JP2001133979A - High molecular compound, chemical amplification resist material and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resist material sensitive to high energy beams, excellent in sensitivity, resolution and plasma etching resistance, giving a resist pattern excellent in heat resistance and reproducibility, usable as a resist material having small absorption particularly at the exposure wavelength of Kr2, F2, ArF or KrF excimer laser light, capable of easily forming a minute pattern perpendicular to a substrate and suitable for use as a minute pattern forming material for the production of a very large scale integrated circuit. SOLUTION: The high molecular compound contains repeating units of formula 1 (where at least one of R1-R3 is F or trifluoromethyl, the remainders are each H or a 1-20C linear, branched or cyclic alkyl; R4 is an acid labile group; 0 <k<=1, 0<=m<1 and k+m=1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymer compound useful as a base polymer of a chemically amplified resist material suitable for a fine processing technique, a chemically amplified 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.

[0004] To shorten the wavelength from KrF to ArF (193 nm), the design rule has to be reduced to 0.13 μm.
Although it is expected to be as follows, conventionally used novolak and polyvinylphenol-based resins are 193 nm.
Since it has a very strong absorption in the vicinity, it cannot be used as a base resin for resist. In order to ensure transparency and required dry etching resistance, an alicyclic resin such as an acrylic resin or a cycloolefin resin has been studied (Japanese Patent Application Laid-Open No. Hei 9 (1998)).
-73173, JP-A-10-10739, JP-A-9
-230595, WO97 / 33198). Further, F ₂ (157) which can be expected to be finer than 0.10 μm
nm), it became more and more difficult to ensure transparency, and it was found that acrylics, which did not transmit light at all, and cycloolefins, which had a carbonyl bond, had strong absorption. Furthermore, according to the study of the present inventors,
Polyvinyl phenol has an absorption window at around 160 nm, which slightly improves the transmittance. However, it is far from the practical level, and it is necessary to reduce the double bond between carbonyl and carbon to secure the transmittance. Turned out to be.

[0005] The present invention has been made in view of the above circumstances,
300 nm or less, especially 157 nm, 146 nm, 126
A novel polymer compound useful as a base polymer of a chemically amplified resist material having excellent transmittance in vacuum ultraviolet light such as nm, a chemically amplified resist material containing the same, and a pattern forming method using the resist material. And

[0006]

Means for Solving the Problems and Embodiments of the Invention The present inventor has conducted intensive studies to achieve the above object, and as a result, by using a resin based on fluorinated polyvinyl alcohol, a transparent resin has been obtained. It has been found that a resist material having sufficient properties and alkali solubility can be obtained.

That is, according to the study of the present inventors, polyvinyl alcohol does not contain a carbonyl group, and therefore has relatively low absorption. Further, halogen-substituted, especially fluorine-substituted, has an effect of improving transmittance, and is practically usable. It was found that a specific transmittance could be obtained. In general, the development process of photolithography is generally a method of paddle or dipping with alkaline water, followed by rinsing with pure water and spin-drying. It is necessary to lower the solubility in water. Polyvinyl alcohol is highly soluble in water as it is used as a base polymer of a resist for water development, and thus is likely to be dissolved not only at the time of alkali development but also at the time of rinsing. Therefore, by increasing the acidity of the alcohol by fluorinating polyvinyl alcohol,
It has been found that it is desirable to increase the solubility in alkali and widen the difference from the solubility in water.

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

[0010] Claim 1: A polymer compound containing a repeating unit represented by the following general formula (1).

[0010]

Embedded image (Wherein at least one of R ¹ , R ² and R ³ is a fluorine atom or a trifluoromethyl group, and the rest is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms) R ⁴ is an acid labile group, and 0 <k ≦ 1, 0
≦ m <1 and k + m = 1. )

[0011] Claim 2: A polymer compound containing a repeating unit represented by the following general formula (2).

[0012]

Embedded image (Wherein at least one of R ¹ , R ² and R ³ is a fluorine atom or a trifluoromethyl group, and the rest is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms) R ⁴ is an acid labile group, R ⁵ is an acid stable group,
0 <k ≦ 1, 0 ≦ m <1, 0 ≦ n <1, k
+ M + n = 1. )

(3) A resist material comprising a polymer compound represented by the general formula (1) or (2).

(4) A chemically amplified positive resist material comprising (A) the polymer compound according to (1) or (2), (B) an organic solvent, and (C) an acid generator.

Claim 5: A chemical amplification negative comprising (A) the polymer compound according to claim 1 or 2, (B) an organic solvent, (C) an acid generator, and (D) a crosslinking agent. Mold resist material.

In a preferred embodiment, the resist composition further comprises (E) a basic compound.

In a preferred embodiment, the resist composition further comprises (F) a dissolution inhibitor.

Claim 8: (1) a step of applying the resist material according to any one of claims 3 to 7 on a substrate; and (2) a heat treatment, followed by a wavelength of 300 nm or less via a photomask. A step of exposing with a high-energy ray or an electron beam, and (3) a step of performing a heat treatment as necessary and then developing with a developer.

Hereinafter, the present invention will be described in more detail.
The polymer compound of the present invention has the following general formula (1) or (2)
And a repeating unit represented by

[0020]

Embedded image (Wherein at least one of R ¹ , R ² and R ³ is a fluorine atom or a trifluoromethyl group, and the rest is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms) R ⁴ is an acid labile group, R ⁵ is an acid stable group,
0 <k ≦ 1, 0 ≦ m <1, 0 ≦ n <1, k + m = 1 in equation (1) and k + m + in equation (2)
n = 1. )

Here, the linear, branched or cyclic alkyl group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a te-butyl group.
rt-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group and the like having 1 to 20 carbon atoms, preferably 1 to 16, more preferably 1 to 1
2 are mentioned.

As the acid labile group represented by R ⁴ , various types can be selected. In particular, groups represented by the following formulas (3) and (4) and tertiary alkyl groups represented by the following formula (5) It is preferable that each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or the like.

[0023]

Embedded image

In the formula (3), R ⁶ has 4 to 2 carbon atoms.
0, preferably a tertiary alkyl group of 4 to 15, each alkyl group being a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or the above general formula (4)
Wherein the tertiary alkyl group is specifically a tert-butyl group, a tert-amyl group,
-Diethylpropyl group, 1-ethylcyclopentyl group,
1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-
A cyclopentenyl group, a 1-ethyl-2-cyclohexenyl group, a 2-methyl-2-adamantyl group, and the like;
Specific examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a dimethyl-tert-butylsilyl group. Specific examples of the oxoalkyl group include a 3-oxocyclohexyl group and a 4-methyl-
A 2-oxooxan-4-yl group, a 5-methyl-2-oxooxolan-5-yl group, and the like. a is 0
6 is an integer.

In the formula (4), R ⁷ and R ^{8 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. ,
Ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group,
Examples thereof include an n-octyl group. R ⁹ has 1 to 1 carbon atoms
8, preferably a monovalent hydrocarbon group which may have 1 to 10 hetero atoms such as an oxygen atom, and may be linear, branched,
Cyclic alkyl groups, some of these hydrogen atoms are hydroxyl groups,
Examples include those substituted with an alkoxy group, an oxo group, an amino group, an alkylamino group, and the like, and specific examples include the following substituted alkyl groups.

[0026]

Embedded image

R ⁷ and R ⁸ , R ⁷ and R ⁹ , and 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.

Specific examples of the acid labile group of the above formula (3) include a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a tert-amyloxycarbonyl group, a 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 group represented by the above formula (4) include the following groups.

[0030]

Embedded image

As the cyclic group among the acid labile groups represented by the above formula (4), 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 (4)
Preferred are an ethoxyethyl group, a butoxyethyl group and an ethoxypropyl group.

Next, in the formula (5), 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 (5) 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.

As the tertiary alkyl group, the following formulas (5-1) to (5-16) can be specifically mentioned.

[0035]

Embedded image

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, especially 1 to 16 alkyl groups, hydroxyalkyl groups, alkoxy groups or alkoxyalkyl groups, and the like, which may be linear, branched, or cyclic. Specifically, methyl, hydroxymethyl, ethyl, hydroxyethyl, propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, methoxy, methoxymethoxy Group, ethoxy group, tert-butoxy group and the like.

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.

The oxoalkyl group having 4 to 20 carbon atoms includes a 3-oxocyclohexyl group and a group represented by the following formula.

[0040]

Embedded image

R ⁵ as an acid-stable group is resistant to etching,
Or it can be introduced to improve adhesion,
A cyclic alkyl group is preferable, and a bridged cyclic alkyl group is more preferable. Specifically, the following formulas (6-1) to
(6-18).

[0042]

Embedded image (In the formula, R ¹⁴ , R ¹⁵ , and R ¹⁶ are the same as above.)

In the equation (1), 0 <k ≦ 1, 0
≦ m <1, but when used for a positive resist, preferably 0.1 ≦ k ≦ 0.9, more preferably 0.15 ≦ k ≦ 0.85, and still more preferably 0.2 ≦ k ≦ 0.85. k ≦
0.8. Note that k + m = 1.

Further, in the equation (2), 0 <k ≦ 1, 0
≦ m <1, 0 ≦ n <1, preferably 0.1 ≦ k
≤ 0.9, more preferably 0.15 ≤ k ≤ 0.85, even more preferably 0.2 ≤ k ≤ 0.8, and preferably 0.1 ≤ n ≤ 0.8, more preferably 0.15 ≦ n
≦ 0.6, more preferably 0.2 ≦ n ≦ 0.5.
Note that k + m + n = 1.

The polymer compound of the present invention has a weight average molecular weight of 1,000 to 1,000,000, especially 2,000 to 1
Preferably it is 100,000.

To obtain the polymer compound of the present invention, the following
Nomer (1a) can be used. RO-CR¹= CR^TwoR^Three (1a) (wherein, R is a group capable of being eliminated and converted to a hydrogen atom, for example,
CF_ThreeGroup, CH_ThreeGroup, CH _ThreeShows a C (= O) group. R¹, R
^Two, R^ThreeIs the same as above. )

After polymerizing the monomer (1a) to obtain a polymer having a unit represented by the following formula (1b),
The group is converted to an OH group.

[0048]

Embedded image

The introduction of R ⁴ and R ⁵ is carried out by the following formula (1 ′)
Can be carried out by introducing an acid labile group or an acid stable group into the OH group after obtaining a polymer having a repeating unit represented by An ordinary method can be adopted as the introduction method.

[0050]

Embedded image

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 polymer compound of the present invention includes those obtained by copolymerizing other copolymerizable monomers with the above-mentioned monomers. Examples of such other monomers include ethylene, propylene, perfluoroethylene, perfluoropropylene, styrene, hydroxystyrene, acrylic acid derivatives, methacrylic acid derivatives, maleic anhydride, norbornene, and vinyl alcohol derivatives.
Those containing a heavy bond can be used. The amount of these monomers used is 1% of the total amount of the monomers (1a).
The copolymerization amount is preferably 5 mol or less, particularly 3 mol or less, per mol.

The polymer compound of the present invention comprises a resist material,
Particularly, it is suitably used as a base resin of a chemically amplified resist material (positive type, negative type).

Accordingly, the present invention provides [I] a resist material comprising a polymer compound represented by the above general formula (1) or (2); [II] (A) a resist material comprising the above general formula (1) Or a chemically amplified positive resist material comprising: a polymer compound represented by (2), (B) an organic solvent, and (C) an acid generator; [III] (A) the above-mentioned general formula (1) Or a chemically amplified negative resist material comprising a polymer compound represented by (2), (B) an organic solvent, (C) an acid generator, and (D) a crosslinking agent; [IV] E) the resist material containing a basic compound,
[V] The present invention further provides the resist material containing (F) a dissolution inhibitor.

Here, the organic solvent of the component (B) used in the present invention may be any organic solvent capable of dissolving an acid generator, a base resin, a dissolution inhibitor and the like. Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol,
1-methoxy-2-propanol, 1-ethoxy-2-
Alcohols such as 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,
Esters such as ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol-mono-tert-butyl ether acetate, and the like, alone or as a mixture of two or more thereof It can be used, 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 a mixed solvent thereof are preferably used.

Examples of the acid generator (C) include an onium salt of the following general formula (11), a diazomethane derivative of the formula (12), a glyoxime derivative of the formula (13), a β-ketosulfone derivative, a disulfone derivative, and nitrobenzyl. Sulfonate derivatives, sulfonic acid ester derivatives, imido-yl sulfonate derivatives, and the like.

[0057] _{^{(R 30) b M + K}} - (11) ( 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, a 2-
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.

[0059]

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.

[0061]

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. . )

As the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group represented by R ³³ , R ³⁴ and R ³⁵ , the same groups as described for R ³¹ and R ³² can be mentioned. The alkylene group for R ³⁴ and R ³⁵ includes a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and the like.

Specifically, for example, diphenyliodonium trifluoromethanesulfonate, phenyliodonium trifluoromethanesulfonate (p-tert-butoxyphenyl), diphenyliodonium p-toluenesulfonate, p-toluenesulfonic acid (p-tert-
(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 mixing amount of the acid generator is 100
The amount is preferably from 0.2 to 15 parts by weight, particularly preferably from 0.5 to 8 parts by weight with respect to parts by weight. If the amount is less than 0.2 parts by weight, the amount of acid generated upon exposure is small, and the sensitivity and resolution are poor. In some cases, when the amount exceeds 15 parts by weight, the transmittance of the resist is reduced, and the resolution may be poor.

As the basic compound as the component (E), a compound capable of suppressing the 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, hybrid amines, and the like.
Aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group,
Examples of the compound include a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, and an imide derivative, and an aliphatic amine is particularly preferably used.

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

Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine and benzyldimethylamine. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (for example, aniline,
N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline , 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-
Dimethyl toluidine, etc.), diphenyl (p-tolyl) amine, methyl diphenylamine, triphenylamine,
Phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole,
2,5-dimethylpyrrole, N-methylpyrrole, etc.),
Oxazole derivatives (eg, oxazole, isoxazole, etc.), thiazole derivatives (eg, thiazole, isothiazole, etc.), imidazole derivatives (eg, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, Pyrroline derivatives (eg, pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (eg, pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg, pyridine, methyl) Pyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridyl , 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 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.

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, etc.), and 3-pyridinesulfonic acid as a nitrogen-containing compound having a sulfonyl group. , 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-quinoline. Diol, 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,
Examples thereof include 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, and N- (2-hydroxyethyl) isonicotinamide. Examples of the amide derivative include formamide, N-methylformamide, N, N-dimethylformamide, acetamido, N-methylacetamido,
N-dimethylacetamide, propionamide, benzamide and the like are exemplified. Examples of the imide derivative include phthalimide, succinimide, and maleimide.

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

[0071]

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

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

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

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

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

Specific examples of the compounds of the above formulas (14) and (15) 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) ethoxy} ethyl] 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, 1,4,1
0,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6
And the like. Especially 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) ethyl} amine, tris [2 -{(2-methoxyethoxy) methyl} ethyl]
Amines, 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.

Component (F): dissolution inhibitor (molecular weight of 3,000 whose solubility in an alkali developing solution is changed by the action of an acid)
As the following compound), a compound in which a part or all of a phenol or carboxylic acid derivative having a low molecular weight of 2,500 or less is substituted with an acid-labile substituent can be added.

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 the dissolution inhibitor preferably used 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-
tert-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'-t
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, 4,4-bis (4 ′-(2 ″-
Tetrahydrofuranyloxy) phenyl) valeric acid ter
t-butyl, tert-butyl 4,4-bis (4′-tert-butoxyphenyl) valerate, 4,4-bis (4-t
tert-butoxycarbonyloxyphenyl) valeric acid t
tertbutyl, tertbutyl 4,4-bis (4′-tert-butoxycarbonylmethyloxyphenyl) valerate, tertbutyl 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′-tetrahydrofuran) Niloxy) 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′-ethoxypropyl) ) 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,
1,2-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 [component (F)] in the resist material of the present invention is 30 parts by weight or less, preferably 20 parts by weight or less based on 100 parts by weight of the solids in the resist material. . If the amount is more than 30 parts by weight, the heat resistance of the resist material decreases because the monomer component increases.

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

The resist composition of the present invention may contain, as an optional component, 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, Florad “FC-430” (Sumitomo 3M Co., Ltd.)
X-70-093 "(Shin-Etsu Chemical Co., Ltd.)
Is mentioned.

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

[0086]

The resist material of the present invention is sensitive to high energy rays, excellent in sensitivity, resolution and plasma etching resistance, and also excellent in heat resistance and reproducibility of the resist pattern. Accordingly, the resist material of the present invention can be a resist material having a small absorption at the exposure wavelength of Kr ₂ , F ₂ , ArF, and KrF excimer laser, because of these characteristics, and is fine and perpendicular to the substrate. A pattern can be easily formed, and therefore, it is suitable as a fine pattern forming material for VLSI manufacturing.

[0087]

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] Synthesis of poly (trifluoromethyl trifluorovinyl ether) A 1 L autoclave was charged with 300 ml of degassed toluene and 2 g of an initiator AIBN under a nitrogen stream, and the temperature was reduced to 78 ° C. While maintaining, 50 g of trifluoromethyltrifluorovinyl ether was blown. After returning to room temperature, the temperature was raised to 60 ° C., and the polymerization reaction was performed for 24 hours.

Next, in order to purify the polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated, separated and dried. As a result, 40 g of a white polymer poly (trifluoromethyl) was obtained. Trifluorovinyl ether) was obtained. This polymer was confirmed to have a weight average molecular weight of 15,500 g / mol by a light scattering method and a dispersity (= Mw / Mn) of 1.60 from a GPC elution curve.

Synthesis Example 2 Synthesis of Poly (trifluorovinyl alcohol) A 1 L flask was charged with 40 g of poly (trifluoromethyltrifluorovinyl ether) obtained in Synthesis Example 1, 72 g of sodium iodide, and 300 ml of acetonitrile. While stirring at room temperature, 53 g of chlorotrimethylsilane was dropped from the dropping funnel while paying attention so that the reaction temperature did not exceed 30 ° C. Thereafter, the temperature was raised to 60 ° C., and aging was performed for 24 hours.

Next, 100 g of pure water was added dropwise under ice-cooling.
After heating to 0 ° C., aging was performed for 10 hours. After decolorization with an aqueous solution of sodium hydrogen sulfite, the reaction solution was transferred to a separating funnel, and the upper layer was taken out. 200 g of ethyl acetate and 100 g of toluene
Was added, and the polymer layer was washed twice with 150 g of water. After the polymer solution was transferred to the dropping funnel, it was poured into hexane, and the obtained polymer was precipitated, separated and dried to obtain 32 g of a white polymer poly (trifluorovinyl alcohol). . This polymer had a weight average molecular weight of 9,000 g / mol as determined by a light scattering method.
From the PC elution curve, it was confirmed that the polymer had a dispersity (= Mw / Mn) of 1.65.

[Synthesis Example 3] Tetrahydropyranylation of poly (trifluorovinyl alcohol) In a 300 ml flask, 20 g of the poly (trifluorovinyl alcohol) obtained in Synthesis Example 2, 0.6 g of trifluoromethanesulfonic acid, and 100 ml of THF were added. I charged.
While stirring at room temperature, 3,4-dihydro- was added through a dropping funnel.
4.0 g of 2H pyran was added dropwise, and the mixture was aged at room temperature for 1 hour.

The reaction was terminated by adding triethylamine to the reaction system, and the solvent was distilled off under reduced pressure. The obtained crude polymer was dissolved in 40 g of acetone, and poured into 5 L of pure water in which 20 g of acetic acid was dissolved to precipitate the polymer. The operation of dissolving the obtained polymer in 40 g of acetone and pouring it into 5 L of pure water to precipitate the polymer was repeated twice, and then the polymer was separated and dried. 15 obtained in this way
g of white polymer 20% tetrahydropyranylated poly (trifluorovinyl alcohol) has a weight average molecular weight of 9,600 g / mol by a light scattering method and a dispersity (= Mw / Mn) of 1. based on a GPC elution curve. It was confirmed that the polymer was No. 60 polymer. Also, by measuring ¹ H-NMR, it was confirmed that 20% of the hydroxyl groups of poly (trifluorovinyl alcohol) were tetrahydropyranylated.

[Synthesis Example 4] Ethoxyethylation of poly (trifluorovinyl alcohol) A 300 ml flask was charged with 20 g of the poly (trifluorovinyl alcohol) obtained in Synthesis Example 2, 0.6 g of trifluoromethanesulfonic acid, and 100 ml of THF. It is.
While stirring at room temperature, 3.4 g of ethyl vinyl ether was added dropwise from the dropping funnel, and the mixture was aged at room temperature for 1 hour.

The reaction was stopped by adding triethylamine to the reaction system, and the solvent was distilled off under reduced pressure. The obtained crude polymer was dissolved in 40 g of acetone, and poured into 5 L of pure water in which 20 g of acetic acid was dissolved to precipitate the polymer. The operation of dissolving the obtained polymer in 40 g of acetone and pouring it into 5 L of pure water to precipitate the polymer was repeated twice, and then the polymer was separated and dried. 1 obtained in this way
4.5 g of the white polymer 20% ethoxyethylated poly (trifluorovinyl alcohol) had a weight average molecular weight of 9,300 g / mol by a light scattering method, and a dispersity (= Mw / Mn) of 1 from the GPC elution curve. It was confirmed that the polymer was .65. Also, by measuring ¹ H-NMR, it was confirmed that 20% of the hydroxyl groups of poly (trifluorovinyl alcohol) were ethoxyethylated.

Synthesis Example 5 Ethoxypropylation of Poly (trifluorovinyl alcohol) A 300 ml flask was charged with 20 g of the poly (trifluorovinyl alcohol) obtained in Synthesis Example 2, 0.6 g of trifluoromethanesulfonic acid, and 100 ml of THF. It is.
While stirring at room temperature, 4.1 g of ethyl propenyl ether was added dropwise from a dropping funnel, and the mixture was aged at room temperature for 1 hour.

The reaction was terminated by adding triethylamine to the reaction system, and the solvent was distilled off under reduced pressure. The obtained crude polymer was dissolved in 40 g of acetone, and poured into 5 L of pure water in which 20 g of acetic acid was dissolved to precipitate the polymer. The operation of dissolving the obtained polymer in 40 g of acetone and pouring it into 5 L of pure water to precipitate the polymer was repeated twice, and then the polymer was separated and dried. 1 obtained in this way
5.5 g of the white polymer 20% ethoxyethylated poly (trifluorovinyl alcohol) had a weight average molecular weight of 9,700 g / mol by a light scattering method and a dispersity (= Mw / Mn) of 1 from the GPC elution curve. .67 was confirmed to be a polymer. Also, by measuring ¹ H-NMR, it was confirmed that 20% of the hydroxyl groups of poly (trifluorovinyl alcohol) were ethoxyethylated.

[Synthesis Example 6] Tert-butoxycarbonylation of poly (trifluorovinyl alcohol) In a 500 ml flask, 20 g of the poly (trifluorovinyl alcohol) obtained in Synthesis Example 2 and 250 m of pyridine
l was charged. While stirring at room temperature, di-
25 ml of tetrahydrofuran in which 10 g of (tert-butyl) dicarbonate was dissolved was added dropwise, and reacted at room temperature for 1 hour.

The solvent was distilled off under reduced pressure, and the obtained crude polymer was dissolved in 40 g of acetone and poured into 5 L of pure water to precipitate the polymer. After the obtained polymer was washed twice with 5 L of pure water, the polymer was separated and dried. 16.0 g of the white polymer 18% tert-
Butoxycarbonylated poly (trifluorovinyl alcohol) has a weight average molecular weight of 9,400 g by a light scattering method.
/ Mol, and the degree of dispersion (= Mw /
Mn) was 1.60. Also, by measuring ¹ H-NMR, 18% of the hydroxyl groups of poly (trifluorovinyl alcohol) were found to be tert-
-Butoxycarbonylation was confirmed.

Comparative polymer: molecular weight 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.

Further, the molecular weight is 15,000 and the dispersity is 1.7.
Of polymethyl methacrylate in Comparative Example 2 polymer, meta / para ratio 40/60, molecular weight 9,000, dispersity 2.5
Was used as the polymer of Comparative Example 3.

Next, 1 g of the polymers of Synthesis Examples 4 to 6 and Comparative Examples 1 to 3 were sufficiently dissolved in 10 g of propylene glycol monomethyl ether acetate.
A polymer solution was prepared by filtration through a 0.2 μm filter.

The polymer solution was spin-coated on a MgF ₂ substrate and baked at 100 ° C. for 90 seconds using a hot plate to form a 300 nm-thick polymer layer on the MgF ₂ substrate. Vacuum ultraviolet photometer (VUV2 manufactured by JASCO Corporation)
00S) using 248 nm, 193 nm, 157 nm
Was measured. Table 1 shows the results.

[0104]

[Table 1]

[Examples and Comparative Examples] A resist solution was prepared by a conventional method using the polymers shown in Table 1 and the components shown below in the amounts shown in Table 2.

Next, a DUV-30 (manufactured by Nissan Chemical Industries, Ltd.) film was formed to a thickness of 55 nm on the silicon wafer using the obtained resist solution, and the reflectance was suppressed to 1% or less with KrF light (248 nm). The substrate was spin-coated and baked at 100 ° C. for 90 seconds using a hot plate to reduce the thickness of the resist film to 300 nm.

An excimer laser stepper (Nikon Corporation, NSR-S202A, NA-0.5, σ0.7
5, 2/3 annular illumination), and immediately after exposure,
Baking was performed at 10 ° C. for 90 seconds, and development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide for 60 seconds to obtain a positive pattern (however, Example 8 was a negative pattern).

The obtained resist pattern was evaluated as follows. The results are shown in Tables 2 and 3. Evaluation method: 0.25 μm line and space:
The exposure amount resolved at 1 was taken as the optimum exposure amount (Eop), and the minimum line width of the line and space separated at this exposure amount was taken as the resolution of the evaluation resist.

In the dry etching resistance test, the wafer after the spin coating of the resist was evaluated under two conditions. (1) Etching test with CHF ₃ / CF ₄ system gas Dry etching equipment TE manufactured by Tokyo Electron Limited
Using -8500P, the difference in thickness of the resist before and after etching was determined. The etching conditions are as shown below. Chamber pressure 40 Pa RF power 1300 W Gap 9 mm CHF ₃ gas flow rate 30 ml / min CF ₄ gas flow rate 30 ml / min Ar gas flow rate 100 ml / min Time 60 sec (2) Etching test with Cl ₂ / BCl ₃ system gas Dry made by Nidec Anelva Corporation Etching equipment L-50
Using 7D-L, the difference in thickness of the resist before and after etching was determined. The etching conditions are as shown below. Chamber pressure 40 Pa RF power 300 W Gap 9 mm Cl ₂ gas flow rate 30 ml / min BCl ₃ gas flow rate 30 ml / min CHF ₃ gas flow rate 100 ml / min O ₂ gas flow rate 2 ml / min Time 360 sec

[0110]

Embedded image

[0111]

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[0112]

[Table 2]

[0113]

[Table 3]

From the results shown in Tables 1, 2, and 3, the resist material using the polymer compound of the present invention was found to be particularly resistant to F ₂ (157n).
m) In the region, sufficient transparency, resolution and sensitivity in KrF exposure are satisfied, and the thickness difference after etching is close to that of the polyhydroxystyrene derivative (Comparative Example 1 polymer).
It was found that it had better dry etching resistance than polymethyl methacrylate (Comparative Example 2 polymer).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 29/10 C08L 29/10 G03F 7/004 501 G03F 7/004 501 7/038 601 7/038 601 7 / 38 7/38 H01L 21/027 H01L 21/30 502R

Claims (8)

[Claims] 1. A polymer compound containing a repeating unit represented by the following general formula (1). Embedded image (Wherein at least one of R ¹ , R ² and R ³ is a fluorine atom or a trifluoromethyl group, and the rest is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms) R ⁴ is an acid labile group, and 0 <k ≦ 1, 0
≦ m <1 and k + m = 1. ) 2. A polymer compound comprising a repeating unit represented by the following general formula (2). Embedded image (Wherein at least one of R ¹ , R ² and R ³ is a fluorine atom or a trifluoromethyl group, and the rest is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms) R ⁴ is an acid labile group, R ⁵ is an acid stable group,
0 <k ≦ 1, 0 ≦ m <1, 0 ≦ n <1, k
+ M + n = 1. ) 3. A resist material comprising a polymer compound represented by the general formula (1) or (2). 4. A chemically amplified positive resist material comprising (A) the polymer compound according to claim 1 or 2, (B) an organic solvent, and (C) an acid generator. 5. A chemically amplified negative resist comprising (A) the polymer compound according to claim 1 or 2, (B) an organic solvent, (C) an acid generator, and (D) a crosslinking agent. material. 6. The resist material according to claim 4, further comprising (E) a basic compound. 7. The resist material according to claim 4, further comprising (F) a dissolution inhibitor. 8. A step of (1) applying the resist material according to claim 3 on 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.