JP2001233917A - Polymer compound, resist material and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist material sensitive to a high-energy ray and excellent in sensitivity, resolution and plasma etching resistance at a wavelength of not longer than 200 nm, particularly not longer than 170 nm. SOLUTION: The resist material comprises a polymer compound containing, as a recurring unit in its main chain, a fluorinated acrylic derivative represented by general formula (1) (wherein R1, R2 and R3 are each a hydrogen or fluorine atom, or a 1-20C linear, branched or cyclic alkyl or fluorinated alkyl group, and at least one of R1, R2 and R3 contains a fluorine atom; and R4 is an acid- labile group). This resist material can be a resist material having low absorption at the exposure wavelengths of an F2 excimer laser in particular due to its characteristics and can easily form a fine pattern perpendicular to a substrate, and therefore is suitable as a fine-pattern forming material for manufacturing an ultra LSI.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist material suitable for microfabrication technology, particularly to a polymer compound useful as a base polymer of a chemically amplified resist material, a resist material, and a pattern forming method using the same.

[0002]

2. Description of the Related Art LSI
With the high integration and high speed of the pattern, the miniaturization of the pattern rule is rapidly progressing. The background of the rapid progress of miniaturization is the increase in NA of projection lenses, improvement of resist material performance,
Shortening of the wavelength is mentioned. Especially from i-line (365 nm) to K
Shortening the wavelength to rF (248 nm) has brought about a major change, and it has become possible to mass-produce devices with the 0.18-micron rule. In order to increase the resolution and sensitivity of resist materials, acid-catalyzed chemically amplified positive resist materials (described in JP-B-2-27660, JP-A-63-27829, etc.) have excellent characteristics. It has become a mainstream resist material particularly for deep ultraviolet lithography.

[0003] Resist materials for KrF excimer lasers have generally begun to be used in 0.3 micron processes,
After the 0.25 micron rule, the application of the 0.18 micron rule to mass production and the study of the 0.15 micron rule have also begun, and the pace of miniaturization is accelerating increasingly. Shortening of the wavelength from KrF to ArF (193 nm) is expected to reduce the design rule to 0.13 μm or less. However, conventionally used novolak and polyvinylphenol-based resins have been reduced to around 193 nm. Since it has very strong absorption, it cannot be used as a base resin for resist. From such a point, acrylic and cycloolefin-based alicyclic resins have been studied in order to ensure transparency and required dry etching resistance (JP-A-9-73173, JP-A-10-10739).
No., JP-A-9-230595, WO97 / 33198
However, as for F ₂ (157 nm), which can be expected to have a fineness of 0.10 μm or less, it becomes more and more difficult to secure transparency, and acrylic does not transmit light at all and cycloolefin does not. Those having a carbonyl bond were found to have strong absorption.

[0004] The present invention has been made in view of the above circumstances,
300 nm or less, particularly F ₂ (157 nm), Kr ₂ (14
6 nm), KrAr (134 nm), Ar ₂ (126 n
It is an object of the present invention to provide a novel polymer compound useful as a base polymer of a resist material having excellent transmittance in vacuum ultraviolet light such as m), a resist material containing the same, and a pattern forming method using the resist material.

[0005]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies to achieve the above object, and as a result, the main chain represented by the following general formula (1) was fluorinated. It has been found that by using a resin based on a polymer compound containing an acrylic derivative as a repeating unit, a resist material having transparency and anti-negative properties can be obtained.

[0006]

Embedded image ^{(Wherein, R 1, R 2, R} 3 is a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms, R ^1, R ² , R ³
At least one contains a fluorine atom. R ⁴ is an acid labile group. )

That is, according to the study of the present inventors, the transmittance of polyvinylphenol at around 160 nm is slightly improved, but it is far from the practical level. It turned out to be a necessary condition for security.

However, the ring structure and the double bond between carbon and carbon greatly contribute to the improvement of dry etching resistance. ArF having an alicyclic structure introduced to eliminate the benzene ring and improve the etching resistance. It is difficult to ensure transparency because the polymer for use has a solubility with carboxylic acid. Therefore, the present inventor has further studied and found that it is effective to use a polymer substituted with fluorine as a means for improving the transparency, in particular, the transparency of an acrylic polymer used as an ArF resist. Investigation was made to improve the properties, and it was found that an acrylic derivative whose main chain was substituted with fluorine was used.

[0009] The problem with shortening the wavelength is not only the decrease in transparency, but also with the positive type resist material, a negative phenomenon occurs in which the exposed portion is not dissolved when the exposure amount is increased. It is pointed out that Since the negative part becomes insoluble not only in an alkali developing solution but also in an organic solvent such as acetone, it is considered that gelation occurs due to crosslinking between molecules. One of the causes of crosslinking is
Radical generation is considered. Exposure energy is increased by shortening the wavelength, and in F ₂ (157 nm) exposure, energy is emitted to excite even the C—C bond and C—H bond, and radicals are generated by the excitation. There is a possibility that they are combined. In the case of a polymer having an alicyclic structure used for ArF exposure, for example, polynorbornene, a particularly remarkable negative phenomenon was observed. Since the alicyclic group has many C—H bonds at the bridge head, it is considered that the structure is easy to crosslink. On the other hand, it is well known that α-methylstyrene or its derivatives are effective for preventing crosslinking. However, although negative conversion could be alleviated by α-methylstyrene, it could not be completely prevented. Since the oxygen absorption is large in the VUV region, it is purged with an inert gas such as nitrogen or Ar, and is exposed in a state where the oxygen concentration is reduced to 1 ppm or less. Since oxygen is an effective radical trapping agent, it is considered that the generated radical has a long lifetime and the crosslinking is likely to proceed. Therefore, as a result of further study, the type of resist polymer was
In particular, a remarkable negative phenomenon was observed in a resist using a polyhydroxystyrene base polymer. In contrast, acrylate-based resists do not show much negative phenomena, and the use of polyacrylate with a fluorinated main chain as the base resin ensures transparency and anti-negativity. The inventors have found that a material can be obtained, and have accomplished the present invention.

That is, the present invention provides the following polymer compound, a chemically amplified resist material, and a pattern forming method. [1] A high molecular compound represented by the above general formula (1), wherein the main chain contains a fluorinated acrylic derivative as a repeating unit; [2] a polymer represented by the above general formula (1) A resist material containing a compound, [3] (A) a polymer compound represented by the general formula (1), (B) an organic solvent, and (C) an acid generator. A chemically amplified positive resist material, [4] the above resist material further containing a basic compound, [5]
Further, the above resist material containing a dissolution inhibitor, [6]
(1) a step of applying the resist material on a substrate;
(2) Then, after the heat treatment, a wavelength of 3
A pattern forming method comprising: a step of exposing with a high energy beam or an electron beam of not more than 00 nm; and (3) a step of performing a heat treatment as necessary and then developing with a developing solution.

Hereinafter, the present invention will be described in more detail.
The polymer compound of the present invention contains, as a repeating unit, an acrylic derivative represented by the following general formula (1) whose main chain is fluorinated.

Embedded image ^{(Wherein, R 1, R 2, R} 3 is a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms, R ^1, R ² , R ³
At least one contains a fluorine atom. R ⁴ is an acid labile group. )

In this case, the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms includes methyl, ethyl, propyl, isopropyl, n-butyl and s.
Examples thereof include an ec-butyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group, a 2-ethylhexyl group, an n-octyl group, and the like, and particularly preferably those having 1 to 12 carbon atoms, particularly preferably 1 to 10 carbon atoms. Note that the fluorinated alkyl group is a group in which part or all of the hydrogen atoms of the above-described alkyl group has been substituted with fluorine atoms, and is a trifluoromethyl group, a 2,2,2-trifluoroethyl group,
3,3-trifluoropropyl group, 1,1,2,2
3,3,3-heptafluoropropyl group and the like.

The acid labile groups represented by R ⁴ include:
Although various selections are made, in particular, groups represented by the following formulas (2) and (3), tertiary alkyl groups having 4 to 40 carbon atoms, and trialkylsilyl groups having 1 to 6 carbon atoms represented by the following formula (4) And an oxoalkyl group having 4 to 20 carbon atoms.

[0014]

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R ⁶ has 4 to 20 carbon atoms, preferably 4 to 1 carbon atoms.
5 tertiary alkyl groups, each alkyl group having 1 carbon atom
A trialkylsilyl group, an oxoalkyl group having 4 to 20 carbon atoms or a group represented by the above general formula (4),
Specific examples of the tertiary alkyl group include a tert-butyl group, a tert-amyl group, a 1,1-diethylpropyl group, a 1-ethylcyclopentyl group, a 1-butylcyclopentyl group, a 1-ethylcyclohexyl group, and a 1-butylcyclohexyl. Group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2-methyl-2-adamantyl group and the like. Specific examples of the trialkylsilyl group include a trimethylsilyl group and a triethylsilyl group. And a dimethyl-tert-butylsilyl group. Specific examples of the oxoalkyl group include a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group and a 5-methyl-2-oxooxolane. −
5-yl group and the like. a is an integer of 0 to 6.

R ⁷ and R ^{8 each} represent a hydrogen atom or a group having 1 to 18 carbon atoms;
It preferably represents 1 to 10 linear, branched or cyclic alkyl groups, specifically, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl. , A cyclopentyl group, a cyclohexyl group, a 2-ethylhexyl group, an n-octyl group and the like. R ⁹ has 1 to 18 carbon atoms, preferably 1 to 1 carbon atoms.
0 represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom, and is a linear, branched, or cyclic alkyl group, and a part of these hydrogen atoms is a hydroxyl group, an alkoxy group, or an oxo group. , An amino group, an alkylamino group, and the like, and specific examples thereof include the following substituted alkyl groups.

[0017]

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R ⁷ and R ⁸ , R ⁷ and R ⁹ , R ⁸ and R ⁹ may form a ring, and when forming a ring, R ⁷ , R ⁸ and R ⁹ each have 1 carbon atom. -18, preferably 1-10, linear or branched alkylene groups.

Examples of the acid labile group of the above formula (2) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group,
1,1-diethylpropyloxycarbonyl group, 1,1
-Diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-
2-cyclopentenyloxycarbonyl group, 1-ethyl-2-cyclopentenyloxycarbonylmethyl group, 1
-Ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

Specific examples of the linear or branched acid labile groups represented by the above formula (3) include the following groups.

[0021]

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As the cyclic group among the acid labile groups represented by the above formula (3), specifically, tetrahydrofuran-
Examples thereof include a 2-yl group, a 2-methyltetrahydrofuran-2-yl group, a tetrahydropyran-2-yl group, and a 2-methyltetrahydropyran-2-yl group. Equation (3)
Preferred are an ethoxyethyl group, a butoxyethyl group and an ethoxypropyl group.

Next, in the equation (4), R ¹⁰ , R ¹¹ , R ¹²
Is a monovalent hydrocarbon group such as a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and oxygen, sulfur, nitrogen,
It may contain a hetero atom such as fluorine, and R ¹⁰ and R ¹¹ ,
R ¹⁰ and R ¹² , and R ¹¹ and R ¹² may be bonded to each other to form a ring.

The tertiary alkyl group represented by the formula (4) includes a tert-butyl group, a triethylcarbyl group,
Ethylnorbonyl group, 1-methylcyclohexyl group, 1
-Ethylcyclopentyl group, 2- (2-methyl) adamantyl group, 2- (2-ethyl) adamantyl group, ter
A t-amyl group and the like can be mentioned.

Further, specific examples of the tertiary alkyl group include the following formulas (4-1) to (4-16).

[0026]

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Here, R ¹³ and R ¹⁴ represent a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n-
Examples thereof include a butyl group, a sec-butyl group, an n-pentyl group, an n-hexyl group, a cyclopropyl group, and a cyclopropylmethyl group. R ¹⁵ is a hydrogen atom, a monovalent hydrocarbon group which may contain a heteroatom having 1 to 6 carbon atoms, or a 1 to 1 carbon atom.
6 represents a monovalent hydrocarbon group such as an alkyl group which may be interposed through 6 hetero atoms. Examples of the hetero atom include an oxygen atom, a sulfur atom and a nitrogen atom, and —OH, —OR (R
Alkyl groups of 1 to 20 carbon atoms, particularly 1 to 16, hereinafter the same), - O -, - S -, - S (= O) -, - NH 2, -
_{NHR, -NR 2, -NH -,} - can contain or intervening as NR-.

R ¹⁶ is a hydrogen atom or a group having 1 to 1 carbon atoms.
20, in particular, 1 to 16 alkyl groups, hydroxyalkyl groups, alkoxyalkyl groups, alkoxy groups or alkoxyalkyl groups, etc., which may be linear, branched or cyclic. Specifically, methyl, hydroxymethyl, ethyl, hydroxyethyl, propyl, isopropyl, n-butyl, se
c-butyl group, n-pentyl group, n-hexyl group, methoxy group, methoxymethoxy group, ethoxy group, tert-
Butoxy groups and the like can be exemplified.

Examples of the trialkylsilyl group in which each alkyl group used as the acid labile group of R ⁴ has 1 to 6 carbon atoms include a trimethylsilyl group, a triethylsilyl group, and a tert-butyldimethylsilyl group.

Examples of the oxoalkyl group having 4 to 20 carbon atoms include a 3-oxocyclohexyl group and a group represented by the following formula.

[0031]

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The polymer compound (fluorine-containing polyacrylate compound) of the present invention is produced using an acid-eliminable substituent-containing monomer represented by the following general formula (1a) which gives the repeating unit of the above formula (1). be able to.

Embedded image (In the formula, R ^{1 to} R ⁴ are the same as above.)

Specific examples of the monomer of the general formula (1a) include those represented by the following formulas (1a) -1 to (1a) -6.

[0034]

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In this case, the fluorine-containing polyacrylate compound of the present invention includes a monomer containing an acid-releasing substituent-containing monomer for improving adhesion and a monomer for improving dry etching resistance. It can be further polymerized. Examples of the monomer for improving the adhesion include those containing a hydrophilic substituent such as phenol, acid anhydride, ester (lactone), carbonate, alcohol, carboxylic acid, carboxylic amide, sulfonic amide, and ketone. The formula (5-
1) to (5-44).

[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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In the formula, R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are a hydrogen atom,
It is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and specific examples of the alkyl group are as described above.

When the above-mentioned polymer compound is produced, generally, the above-mentioned monomers and a solvent are mixed, and a catalyst is added thereto.
In some cases, the polymerization reaction is performed while heating or cooling. The polymerization reaction is also governed by the type of initiator (or catalyst), initiation method (light, heat, radiation, plasma, etc.), polymerization conditions (temperature, pressure, concentration, solvent, additives) and the like. In the polymerization of the polymer compound of the present invention, AIB
Radical copolymerization, in which polymerization is initiated by a radical such as N, and ionic polymerization (anionic polymerization) using a catalyst such as alkyllithium are common. These polymerizations can be carried out according to the usual methods.

The above-mentioned polymer compound has a weight average molecular weight of 1,000 to 1,000,000, especially 2,000 to 1
Preferably it is 100,000.

The polymer compound of the present invention comprises a resist material,
In particular, it can be used as a chemically amplified positive resist material.

Accordingly, the present invention provides a chemically amplified positive resist composition comprising (A) the above-mentioned polymer compound (base resin), (B) an organic solvent, and (C) an acid generator. .

In this case, these resist materials may further contain (D) a basic compound and (E) a dissolution inhibitor.

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 an onium salt of the following general formula (6), a diazomethane derivative of the formula (7), a glyoxime derivative of the formula (8), a β-ketosulfone derivative, a disulfone derivative, and nitrobenzyl. Sulfonate derivatives, sulfonic acid ester derivatives, imido-yl sulfonate derivatives, and the like.

[0050] _{^{(R 30) b M + K}} - (6) ( where, R ³⁰ is a straight-chain having 1 to 12 carbon atoms, branched or cyclic alkyl group, an aryl group or a carbon number of 6 to 12 carbon atoms Represents 7 to 12 aralkyl groups, M ⁺ represents iodonium or sulfonium, K ⁻ represents a non-nucleophilic counter ion, and b is 2 or 3.)

As the alkyl group for R ^30, 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.

[0052]

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 of 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.

[0054]

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.

More 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 (D), a compound capable of suppressing the diffusion rate when the acid generated from the acid generator diffuses 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, mixed 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, 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, 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 (9) and (10) can be blended.

[0064]

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 of 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, 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 (9) and (10) include tris {2- (methoxymethoxy) ethyl} amine, tris {2- (methoxyethoxy) ethyl} amine, and 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, especially 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.

Next, as the dissolution inhibitor of the component (E),
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, particularly a part or all of a phenol or carboxylic acid derivative having a low molecular weight of 2,500 or less with an acid-labile substituent. Substituted compounds can be mentioned.

Examples of phenol or carboxylic acid derivatives 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 are mentioned, and as the acid-labile substituent, the same as those described above can be mentioned.

Examples of preferably used 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′-
Tert-butyl (2 ″ tetrahydropyranyloxy) phenyl) valerate, tert-butyl 4,4-bis (4 ′-(2 ″ tetrahydrofuranyloxy) phenyl) valerate
-Butyl, tert-butyl 4,4-bis (4′-tert-butoxyphenyl) valerate, 4,4-bis (4-
tert-butoxycarbonyloxyphenyl) tert-butyl valerate, 4,4-bis (4′-tert-butoxycarbonylmethyloxyphenyl) valerate
tert-butyl, tert-butyl 4,4-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) valerate, 4,4
Tert-butyl bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) valerate, tris (4- (2 ′
Tetrahydropyranyloxy) phenyl) methane, tris (4- (2′tetrahydrofuranyloxy) phenyl) methane, tris (4-tert-butoxyphenyl) 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 amount of the dissolution inhibitor added to the resist composition of the present invention is 20 parts by weight or less, preferably 15 parts by weight or less based on 100 parts by weight of the solids in the resist composition. If the amount is more than 20 parts by weight, the heat resistance of the resist material decreases because the monomer component increases.

The resist composition of the present invention may contain, as an optional component, a surfactant which is commonly used for improving coating properties, in addition to the above components. 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.

Here, 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 a known lithography technique. For example, a film having a thickness of 0 is formed on a substrate such as a silicon wafer by spin coating or the like. .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 F ₂ , 146 nm Kr ₂ , 134 nm KrA
r, it is best suited for fine patterning with an excimer laser, X-rays and electron beams, such as Ar ₂ in 126 nm. In addition, when the above range is out of the upper limit and the lower limit, a desired pattern may not be obtained.

[0078]

The resist material of the present invention is sensitive to high energy rays and has excellent sensitivity, resolution and plasma etching resistance at a wavelength of 200 nm or less, particularly 170 nm or less. Therefore, the resist material of the present invention can be a resist material having a small absorption at the exposure wavelength of the F ₂ excimer laser due to these characteristics, and can easily form a fine and perpendicular pattern to the substrate, Therefore, it is suitable as a fine pattern forming material for VLSI manufacturing.

[0079]

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] Synthesis of poly (1-ethylcyclopentyl 2,3,3-trifluoroacrylate) In a 500 ml flask, 25 g of 1-ethylcyclopentyl 2,3,3-trifluoroacrylate was added to toluene 1
After dissolving in 20 ml and thoroughly removing oxygen in the system,
0.74 g of an initiator AIBN was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours. To purify the obtained polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated. Further, the operation of dissolving the obtained polymer in acetone and pouring it into 5 L of methanol to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The thus obtained 19.5 g of white polymer poly (1-ethylcyclopentyl 2,3,3,3-trifluoroacrylate) had a weight average molecular weight of 9,800 g / mol by a light scattering method and was eluted with GPC. From the curve, it was confirmed that the polymer had a dispersity (= Mw / Mn) of 1.90.

Synthesis Example 2 Synthesis of Poly (2-ethylnorbornyl 2,3,3-trifluoroacrylate) 2-Ethylnorbornyl 2,3,3-trifluoroacrylate in a 500 ml flask 25 g of toluene 12
After dissolving in 0 ml, oxygen in the system was sufficiently removed, 0.66 g of AIBN was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours. To purify the obtained polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated. Further, the operation of dissolving the obtained polymer in acetone and pouring it into 5 L of methanol to precipitate the polymer was repeated twice, and then the polymer was separated and dried. 20.3 g of the white polymer poly (2-ethylnorbornyl 2,3,3-trifluoroacrylate) thus obtained had a weight average molecular weight of 10,
It was 500 g / mol, and it was confirmed from the GPC elution curve that the polymer had a dispersity (= Mw / Mn) of 1.85.

[Synthesis Example 3] Synthesis of poly (adamantyl 2,3,3-trifluoroacrylate) In a 500 ml flask, 25 g of adamantyl 2,3,3-trifluoroacrylate was dissolved in 120 ml of toluene and sufficiently dissolved. After removing oxygen in the system, the initiator AIB
0.63 g of N was charged and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours. In order to purify the obtained polymer,
The reaction mixture was poured into methanol to precipitate the obtained polymer. Further, the operation of dissolving the obtained polymer in acetone and pouring it into 5 L of methanol to precipitate the polymer was repeated twice, and then the polymer was separated and dried. 19.0 g of the white polymer poly (2,2) thus obtained was obtained.
(3,3-adamantyl trifluoroacrylate) is a polymer having a weight average molecular weight of 11,000 g / mol by a light scattering method and a dispersity (= Mw / Mn) of 1.90 from a GPC elution curve. It could be confirmed.

[Synthesis Example 4] Synthesis of poly (t-butyl 2,3,3-trifluoroacrylate) In a 500 ml flask, 25 g of t-butyl 2,3,3-trifluoroacrylate was dissolved in 120 ml of toluene. After sufficient removal of oxygen in the system, the initiator AIBN
0.90 g was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours. To purify the obtained polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated. Further, the operation of dissolving the obtained polymer in acetone and pouring it into 5 L of methanol to precipitate the polymer was repeated twice, and then the polymer was separated and dried. 18.5 g of the white polymer poly (2,3,
(T-butyl 3-trifluoroacrylate) has a weight average molecular weight of 9,200 g / mol according to a light scattering method.
From the PC elution curve, it was confirmed that the polymer had a dispersity (= Mw / Mn) of 1.95.

[Synthesis Example 5] Synthesis of poly (1-ethylcyclopentyl 3-trifluoromethyl-2,3-difluoroacrylate) In a 500 ml flask, 3-trifluoromethyl-
After dissolving 25 g of 1-ethylcyclopentyl 2,3-difluoroacrylate in 120 ml of toluene and sufficiently removing oxygen in the system, 0.60 g of an initiator AIBN was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours. went. To purify the obtained polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated. Further, the operation of dissolving the obtained polymer in acetone and pouring it into 5 L of methanol to precipitate the polymer was repeated twice, and then the polymer was separated and dried. 2 obtained in this way
0.5 g of white polymer poly (3-trifluoromethyl-
1-ethylcyclopentyl 2,3-difluoroacrylate) has a weight average molecular weight of 11,000 g by a light scattering method.
/ Mol, and the degree of dispersion (= Mw /
Mn) was 1.95.

Synthesis Example 6 Synthesis of Poly (1-ethylcyclopentyl 2-trifluoromethyl-3,3-difluoroacrylate) In a 500 ml flask, 2-trifluoromethyl-
After dissolving 25 g of 1-ethylcyclopentyl 3,3-difluoroacrylate in 120 ml of toluene and sufficiently removing oxygen in the system, 0.60 g of an initiator AIBN was charged, the temperature was raised to 60 ° C., and the polymerization reaction was performed for 24 hours. went. To purify the obtained polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated. Further, the operation of dissolving the obtained polymer in acetone and pouring it into 5 L of methanol to precipitate the polymer was repeated twice, and then the polymer was separated and dried. 1 obtained in this way
9.1 g of white polymer poly (2-trifluoromethyl-
1,3-ethylfluoropentyl 3,3-difluoroacrylate) has a weight average molecular weight of 10,500 g by a light scattering method.
/ Mol, and the degree of dispersion (= Mw /
Mn) was 1.92.

Synthesis Example 7 Synthesis of Poly (2,3,3-trifluoroadamantyl trifluoroacrylate) and γ-butyrolactone acrylate copolymer (6: 4) 2,3,3-triol in a 500 ml flask After dissolving 18 g of adamantyl fluoroacrylate and 10 g of γ-butyrolactone acrylate in 120 ml of toluene and sufficiently removing oxygen in the system, 0.63 g of an initiator AIBN was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours. went. To purify the obtained polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated. Further, the obtained polymer is dissolved in acetone, and methanol 5L
After the operation of pouring into the mixture and precipitating the polymer was repeated twice, the polymer was separated and dried. 19.0 g of the thus obtained white polymer poly (adamantyl 2,3,3-trifluoroacrylate, -co-acrylic acid γ)
-Butyrolactone) was found to be a polymer having a weight average molecular weight of 9,500 g / mol by a light scattering method and a dispersity (= Mw / Mn) of 2.05 from a GPC elution curve. Further, ¹ H-NMR measurement showed that the obtained polymer contained adamantyl 2,3,3-trifluoroacrylate and γ-butyrolactone acrylate in a ratio of 6: 4.

[Synthesis Example 8] Poly (2,3,3-trifluoroadamantyl acrylate) and 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonane-2-acrylate Synthesis of yl copolymer (6: 4) 18 g of adamantyl 2,3,3-trifluoroacrylate and 5-oxo-acrylate in a 500 ml flask
4-oxatricyclo [4.2.1.0 ^3,7 ] nonane-
After dissolving 12 g of 2-yl in 120 ml of toluene and sufficiently removing oxygen in the system, 0.63 g of an initiator AIBN
And the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours. To purify the obtained polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated. Further, the obtained polymer is dissolved in acetone, and methanol 5L
After the operation of pouring into the mixture and precipitating the polymer was repeated twice, the polymer was separated and dried. 19.0 g of the thus obtained white polymer poly (adamantyl 2,3,3-trifluoroacrylate, -co-acrylic acid 5)
-Oxo-4-oxatricyclo [4.2.1.
0 ^3,7 ] nonan-2-yl) is a polymer having a weight average molecular weight of 9,000 g / mol by a light scattering method and a dispersity (= Mw / Mn) of 2.02 from a GPC elution curve. Was confirmed. Further, by ¹ H-NMR measurement,
The composition ratio of the above copolymer was found to be 6: 4.

Synthesis Example 9 Poly (2-trifluoromethyl adamantyl acrylate) and 5-oxo-acrylate
4-oxatricyclo [4.2.1.0 ^3,7 ] nonane-
Synthesis of 2-yl copolymer (5: 5) 18 g of adamantyl 2-trifluoromethylacrylate and 5-oxo-4 acrylate in a 500 ml flask
-Oxatricyclo [4.2.1.0 ^3,7 ] nonane-2
After dissolving 12.4 g of yl in 120 ml of toluene and sufficiently removing oxygen in the system, the initiator AIBN 0.63
g, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours. To purify the obtained polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated. Further, the obtained polymer was dissolved in acetone, and methanol 5
After the operation of pouring into L and precipitating the polymer was repeated twice, the polymer was separated and dried. 19.6 g of the thus obtained white polymer poly (adamantyl 2-trifluoromethylacrylate, -co-acrylic acid 5)
-Oxo-4-oxatricyclo [4.2.1.
0 ^3,7 ] nonan-2-yl) is a polymer having a weight average molecular weight of 8,000 g / mol by a light scattering method and a dispersity (= Mw / Mn) of 1.85 from a GPC elution curve. Was confirmed. Further, by ¹ H-NMR measurement,
The composition ratio of the above copolymer was found to be 5: 5.

Next, 1 g of the polymer obtained above was sufficiently dissolved in 10 g of propylene glycol monomethyl ether acetate and filtered with a 0.2 μm filter.
A polymer solution was prepared. On the other hand, the molecular weight is 10,000,
A polymer in which 30% of monodisperse polyhydroxystyrene having a dispersity (= Mw / Mn) of 1.10 was substituted with a tetrahydropyranyl group was synthesized, and this was designated as Comparative Example 1 polymer. Also,
Comparative Example 2 Polymethyl methacrylate having a molecular weight of 15,000 and a dispersity of 1.7 was prepared using a polymer having a meta / para ratio of 40/60
A novolak polymer having a molecular weight of 9,000 and a dispersity of 2.5 was used as a polymer of Comparative Example 3. 1 g of the obtained polymer was mixed with propylene glycol monomethyl ether acetate 1
The polymer solution was sufficiently dissolved in 0 g, and filtered through a 0.2 μm filter to prepare a polymer solution. These polymer solutions were spin-coated on a MgF ₂ substrate and baked at 100 ° C. for 90 seconds using a hot plate to obtain a thickness of 300 nm.
Was formed on a MgF ₂ substrate. 248 n using a vacuum ultraviolet photometer (VUV200S, manufactured by JASCO Corporation)
The transmittance at m, 193 nm and 157 nm was measured. Table 1 shows the results.

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[Table 1]

[Examples and Comparative Examples] A resist solution was prepared by a conventional method using the above polymers and the components shown below in the amounts shown in Table 2. Next, the obtained resist solution is formed into a film of DUV-30 (manufactured by Nissan Chemical Industries, Ltd.) on a silicon wafer with a thickness of 55 nm, and the reflectance is 1% with KrF light (248 nm).
The substrate was spin-coated on the following substrate, and baked at 100 ° C. for 90 seconds using a hot plate to reduce the thickness of the resist to 300 nm.

An excimer laser stepper (Nikon Corporation, NSR-2005EX8A, NA-0.5, σ)
0.7 ordinary illumination) and stepping exposure while changing the exposure amount over an exposure area of 4 mm square,
Baking was performed at 0 ° C. for 90 seconds, and development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide for 60 seconds, and the relationship between the exposure amount and the remaining film ratio was determined. The sensitivity of the resist was determined by setting the exposure amount at which the film thickness became 0 as Eth.

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[Table 2] PGMEA: Propylene glycol monomethyl ether acetate

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From Table 2, it can be seen that sufficient transparency can be ensured even at a wavelength of F ₂ (157 nm), and that the film thickness decreases with an increase in the amount of exposure in KrF exposure, exhibiting the characteristics of a positive resist. Was.

Claims (6)

[Claims] 1. A polymer compound represented by the following general formula (1), which comprises, as a repeating unit, an acrylic derivative whose main chain is fluorinated. Embedded image ^{(Wherein, R 1, R 2, R} 3 is a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms, R ^1, R ² , R ³
At least one contains a fluorine atom. R ⁴ is an acid labile group. ) 2. A resist material comprising the polymer compound according to claim 1. (A) the polymer compound according to (1),
A chemically amplified positive resist composition comprising (B) an organic solvent and (C) an acid generator. 4. The method according to claim 3, further comprising a basic compound.
The resist material as described. 5. The resist material according to claim 3, further comprising a dissolution inhibitor. 6. A step of (1) applying the resist material according to any one of claims 2 to 5 onto a substrate; and (2)
Next, after the heat treatment, a wavelength of 300 n is passed through a photomask.
A pattern forming method comprising: exposing with a high-energy ray or an electron beam of m or less; and (3) performing a heat treatment as necessary and then developing with a developer.