition. In addition to using the above polymer compound as a base polymer, an organic solvent, a photoacid generator, a dissolution inhibitor, a basic compound Ordinary components such as the above can be blended.

Here, the organic solvent is butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate,
Methyl ethyl ketone, methyl amyl ketone, cyclohexanone, cyclopentanone, 3-ethoxyethyl propionate, 3-ethoxymethyl propionate, 3-methoxymethyl propionate, methyl acetoacetate, ethyl acetoacetate, diacetone alcohol, pyruvate Methyl, ethyl pyruvate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether,
Ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, N-methylpyrrolidone, dimethyl sulfoxide, γ
-Butyrolactone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, ethyl lactate, propyl lactate, tetramethylene sulfone, and the like, but are not limited thereto. Particularly preferred are propylene glycol alkyl ether acetate and alkyl lactate.

The alkyl group of the propylene glycol alkyl ether acetate has 1 to 4 carbon atoms, such as a methyl group, an ethyl group and a propyl group. Of these, a methyl group and an ethyl group are preferred. The propylene glycol alkyl ether acetate includes a 1,2-substituted product and a 1,3-substituted product. There are three types of isomers depending on the combination of substitution positions. The alkyl group of the above-mentioned alkyl lactate has 1 to 4 carbon atoms, such as a methyl group, an ethyl group, and a propyl group. Among them, a methyl group and an ethyl group are preferable. These solvents may be used alone or in combination of two or more. Examples of preferred mixed solvents are propylene glycol alkyl ether acetate and alkyl lactate. The mixing ratio is also optional, but propylene glycol alkyl ether acetate 50 to 9
It is desirable to mix the alkyl lactate in an amount of 1 to 50 parts by weight to 9 parts by weight. More preferably,
6 propylene glycol alkyl ether acetate
It is preferable that the proportion of the alkyl lactate is 0 to 95% by weight and the proportion of the alkyl lactate is 5 to 40% by weight. When the amount of propylene glycol alkyl ether acetate is small, there is a problem such as deterioration of coating properties, and when too large, there is a problem of insufficient solubility and generation of particles and foreign matters. When the amount of the alkyl lactate is too small, there are problems such as insufficient solubility, increase of particles and foreign substances, and when too much, there is a problem that the viscosity is increased to deteriorate the coating property and the storage stability is deteriorated. The amount of the organic solvent used is 300 to 100 parts by weight of the base polymer.
2,000 parts by weight, especially 400 to 1,000 parts by weight, are common.

Next, examples of the photoacid generator which generates an acid upon irradiation with high energy rays include, but are not limited to, the following. These can be used alone or in combination of two or more.

The sulfonium salt is a salt of a sulfonium cation and a sulfonate. As the sulfonium cation, triphenylsulfonium, (4-tert-butoxyphenyl) diphenylsulfonium, bis (4-ter
t-butoxyphenyl) phenylsulfonium, tris (4-tert-butoxyphenyl) sulfonium,
(3-tert-butoxyphenyl) diphenylsulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxyphenyl) sulfonium, (3,4-ditert-butoxyphenyl) diphenylsulfonium, bis ( 3,4-
Di-tert-butoxyphenyl) phenylsulfonium, tris (3,4-ditert-butoxyphenyl)
Sulfonium, diphenyl (4-thiophenoxyphenyl) sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl) diphenylsulfonium, tris (4-tert-butoxycarbonylmethyloxyphenyl) sulfonium, (4-tert-butoxyphenyl) bis ( 4-dimethylaminophenyl) sulfonium, tris (4-dimethylaminophenyl) sulfonium, 2-naphthyldiphenylsulfonium, dimethyl 2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, diphenylmethylsulfonium , Methyl-2-oxopropylphenylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium And trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, and the like. -Trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, and the like, and a sulfonium salt of these combinations is included. No.

The iodonium salt is a salt of an iodonium cation and a sulfonate, such as diphenyliodonium, bis (4-tert-butylphenyl) iodonium,
-Tert-butoxyphenylphenyliodonium,
Aryliodonium cations such as 4-methoxyphenylphenyliodonium and sulfonates as trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate,
2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, Methanesulfonate and the like,
These combinations include iodonium salts.

As the sulfonyldiazomethane, bis (ethylsulfonyl) diazomethane, bis (1-methylpropylsulfonyl) diazomethane, bis (2-methylpropylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexyl) Sulfonyl) diazomethane, bis (perfluoroisopropylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (2-naphthylsulfonyl) diazomethane , 4-methylphenylsulfonylbenzoyldiazomethane, tertbutylcarbonyl-4-methylphenylsulfonyldiazomethane,
2-naphthylsulfonylbenzoyldiazomethane, 4-
Methylphenylsulfonyl 2-naphthoyldiazomethane, methylsulfonylbenzoyldiazomethane, ter
bissulfonyldiazomethane such as t-butoxycarbonyl-4-methylphenylsulfonyldiazomethane; and sulfonyl-carbonyldiazomethane.

Examples of the N-sulfonyloxyimide type photoacid generator include succinimide, naphthalenedicarboxylic acid imide, phthalic acid imide, cyclohexyldicarboxylic acid imide, 5-norbornene-2,3-dicarboxylic acid imide, and 7-oxabicycloimide. [2.2.1] imide skeleton such as -5-heptene-2,3-dicarboxylic imide and trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate;
2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butane Combination compounds such as sulfonates, methanesulfonates and the like can be mentioned.

Examples of the benzoin sulfonate type photoacid generator include benzoin tosylate and benzoin mesylate benzoin butane sulfonate.

Examples of the pyrogallol trisulfonate type photoacid generator include all of the hydroxyl groups of pyrogallol, phloroglysin, catechol, resorcinol and hydroquinone as trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2 -Trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, etc. Embedded image

The nitrobenzylsulfonate type photoacid generator includes 2,4-dinitrobenzylsulfonate,
-Nitrobenzylsulfonate, 2,6-dinitrobenzylsulfonate, and as the sulfonate,
Specifically, trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate Benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate and the like. A compound in which the nitro group on the benzyl side is replaced with a trifluoromethyl group can also be used in the same manner.

Examples of sulfone-type photoacid generators include bis (phenylsulfonyl) methane, bis (4-methylphenylsulfonyl) methane, bis (2-naphthylsulfonyl) methane, and 2,2-bis (phenylsulfonyl) propane. , 2,2-bis (4-methylphenylsulfonyl)
Propane, 2,2-bis (2-naphthylsulfonyl) propane, 2-methyl-2- (p-toluenesulfonyl)
Propiophenone, 2-cyclohexylcarbonyl)-
2- (p-toluenesulfonyl) propane, 2,4-dimethyl-2- (p-toluenesulfonyl) pentane-3
-On and the like.

Examples of the glyoxime derivative type photoacid generator include 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-dimethylglyme Oxime, bis-o- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o- (t
ert-butanesulfonyl) -α-dimethylglyoxime, bis-o- (perfluorooctanesulfonyl)-
α-dimethylglyoxime, bis-o- (cyclohexylsulfonyl) -α-dimethylglyoxime, bis-o
-(Benzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl)-
α-dimethylglyoxime, bis-o- (p-tert
-Butylbenzenesulfonyl) -α-dimethylglyoxime, bis-o- (xylenesulfonyl) -α-dimethylglyoxime, bis-o- (camphorsulfonyl)
-Α-dimethylglyoxime and the like.

Among the photoacid generators that are preferably used, sulfonium salts, bissulfonyldiazomethane,
N-sulfonyloxyimide. The optimum anion of the generated acid varies depending on the easiness of cleavage of the acid labile group used in the polymer, etc. In general, those having no volatility and those having extremely low diffusivity are selected. In this case, preferred anions are benzenesulfonic acid anion, toluenesulfonic acid anion, pentafluorobenzenesulfonic acid anion, 2,2,2-trifluoroethanesulfonic acid anion, nonafluorobutanesulfonic acid anion, heptadecafluorooctanesulfone. Acid anion and camphorsulfonic acid anion.

The amount of the photoacid generator to be added is 0.5 to 100 parts by weight of the base polymer in the resist material.
-20 parts by weight, preferably 1-10 parts by weight. The above photoacid generators can be used alone or in combination of two or more. Furthermore, a photoacid generator having a low transmittance at the exposure wavelength can be used, and the transmittance in the resist film can be controlled by the amount of addition.

Further, to the resist composition of the present invention, a compound which is decomposed by an acid to generate an acid (an acid multiplying compound) may be added. These compounds are described in Photopo
lym. Sci. and Tech. , 8.43-4
4, 45-46 (1995); Photopoly
m. Sci. and Tech. , 9.29-30 (1
996).

Examples of acid-propagating compounds include tert-butyl 2-methyl 2-tosyloxymethyl acetoacetate, 2-phenyl 2- (2-tosyloxyethyl) 1,3
-Dioxolan and the like, but are not limited thereto. Among the known photoacid generators, compounds having poor stability, especially heat stability, often show properties as acid-proliferating compounds.

The amount of the acid-propagating compound to be added to the resist composition of the present invention is 2 parts by weight or less, preferably 1 part by weight or less, based on 100 parts by weight of the base polymer in the resist composition. When the addition amount is too large, it is difficult to control the diffusion, and the resolution and the pattern shape deteriorate.

As the dissolution inhibitor, a compound having a molecular weight of 3,000 or less, whose solubility in an alkali developing solution is changed by the action of an acid, can be used. In particular, a phenol or carboxylic acid derivative having a low molecular weight of 2,500 or less can be used. It is also possible to add a compound in which a part or all of the compound is substituted with an acid-labile substituent.

Examples of the phenol or carboxylic acid derivative having a molecular weight of 2,500 or less include bisphenol A, bisphenol H, bisphenol S, 4,4-bis (4 ′
-Hydroxyphenyl) valeric acid, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4′-hydroxyphenyl) ethane, 1,1,2-tris (4′-
Hydroxyphenyl) ethane, phenolphthalein,
Thymolphthalein and the like can be mentioned, and as the acid-labile substituent, those exemplified as the acid-labile group of the polymer can be mentioned again.

Examples of suitable dissolution inhibitors include bis (4- (2'tetrahydropyranyloxy) phenyl) methane, bis (4- (2'tetrahydrofuranyloxy) phenyl) methane, bis (4- tert-butoxyphenyl) methane, bis (4-tert-butoxycarbonyloxyphenyl) methane, bis (4-te
rt-butoxycarbonylmethyloxyphenyl) methane, bis (4- (1′-ethoxyethoxy) phenyl)
Methane, bis (4- (1'-ethoxypropyloxy)
Phenyl) methane, 2,2-bis (4 ′-(2 ″ tetrahydropyranyloxy)) propane, 2,2-bis (4 ′-(2 ″ tetrahydrofuranyloxy) phenyl) propane, 2,2- Bis (4'-tert-butoxyphenyl) propane, 2,2-bis (4'-tert
-Butoxycarbonyloxyphenyl) propane, 2,
2-bis (4-tert-butoxycarbonylmethyloxyphenyl) propane, 2,2-bis (4′-
(1 ″ -ethoxyethoxy) phenyl) propane,
2,2-bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) propane, 4,4-bis (4′-
(2 ″ tetrahydropyranyloxy) phenyl) tertbutyl valerate, 4,4-bis (4 ′-(2′tetrahydrofuranyloxy) phenyl) tertbutyl valerate, 4,4-bis (4′-tert) -Butoxyphenyl) tert-butyl valerate, 4,4-bis (4-ter
t-butoxycarbonyloxyphenyl) valeric acid ter
t-butyl, tert-butyl 4,4-bis (4′-tert-butoxycarbonylmethyloxyphenyl) valerate, tert-butyl 4,4-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) valerate Tert-butyl, 4-bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) valerate, tris (4- (2′tetrahydropyranyloxy) phenyl) methane, tris (4
-(2'tetrahydrofuranyloxy) phenyl) methane, tris (4-tert-butoxyphenyloxy) methane, tris (4-tert-butoxycarbonyloxyphenyl) methane, tris (4-tert-butoxycarbonyloxymethylphenyl) methane, Tris (4-
(1′-ethoxyethoxy) phenyl) methane, tris (4- (1′-ethoxypropyloxy) phenyl) methane, 1,1,2-tris (4 ′-(2 ″ tetrahydropyranyloxy) phenyl) ethane 1,1,2-tris (4 ′-(2 ″ tetrahydrofuranyloxy) phenyl) ethane, 1,1,2-tris (4′-tert
-Butoxyphenyl) ethane, 1,1,2-tris (4'-tert-butoxycarbonyloxyphenyl) ethane, 1,1,2-tris (4'-tert-butoxycarbonylmethyloxyphenyl) ethane, 1,
1,2-tris (4 ′-(1′-ethoxyethoxy) phenyl) ethane, 1,1,2-tris (4 ′-(1′-
Ethoxypropyloxy) phenyl) ethane and the like.

The addition amount of the dissolution inhibitor in the resist material of the present invention is determined by the amount of base polymer 100 in the resist material.
It is 20 parts by weight or less, preferably 15 parts by weight or less based on parts by weight. If the amount is more than 20 parts by weight, the heat resistance of the resist material decreases because the monomer component increases.

As the basic compound, a compound capable of suppressing the diffusion rate when the acid generated from the photoacid generator diffuses into the resist film is suitable. The resolution is improved by suppressing the acid diffusion rate in the film, the change in sensitivity after exposure can be suppressed, the dependence on the substrate and the environment can be reduced, and the exposure margin and pattern profile can be improved.

Such basic compounds include primary, secondary and tertiary aliphatic amines, mixed amines,
Aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group,
Examples 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.

Specifically, as primary aliphatic amines, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tertiary amine
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, -Methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline,
-Nitroaniline, 2,4-dinitroaniline, 2,6
-Dinitroaniline, 3,5-dinitroaniline, N,
N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyl diphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (for example, pyrrole, 2H
-Pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole and the like), oxazole derivatives (for example, oxazole,
Isoxazole, etc.), thiazole derivatives (eg, thiazole, isothiazole, etc.), imidazole derivatives (eg, imidazole, 4-methylimidazole,
-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-methyl) Pyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (for example, pyridine, methylidylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine , 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, 1
H-indazole derivative, indoline derivative, quinoline derivative (for example, quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivative, cinnoline derivative, quinazoline derivative, quinoxaline derivative, phthalazine derivative, purine derivative, pteridine derivative, carbazole derivative, phenanthridine Derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives,
Adenine derivatives, adenosine derivatives, guanine derivatives,
Guanosine derivatives, uracil derivatives, uridine derivatives and the like are exemplified.

Examples of the nitrogen-containing compound having a carboxy group include, for example, aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (eg, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycyl Leucine,
Leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine), and the like. Examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate, and the like. 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′-iminodiethanol, 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, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl)
Isonicotinamide and the like are exemplified. Amide derivatives include formamide, N-methylformamide, N, N
-Dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like. Examples of the imide derivative include phthalimide, succinimide, and maleimide.

Further, compounds in which a part or all of the hydroxyl groups of the nitrogen-containing compound having a hydroxy group are substituted with a methyl group, an ethyl group, a methoxymethyl group, a methoxyethoxymethyl group, an acetyl group, an ethoxyethyl group, etc. , Ethanolamine, diethanolamine,
Methyl-substituted, acetyl-substituted, methoxymethyl-substituted and methoxyethoxymethyl-substituted triethanolamine are preferably used. Specifically, tris (2-methoxyethyl) amine, tris (2-ethoxyethyl)
Amine, tris (2-acetoxyethyl) amine, 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)
Ethylamine, tris {2- (1-ethoxypropoxy) ethyl} amine, and tris [2-{(2-hydroxyethoxy) ethoxy} ethyl] amine.

The basic compound can be used alone or in combination of two or more. The compounding amount is from 0 to 2 parts by weight based on 100 parts by weight of the base polymer in the resist material. Particularly, a mixture of 0.01 to 1 part by weight is preferable. If the amount exceeds 2 parts by weight, the sensitivity may be too low.

In the resist material of the present invention, additives such as a surfactant for improving coating properties and a light absorbing material for reducing irregular reflection from the substrate can be added.

Examples of the surfactant include, but are not particularly limited to, polyoxyethylene alkyl such as polyoxyethylene lauryl ether, polyoxyethylene steryl ether, polyoxyethylene cetyl ether, and polyoxyethylene olein ether. Ethers, polyoxyethylene octyl phenol ether,
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers,
Sorbitan monolaurate, sorbitan monopalmitate, sorbitan fatty acid esters such as sorbitan monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate,
Nonionic surfactants of fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, EFTOP EF301, EF303, EF35
2 (Tochem Products), Mega Fuck F171, F
172, F173 (Dainippon Ink & Chemicals), Florad FC430, FC431 (Sumitomo 3M), Asahigard AG710, Surflon S-381, S-38
2, SC101, SC102, SC103, SC10
4, SC105, SC106, Surfinol E100
4, KH-10, KH-20, KH-30, KH-40
(Asahi Glass) and other fluorinated surfactants, organosiloxane polymers KP341, X-70-092, X-70-0
93 (Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based polyflow No. 93 75, no. 95 (Kyoeisha Yushi Kagaku Kogyo), among which FC430, Surflon S
-381 and Surfanol E1004 are preferred. These can be used alone or in combination of two or more.

The amount of the surfactant to be added to the resist composition of the present invention is determined by the amount of the base polymer 1 in the resist composition.
It is 2 parts by weight or less, preferably 1 part by weight or less based on 00 parts by weight.

Further, an ultraviolet absorber can be added to the resist composition of the present invention. Specifically, pentalene, indene, naphthalene, azulene, heptalene, biphenylene, indacene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, acephenanthrylene, aceanthrylene, triphenylene,
Pyrene, chrysene, naphthalene, pleiadene, picene, perylene, pentaphen, pentacene, benzophenanthrene, anthraquinone, anthrone, benzanthrone, 2,7-dimethoxynaphthalene, 2-ethyl-
9,10-dimethoxyanthoselan, 9,10-dimethylanthracene, 9-ethoxyanthracene, 1,2-
Naphthoquinone, 9-fluorene, the following general formula (D1),
Condensed polycyclic hydrocarbon derivatives such as (D2), condensed heterocyclic derivatives such as thioxanthen-9-one, thianthrene, dibenzothiophene, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetra Hydroxybenzophenone, 2,4-dihydroxybenzophenone, 3,5
-Dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 4,4'-bis (dimethylamino)
Benzophenone derivatives such as benzophenone, squaric acid, squaric acid derivatives such as dimethyl squarate,
Diarylsulfoxides such as bis (4-hydroxyphenyl) sulfoxide, bis (4-tert-butoxyphenyl) sulfoxide, bis (4-tert-butoxycarbonyloxyphenyl) sulfoxide, bis [4- (1-ethoxyethoxy) phenyl] sulfoxide and the like Derivatives, bis (4-hydroxyphenyl) sulfone,
Bis (4-tert-butoxyphenyl) sulfone, bis (4-tert-butoxycarbonyloxyphenyl) sulfone, bis [4- (1-ethoxyethoxy) phenyl] sulfone, bis [4- (1-ethoxypropoxy) phenyl] Diaryl sulfone derivatives such as sulfone, benzoquinonediazide, naphthoquinonediazide, anthraquinonediazide, diazofluorene, diazotetralone, diazo compounds such as diazophenanthrone, naphthoquinone-1,2-diazide-5-sulfonic acid chloride and 2,3 Complete or partial ester compound with 4-trihydroxybenzophenone, naphthoquinone-1,2-
Quinonediazide group-containing compounds such as complete or partial ester compounds of diazide-4-sulfonic acid chloride and 2,4,4'-trihydroxybenzophenone, tert-butyl 9-anthracenecarboxylate, tert-amyl 9-anthracenecarboxylate Tert-methoxymethyl 9-anthracenecarboxylate, tert-ethoxyethyl 9-anthracenecarboxylate, 2-tert-tetrahydropyranyl 9-anthracenecarboxylate, 9
-Tert-tetrahydrofuranyl-anthracenecarboxylic acid;

[0062]

Embedded image(Where R⁶¹~ R⁶³Are each independently a hydrogen atom, linear
Or a branched alkyl group, a linear or branched
Alkoxy group, linear or branched alkoxyal
A kill group, a linear or branched alkenyl group or an ant
A group. R ⁶⁴Is a substitution optionally containing an oxygen atom
Or an unsubstituted divalent aliphatic hydrocarbon group or an oxygen atom
A substituted or unsubstituted divalent alicyclic carbon which may be contained
Hydrogenated group, substituted or unsubstituted which may contain an oxygen atom
A substituted divalent aromatic hydrocarbon group or an oxygen atom;
⁶⁵Is the same acid labile group as described above. J is 0 or 1
You. E, F and G are each 0 or an integer of 1 to 9, and H is 1
A positive integer of 〜１０10 and satisfies E + F + G + H ≦ 10
I do. )

The amount of the ultraviolet absorber is from 0 to 10 parts by weight, preferably from 0.5 to 10 parts by weight, more preferably from 1 to 5 parts by weight, based on 100 parts by weight of the base polymer.

When the chemically amplified resist material of the present invention is used for manufacturing various integrated circuits, there is no particular limitation, but a known lithography technique can be used.

A substrate (Si, SiO ₂ ,
SiN, SiON, TiN, WSi, BPSG, SO
G, organic antireflection film, etc.), spin coating, roll coating, flow coating, dip coating, spray coating,
It is applied by an appropriate application method such as doctor coating so that the applied film thickness is 0.1 to 2.0 μm, and is applied on a hot plate at 60 to 150 ° C. for 1 to 10 minutes, preferably 80 to
Pre-bake at ~ 120 ° C for 1-5 minutes. Next, ultraviolet light, far ultraviolet light, electron beam, X-ray, excimer laser, γ
A desired pattern is exposed through a predetermined mask with a light source selected from radiation, synchrotron radiation and the like, preferably at an exposure wavelength of 300 nm or less. Exposure is 1 to 200
about mJ / cm ² , preferably 10 to 100 mJ / cm ²
Exposure is preferably performed to a degree. 60-150 ° C. on a hot plate for 1-5 minutes, preferably 80
Post-exposure bake (PEB) at ~ 120 ° C for 1-3 minutes.

Further, 0.1-5%, preferably 2-3%
Using a developer of an aqueous alkali solution such as tetramethylammonium hydroxide (TMAH) for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, a dipping method, a puddle method, and a spray method. A target pattern is formed on the substrate by developing by a conventional method such as a method. In addition, the material of the present invention is, particularly, a high-energy ray, a deep ultraviolet ray of 254 to 193 nm, an electron beam, X-ray.
Most suitable for fine patterning by X-ray, excimer laser, γ-ray, synchrotron radiation. In addition, when the above range is out of the upper limit and the lower limit, a desired pattern may not be obtained.

[0067]

According to the chemically amplified resist material of the present invention, the resolution is improved as compared with the conventional base resin having a wide degree of dispersion due to the narrow dispersion effect of the polymer. In addition, since the low molecular weight portion of the polymer is removed, the shape of the resist pattern becomes good, and the storage stability as a resist is also improved. Therefore, higher resolution, better pattern shape, and storage stability can be obtained as compared with conventional resist materials.

[0068]

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

Synthesis Example 1 A 2 L flask was charged with 113.4 g of acetoxystyrene, 54.7 g of 1-ethylcyclopentyl methacrylate, and 1.5 L of toluene as a solvent. The reaction vessel was placed in a nitrogen atmosphere at -7
After cooling to 0 ° C., degassing under reduced pressure and nitrogen flow were repeated three times. After raising the temperature to room temperature, AIBN was added as a polymerization initiator in 1
After adding 3.1 g, the mixture was heated to 60 ° C. and reacted for 15 hours. The reaction solution was concentrated to 1/2, and methanol 10
L, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 132 g of a white polymer. This polymer was redissolved in 0.5 L of methanol and 1.0 L of tetrahydrofuran, and 140 g of triethylamine and 30 g of water were added to carry out a deprotection reaction and neutralized with acetic acid. After concentrating the reaction solution, it was dissolved in 0.5 L of acetone, and precipitated, filtered and dried in the same manner as described above to obtain 109 g of a white polymer.

The obtained polymer was analyzed by ¹³ C, ¹ H-NMR and GPC measurement, and the following results were obtained. Copolymer composition ratio hydroxystyrene: 1-ethylcyclopentyl methacrylate = 72: 28 Weight average molecular weight (Mw) = 11,000 Molecular weight distribution (Mw / Mn) = 1.65 This is designated as (poly-1).

50 g of (poly-1) was added to 200 of acetone.
Dissolved in 10 ml (poor solvent) of diethyl ether and left for 1 hour to separate into two layers. This lower layer (polymer layer) was separated, precipitated in 10 L of a hexane solvent, filtered and dried to obtain 42 g of a white polymer. Weight average molecular weight (Mw) = 12,800 Molecular weight distribution (Mw / Mn) = 1.31 This is defined as (poly-B1).

Synthesis Example 2 A 2 L flask was charged with 113.4 g of acetoxystyrene, 56.8 g of 1-ethylcyclohexyl methacrylate, and 1.5 L of toluene as a solvent. The reaction vessel was placed in a nitrogen atmosphere at -7
After cooling to 0 ° C., degassing under reduced pressure and nitrogen flow were repeated three times. After raising the temperature to room temperature, AIBN was added as a polymerization initiator in 1
After adding 2.9 g, the mixture was heated to 60 ° C. and reacted for 15 hours. The reaction solution was concentrated to 1/2, and methanol 10
L, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 135 g of a white polymer. This polymer was redissolved in 0.5 L of methanol and 1.0 L of tetrahydrofuran, and 140 g of triethylamine and 30 g of water were added to carry out a deprotection reaction and neutralized with acetic acid. After concentrating the reaction solution, it was dissolved in 0.5 L of acetone, and the same precipitation, filtration and drying were performed as described above to obtain 110 g of a white polymer.

The obtained polymer was analyzed by ¹³ C, ¹ H-NMR and GPC measurement, and the following results were obtained. Copolymer composition ratio hydroxystyrene: 1-ethylcyclohexyl methacrylate = 73: 27 Weight average molecular weight (Mw) = 10,900 Molecular weight distribution (Mw / Mn) = 1.62 This is designated as (poly-2).

50 g of (poly-2) was added to 200 acetone.
After dissolving in 10 ml of hexane / 0.5 L of ethyl acetate (poor solvent), the mixture was separated for 1 layer after standing for 1 hour. This lower layer (polymer layer) was separated, precipitated in 10 L of hexane solvent, filtered and dried to obtain a white polymer 40.
g was obtained. Weight average molecular weight (Mw) = 13,000 Molecular weight distribution (Mw / Mn) = 1.32 This is designated as (poly-B2).

[Synthesis Example 3] Bicyclo [2.2.1] hept-5-ene-2-carboxylic acid 1 was placed in a 1-L flask.
296.2 g of ethyl cyclopentyl ester, 118.0 g of maleic anhydride, and 100 g of dioxane as a solvent
Was added. The reaction vessel was cooled to -70 ° C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen flow were repeated three times. After the temperature was raised to room temperature, 17.9 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by a reaction for 15 hours. This reaction solution was precipitated in 10 L of isopropyl alcohol, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 290 g of a white polymer.

The obtained polymer was analyzed by ¹³ C, ¹ H-NMR and GPC measurement, and the following results were obtained. Copolymer composition ratio bicyclo [2.2.1] hept-5-ene-2-carboxylic acid 1-ethylcyclopentyl ester: maleic anhydride = 50: 50 weight average molecular weight (Mw) = 8,700 molecular weight distribution (Mw / Mn) = 1.63 This is (poly-3).

50 g of (poly-3) was added to 200 acetone.
Dissolved in 10 ml (poor solvent) of diethyl ether and left for 1 hour to separate into two layers. This lower layer (polymer layer) was separated, precipitated in 10 L of a hexane solvent, filtered and dried to obtain 39 g of a white polymer. Weight average molecular weight (Mw) = 11,000 Molecular weight distribution (Mw / Mn) = 1.35 This is designated as (poly-B3).

[Synthesis Example 4] Bicyclo [2.2.1] hept-5-ene-2-carboxylic acid 1 was placed in a 1-L flask.
309.5 g of ethyl cyclohexyl ester, 110.0 g of maleic anhydride, 100 g of dioxane as a solvent
Was added. The reaction vessel was cooled to -70 ° C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen flow were repeated three times. After the temperature was raised to room temperature, 17.1 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by a reaction for 15 hours. This reaction solution was precipitated in 10 L of isopropyl alcohol, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 299 g of a white polymer.

The obtained polymer was analyzed by ¹³ C, ¹ H-NMR and GPC measurement, and the following results were obtained. Copolymer composition ratio Bicyclo [2.2.1] hept-5-ene-2-carboxylic acid 1-ethylcyclohexyl ester: maleic anhydride = 50: 50 Weight average molecular weight (Mw) = 9,000 Molecular weight distribution (Mw / Mn) = 1.71 This is designated as (poly-4).

50 g of (poly-4) was added to 200 acetone.
Dissolved in 10 ml of hexane / 1.0 L of ethyl acetate (poor solvent) and left for 1 hour to separate into two layers. This lower layer (polymer layer) was separated, precipitated in 10 L of hexane solvent, filtered and dried to obtain a white polymer 39.
g was obtained. Weight average molecular weight (Mw) = 11,700 Molecular weight distribution (Mw / Mn) = 1.31 This is defined as (poly-B4).

[Synthesis Example 5] The following polymer was obtained in the same manner as described above. Copolymer composition ratio bicyclo [2.2.1] hept-5-ene-2-carboxylic acid 1-ethylcyclopentyl ester: bicyclo [2.2.1] hept-5-ene-2-carboxylic acid = 8
0:20 Weight average molecular weight (Mw) = 13,000 Molecular weight distribution (Mw / Mn) = 1.82 This is designated as (poly-5).

50 g of (poly-5) was added to 200 acetone.
Dissolved in 10 ml of hexane / 1.0 L of ethyl acetate (poor solvent) and left for 1 hour to separate into two layers. This lower layer (polymer layer) was separated, precipitated in 10 L of hexane solvent, filtered and dried to obtain a white polymer 27.
g was obtained. Weight average molecular weight (Mw) = 15,500 Molecular weight distribution (Mw / Mn) = 1.37 This is designated as (poly-B5).

[Synthesis Example 6] The following polymer was obtained in the same manner as described above. Copolymer composition ratio bicyclo [2.2.1] hept-5-ene-2-carboxylic acid 1-ethylcyclopentyl ester: 5-methoxycarbonyl-5-methoxycarbonylmethyl-bicyclo [2.2.1] heptene = 60 : 40 Weight average molecular weight (Mw) = 11,000 Molecular weight distribution (Mw / Mn) = 1.77 This is designated as (poly-6).

50 g of (poly-6) was added to 200 parts of acetone.
Dissolved in 10 ml of hexane / 1.0 L of ethyl acetate (poor solvent) and left for 1 hour to separate into two layers. This lower layer (polymer layer) was separated, precipitated in 10 L of hexane solvent, filtered and dried to obtain a white polymer 31.
g was obtained. Weight average molecular weight (Mw) = 13,200 Molecular weight distribution (Mw / Mn) = 1.42 This is designated as (poly-B6).

The structural formula of the synthesized polymer compound is shown below.

Embedded image

Examples 1 and 2 and Comparative Examples 1 and 2 (poly-B1) and (poly-B2) obtained in the above synthesis examples.
As a base resin (parts by weight = 80), a triphenylsulfonium derivative of p-toluenesulfonic acid (parts by weight = 3) as an acid generator, and triethanolamine (parts by weight = 0.1) as a basic compound. 2,2-bis (4-t-butylcarboxyphenyl) as a dissolution inhibitor
Propane (parts by weight = 0.2) was mixed with propylene glycol monomethyl ether acetate / ethyl lactate (parts by weight = 5).
30, 7/3) to prepare a resist material, and each composition was filtered through a 0.2 μm Teflon (registered trademark) filter to prepare a resist solution. For comparison, (poly-1), (pol)
Using a polymer represented by y-2) as a base resin, a resist solution was prepared in the same manner as described above.

The obtained resist solution was spin-coated on a silicon wafer and applied to a thickness of 0.8 μm. Next, the silicon wafer was baked at 100 ° C. for 120 seconds using a hot plate. This is called KrF
Excimer Laser Stepper (Nikon Corporation, NSR-20
05EX8A, NA = 0.5) at 90 ° C.
After baking for 60 seconds and developing with an aqueous solution of 2.38% tetramethylammonium hydroxide, a positive pattern could be obtained. The obtained resist pattern was evaluated as follows. The results are shown in Table 1.

Evaluation method: First, the sensitivity (Eth) was determined. The sensitivity (mJ) is defined as the optimal exposure (Eop), which is the exposure that resolves a 0.35 μm line and space at a ratio of 1: 1.
/ Cm ² ). Next, the minimum line width of the separated line and space at this exposure amount was defined as the resolution of the evaluation resist. The unevenness (pattern shape) of the 0.20 μm line and space was measured with a scanning electron microscope.

[0089]

[Table 1]

Examples 3 to 6 and Comparative Examples 3 to 6 (poly-B3) to (poly-B6) obtained in the above synthesis examples.
Is used as a base resin (parts by weight = 80), a triphenylsulfonium trifluoromethanesulfonate derivative (parts by weight = 3) as an acid generator, and trismethoxymethoxyethylamine (parts by weight = 0.1) as a basic compound.
1) and 2,2-bis (4-t-butylcarboxyphenyl) propane (parts by weight = 0.2) as a dissolution inhibitor were added to propylene glycol monomethyl ether acetate /
A resist material was prepared by dissolving in ethyl lactate (parts by weight = 530, 7/3), and each composition was filtered through a 0.2 μm Teflon filter to prepare resist solutions. For comparison, (poly-3)
(Poly-6) was used as a base resin to prepare a resist solution in the same manner as described above.

The obtained resist solution was spin-coated on a silicon wafer and applied to a thickness of 0.8 μm. Next, the silicon wafer was baked at 100 ° C. for 120 seconds using a hot plate. This is ArF
Excimer laser stepper (Nikon, NA = 0.5
Exposure was performed using 5), baking was performed at 110 ° C. for 90 seconds, and development was performed using a 2.38% aqueous solution of tetramethylammonium hydroxide, whereby a positive pattern could be obtained. The obtained resist pattern was evaluated as follows. The results are shown in Table 2.

Evaluation method: First, the sensitivity (Eth) was determined. The sensitivity (mJ) is defined as the optimum exposure (Eop), which is the exposure that resolves a 0.25 μm line and space at 1: 1.
/ Cm ² ). Next, the minimum line width of the separated line and space at this exposure amount was defined as the resolution of the evaluation resist. The unevenness (pattern shape) of the 0.20 μm line and space was measured with a scanning electron microscope.

[0093]

[Table 2]

From the results shown in Tables 1 and 2, it was confirmed that the chemically amplified positive resist composition of the present invention can form a pattern having a high resolution and an improved pattern shape.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 232/00 C08F 232/00 232/04 232/04 H01L 21/027 H01L 21/30 502R (72) Invention Person Atsushi Watanabe 28-1 Nishifukushima, Nippon-mura, Nakakujuku-gun, Niigata Prefecture Inside the Synthetic Technology Research Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inventor Jun Hatakeyama 28-1, Nishifukushima, Nishi-Fukushima, Nishi-Fukushima, Niigata Prefecture Shin-Etsu Chemical Co., Ltd. Within the Synthetic Technology Research Institute (72) Inventor Tsunehiro Nishi 28-1 Nishifukushima, Niigata-ku, Niigata Pref.Shin-Etsu Chemical Co., Ltd. 28-1 Nishifukushima Shin-Etsu Chemical Co., Ltd.

Claims (4)

[Claims] 1. A polymer compound comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2): a polymer compound comprising a repeating unit represented by the following formula (2): A polymer compound comprising a repeating unit represented by the formula (2) and a repeating unit represented by the following formula (4), a polymer compound comprising a repeating unit represented by the following formula (3), and a polymer compound represented by the following formula (4) It is selected from the high molecular compounds consisting of the repeating units shown and has a molecular weight distribution of 1.
A chemically amplified resist material comprising 0 to 1.5 polymer compound. Embedded image (Wherein, R ¹ represents an alkyl group, an alkoxyalkyl group, an acetyl group or a carbonylalkoxy group,
Each unit may be composed of one type or two or more types. p is a positive number, q is 0 or a positive number, and is a number satisfying 0 <p / (p + q) ≦ 1. ) (Wherein, R ² represents a hydrogen atom or a methyl group, and R ³ represents a tertiary hydrocarbon group having 4 to 30 carbon atoms.) (Wherein, R ⁴ represents a tertiary hydrocarbon group having 4 to 30 carbon atoms, and R ^{5 to} R ⁸ each independently represent a hydrogen atom, an ester group, an alkoxycarbonylalkyl group, a lactone group, a carboxyl group, or a cyclic group. Represents an acid anhydride group;
Any two of ^{5 to} R ⁸ may combine to form a cyclic lactone group or an acid anhydride group. r is a positive number, s is 0 or a positive number, and is a number satisfying 0 <r / (r + s) ≦ 1. ) (In the formula, R ⁹ represents a tertiary hydrocarbon group having 4 to 30 carbon atoms, and n is 0 or 1.) 2. The resist material according to claim 1, comprising a polymer compound having a molecular weight distribution of 1.0 to 1.4. 3. A high molecular compound is dissolved in a good solvent for the high molecular compound, the solution is poured into a poor solvent for the high molecular compound, and low molecular weight components in the high molecular compound are separated and removed. The resist material according to claim 1, further comprising a polymer compound having a molecular weight distribution of 1.0 to 1.5. 4. The poor solvent and the good solvent are water, acetone, ethyl acetate, methyl acetate, diethyl ether, tetrahydrofuran, cyclohexanone, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, propylene glycol monomethyl ether acetate, ethyl lactate, The resist material according to claim 3, wherein the resist material is selected from methanol, ethanol, isopropyl alcohol, pentane, hexane, toluene, benzene, and xylene, and is selected according to a polymer compound to be fractionated.