JP2000128930A - Polymer compound, chemical amplification resist material and pattern formation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer compound for providing a resist material having improved dry etching resistance by crosslinking a polymer with a crosslinkable group stable to an acid within or between polymers. SOLUTION: For example, any monomer of monomers of formula I, formula II (R1 is O, N, S or the like; R2 is H or a 1-10C alkyl; R3 is a 1-8C alkyl; (m) is 0-4), or the like, is mixed with a solvent and a catalyst, optionally heated or cooled, polymerized by using a radical polymerization initiator such as AIBN, and crosslinked within or between polymers to give the objective polymer compound containing any of repeating units of formula III to V crosslinked within or between polymers. The polymer compound is mixed with an organic solvent (e.g. diethylene glycol dimethyl ether, or the like), an acid generator (e.g. trifluoromethanesulfonate diphenyliodonium, or the like) to give a resist material useful as a chemical amplification type resist.

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

[0003] From such a viewpoint, an acid-catalyzed chemically amplified positive resist material recently developed (Japanese Patent Publication No. 2-2)
No. 7660, described in JP-A-63-27829, etc.)
Has high sensitivity, high resolution and excellent features.
It is a particularly promising resist material for deep ultraviolet lithography.

[0004] 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 begun. The miniaturization of KrF excimer laser lithography is accelerating. With the miniaturization of design rules, further improvement in resolution of resist materials has been demanded. However, demand for improvement in dry etching resistance has been further increased. It is generally said that polyhydroxystyrene has lower etching resistance than novolak, and that a resin obtained by replacing polyhydroxystyrene with acetal has low resistance particularly to etching using a chlorine-based gas. It is said that there is a correlation between etching resistance and heat resistance, and it is known that a cross-linked polymer having a three-dimensional structure in which resins are cross-linked is effective for improving heat resistance (Japanese Patent Application Laid-Open No. 8-30525). . However, since it has an acetal group as a cross-linking point, the effect of improving dry etching properties is small, and further improvement in dry etching resistance has been desired.

SUMMARY OF THE INVENTION The present invention has been made in order to meet the above-mentioned demand, and is intended to provide a novel polymer compound useful as a base polymer of a chemically amplified resist material having excellent dry etching resistance, a chemically amplified resist material containing the same, and this resist material. It is an object to provide a pattern forming method used.

[0006]

Means for Solving the Problems and Embodiments of the Invention As a result of diligent studies to achieve the above object, the present inventor has found that an acid-stable crosslinking group is used to crosslink inside or between polymers. It has been found that by using a resist material using a polymer having a three-dimensional structure, the dry etching resistance can be greatly improved, and the present invention has been accomplished.

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

Claim 1: The following general formulas (1a) and (1)
(b) A polymer compound crosslinked intramolecularly or intermolecularly, having any of the repeating units represented by (1c).

[0009]

Embedded image (Wherein, R ¹ is an oxygen atom, a nitrogen atom, a sulfur atom, a linear, branched or cyclic unsubstituted or aryl-substituted alkylene or alkylidene group having 1 to 20 carbon atoms, An unsubstituted or alkyl group-substituted arylene group or arylidine group, or a divalent or trivalent group in which an alkylene group or an alkylidine group is bonded to an arylene group or an arylidine group, the alkylene group, an alkylidine group, an arylene group, The divalent or trivalent group in which the arylidine group and the alkylene group or the alkylidine group are bonded to the arylene group or the arylidine group may include a heteroatom, wherein R ² is a hydrogen atom or a carbon atom having 1 to 10 carbon atoms.
Is a linear, branched or cyclic alkyl group. R
³ is a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. m is an integer of 0-4. )

Claim 2: The above-mentioned general formulas (1a), (1)
(b) a polymer compound crosslinked intramolecularly or intermolecularly having any of the repeating units represented by (1c), further comprising any one of the following general formulas (2a), (2b), and (2c) And the following general formulas (3a) and (3
The polymer compound according to claim 1, which has a repeating unit represented by (b) or (3c), and has a weight average molecular weight of 1,000 to 500,000.

[0011]

Embedded image (Wherein, R ² and R ³ have the same meanings as above, and R ⁴ is an acid labile group. M is an integer of 0 to 4, n is an integer of 1 to 5, p is 1 to 5) It is an integer, but m + n ≦ 5, m + p ≦
5 )

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

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

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

Claim 6: (1) a step of applying the chemically amplified resist material according to any one of claims 3, 4, and 5 on a substrate; and (2) a heating process followed by a photomask. A step of exposing with a high-energy ray or an electron beam having a wavelength of 300 nm or less, 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)
a) having at least one of the repeating units represented by (a), (1b) and (1c).

[0018]

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Here, R ¹ is an oxygen atom, a nitrogen atom, a sulfur atom, or a linear, branched or cyclic unsubstituted or substituted group having 1 to 20, preferably 1 to 16, more preferably 1 to 14 carbon atoms. An aryl group (such as a phenyl group) -substituted alkylene group or alkylidyne group, an unsubstituted or alkyl-substituted arylene group having 6 to 20, preferably 6 to 16, and more preferably 6 to 14 carbon atoms (phenylene group, biphenylene group, A divalent group in which an alkylene group or an alkylidine group is bonded to an arylene group or an arylidine group, such as an alkylene group, an alkylidine group, an arylidine group, an arylene group, an arylidine group, an alkylene group, or an alkylidine group. A group in which a group is bonded to an arylene group or an arylidine group is an oxygen atom, a nitrogen atom, a sulfur It may contain a hetero atom such as children.

The alkylidyne group means a trivalent group from which one hydrogen atom of an alkylene group has been eliminated, and the arylidine group means a trivalent group from which one hydrogen atom of an arylene group has been eliminated.

Specific examples of the above R ¹ include the following, but are not limited thereto.

[0022]

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[0023]

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[0024]

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[0025]

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The above formulas (1a), (1b) and (1
In c), R ² is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom or a methyl group, and R ³ has 1 to 8 carbon atoms, preferably 1 to 6 linear, branched or cyclic alkyl groups. m is an integer of 0 to 4, preferably 0 or 1. In addition, as a linear, branched or cyclic alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a cyclohexyl group, a cyclopentyl group and the like can be exemplified. .

The polymer compound of the present invention has the general formula (1)
a) In addition to the repeating unit represented by (1b) or (1c), the following general formulas (2a), (2b) and (2c)
And at least one of the repeating units represented by the following general formulas (3a), (3b) and (3c).

[0028]

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In the formula, R ² and R ³ have the same meaning as described above, and R ⁴ is an acid labile group. Further, m is an integer of 0 to 4, preferably 0 or 1, n is an integer of 1 to 5, preferably 1 or 2, and more preferably 1, and p is an integer of 1 to 5, preferably 1 or 2. , More preferably 1. However, m + n ≦ 5 and m + p ≦ 5.

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

[0031]

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In the formula, R ⁵ and R ⁶ are a hydrogen atom or a group having 1 to 1 carbon atoms.
8, preferably 1 to 6, more preferably 1 to 5, a linear, branched or cyclic alkyl group, and R ⁷ has 1 to 18 carbon atoms, preferably 1 to 10, more preferably 1 to 8 carbon atoms.
A monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom of R ⁵ and R ⁶ , R ⁵ and R ⁷ , R ⁶ and R ⁷ may form a ring, When a ring is formed, R ⁵ , R ⁶ , R
⁷ represents a linear or branched alkylene group having 1 to 18, preferably 1 to 10, and more preferably 1 to 8 carbon atoms. R ⁸ has 4 to 20, preferably 4 to 15, carbon atoms;
More preferably, a tertiary alkyl group having 4 to 10 carbon atoms, each alkyl group having 1 to 6 carbon atoms, preferably a trialkylsilyl group having 1 to 4 carbon atoms, and 4 to 20 carbon atoms, preferably 4 to 1 carbon atoms.
5, more preferably 4 to 10 oxoalkyl groups or-
And a group represented by CR ⁵ R ⁶ OR ⁷ . A is 0 to 6
Is an integer.

As the linear, branched or cyclic alkyl group having 1 to 8 carbon atoms for R ⁵ and R ⁶ , the same groups as described for R ² and R ³ can be mentioned.

R ⁷ is a linear, branched or cyclic alkyl group, phenyl group, p-methylphenyl group, p-methylphenyl group,
Unsubstituted or substituted aryl groups such as alkoxy-substituted phenyl groups such as ethylphenyl group and p-methoxyphenyl group; aralkyl groups such as benzyl group and phenethyl group; and those groups having an oxygen atom or bonded to a carbon atom Examples of such groups include an alkyl group represented by the following formula, in which a hydrogen atom is substituted by a hydroxyl group, or two hydrogen atoms are substituted by an oxygen atom to form a carbonyl group.

[0035]

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Examples of the tertiary alkyl group having 4 to 20 carbon atoms for R ⁸ include tert-butyl, 1-methylcyclohexyl, 2- (2-methyl) adamantyl, and te.
Examples thereof include an rt-amyl group, and groups represented by the following formulas (6) to (9).

[0037]

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Here, R ⁹ represents 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, an n-butyl group, Examples thereof include a sec-butyl group, an n-pentyl group, an n-hexyl group, a cyclopropyl group, and a cyclopropylmethyl group. R ¹⁰ represents a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms, specifically, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and an n-pentyl group. , N-hexyl group, cyclopropyl group, cyclopropylmethyl group and the like. R ¹¹ represents a hydrogen atom, a monovalent hydrocarbon group which may contain a heteroatom having 1 to 6 carbon atoms, or a monovalent hydrocarbon group which may be interposed via a heteroatom having 1 to 6 carbon atoms. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom.
-OR (R is an alkyl group, the same applies hereinafter), -O-, -S
-, - S (= O) -, - NH 2, -NHR, -NR 2, -
It can be contained or intervened as NH-, -NR-.

Examples of R ¹¹ include a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxy group and an alkoxyalkyl group.
These 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.

Each alkyl group of R ⁸ has 1 to 1 carbon atoms.
Examples of the trialkylsilyl group 6 include a trimethylsilyl group, a triethylsilyl group, and a dimethyl-tert-butylsilyl group. Examples of the oxoalkyl group having 4 to 20 carbon atoms of R ⁸ include a 3-oxoalkyl group, a group represented by the following formula, and the like.

[0041]

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Specific examples of the acid labile group represented by the above formula (4) include, for example, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxyethyl group, 1-n-butoxyethyl group, 1
-Isobutoxyethyl group, 1-sec-butoxyethyl group, 1-tert-butoxyethyl group, 1-tert-
An amyloxyethyl group, a 1-ethoxy-n-propyl group,
1-cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-
Examples thereof include a linear or branched acetal group such as an ethyl group and a 1-ethoxy-1-methyl-ethyl group, and a cyclic acetal group such as a tetrahydrofuranyl group and a tetrahydropyranyl group, and preferably an ethoxyethyl group and a butoxyethyl group. And ethoxypropyl groups. On the other hand, as the acid labile group of the above formula (5), for example, a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a tert-amyloxycarbonyl group, a tert-amyloxycarbonylmethyl group, a 1-ethoxyethoxycarbonylmethyl group , 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like. Further, a tertiary alkyl group having 4 to 20 carbon atoms as an acid labile group, a trialkylsilyl group having 1 to 6 carbon atoms each as an alkyl group, and an oxoalkyl group having 4 to 20 carbon atoms are each represented by R ⁸ . The same groups as described may be mentioned.

The polymer compound of the present invention has the R
Formula (1a) having a cross-linking group represented by ^1, (1b) or bridging unit (1c) and (A unit), the formula with an acid labile group represented by R ⁴ (2a), (2b) or ( 2c) an acid labile group-containing unit (B unit) and the above formulas (3a) and (3
It is preferable that the polymer is a polymer represented by the following formula (10), comprising a unit (C unit) represented by b) or (3c).

[0044]

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In this case, it is preferable that a, b, and c are positive numbers satisfying the following equations.

0 <a / (a + b + c) ≦ 0.5, preferably 0.01 ≦ a / (a + b + c) ≦ 0.5, more preferably 0.02 ≦ a / (a + b + c) ≦ 0.3 0 <b /(A+b+c)≦0.9, preferably 0.1 ≦ b / (a + b + c) ≦ 0.8, more preferably 0.2 ≦ b / (a + b + c) ≦ 0.70 <c / (a + b + c) ≦ 0 .98, preferably 0.2 ≦ c / (a + b + c) ≦ 0.96, more preferably 0.3 ≦ c / (a + b + c) ≦ 0.94

The polymer compound is an alkali-insoluble or sparingly soluble resin, which becomes alkali-soluble by the elimination of the acid labile group.

As described above, the polymer compound of the present invention
The ratio of the crosslinking unit (A unit) exceeds 0 mol% on average, and
Mol% or less, particularly preferably 0.2 to 20 mol%. When the content is 0 mol%, the dry etching resistance is reduced, and the advantages of the crosslinking group cannot be brought out. On the other hand, if it exceeds 50 mol%, it crosslinks too much and gels and loses its solubility in alkali, causes a change in film thickness, generation of stress in the film or generation of bubbles during alkali development, and adhesion to the substrate. May be inferior.

The ratio of the acid labile group-containing unit is more than 0 mol% on average and 90 mol% or less, preferably 10 to 50 mol%. At 0 mol%, the contrast of the alkali dissolution rate becomes small, and the resolution becomes poor. On the other hand, 9
If it exceeds 0 mol%, the solubility in alkali may be lost, or the affinity with a developing solution may be reduced during alkali development, resulting in poor resolution.

The polymer has a weight average molecular weight of preferably 1,000 to 500,000, more preferably 3,000 to 50,000. If the weight-average molecular weight is less than 1,000, the resist material becomes poor in heat resistance, and if it exceeds 500,000, alkali solubility may be reduced and resolution may be deteriorated.

As a method for producing the above-mentioned polymer, any one of the following formulas (1a ′) to (1c ′) is polymerized.
a ′) to (2c ′) and a monomer of any of the following formulas (3a ′) to (3c ′).

[0052]

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[0053]

Embedded image (R ¹ , R ² , R ³ , R ⁴ , m, n, and p have the same meaning 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.
Depending on the case, the polymerization reaction is carried out 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 chemically amplified resist material of the present invention uses the above polymer compound as a base resin, and contains (A) the above polymer compound, (B) an organic solvent, and (C) an acid generator. (D) a basic compound, (E) an aromatic compound having a group represented by ≡C-COOH in the molecule, (F) a base resin different from the component (A),
It may contain a dissolution inhibitor, (H) an ultraviolet absorber, and (I) an acetylene alcohol derivative.

The resist material of the present invention can be used in either a positive type or a negative type. Particularly, the resist material is effectively used as a chemically amplified type, and is particularly preferably used as a chemically amplified positive type.

Here, the organic solvent of the component (B) used in the present invention may be any organic solvent which can dissolve the acid generator, base resin, dissolution inhibitor and the like. Examples of such an organic solvent include ketones such as cyclohexanone, methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol,
Alcohols such as -methoxy-2-propanol and 1-ethoxy-2-propanol, and ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether and diethylene glycol dimethyl ether , Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3
Esters such as ethyl ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol-mono-tert-butyl ether acetate; one of these alone or as a mixture of two or more; However, the present invention is not limited to these. 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.

The acid generator of the component (C) includes 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.

[0059] _{^{(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.

[0061]

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 or halogenated aryl group having 6 to 12 carbon atoms, or a C ⁷ to C 12 12 represents an aralkyl group)

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.

[0063]

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 of 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-toluenesulfonate (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-dinitrop-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
The amount is preferably from 0.2 to 15 parts, more preferably from 0.5 to 8 parts with respect to the part. If the amount is less than 0.2 part, the amount of acid generated during exposure is small, and the sensitivity and the resolving power may be poor. If the amount exceeds 15 parts, the transmittance of the resist decreases, and the resolution may be poor.

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

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

Specifically, 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 (For example, quinoline, 3-quinolinecarbonitrile, etc.), 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 amide derivatives 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.

[0073]

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 to 20 carbon atoms.
-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, further preferably 1 to 8.

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

The basic compounds can be used alone or in combination of two or more. The compounding amount is 0.01 to 2 parts, preferably 0.01 to 2 parts, per 100 parts of the total base resin. ~ 1 part is preferred. If the amount is less than 0.01 part, the effect is not obtained, and if it exceeds 2 parts, the sensitivity may be too low.

Further, in the resist composition of the present invention, 分子 C—COOH, preferably —R ⁵⁷ —COOH (R ⁵⁷ is a linear or branched chain having 1 to 10 carbon atoms) is incorporated in the molecule blended as the component (E). As the aromatic compound having a group represented by the following formulae, for example, one or more compounds selected from the following groups I and II can be used, but is not limited thereto. . By blending the component (E), the PED stability of the resist can be improved, and the edge roughness on the nitride film substrate can be improved. [Group I] A part or all of the hydrogen atoms of the phenolic hydroxyl group of the compounds represented by the following general formulas (16) to (25) is-
R ⁵⁷ —COOH (R ⁵⁷ is a linear or branched alkylene group having 1 to 10 carbon atoms), and a phenolic hydroxyl group (C) in the molecule and a group represented by ≡C—COOH ( D) molar ratio with C / (C + D) = 0.1 to
A compound that is 1.0. [Group II] Compounds represented by the following general formulas (26) and (27).

[0081]

Embedded image

[0082]

Embedded image (Where R ² is a hydrogen atom or a methyl group,
R ⁵¹ and R ⁵² each represent a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms;
⁵³ is a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, or — (R ⁵⁷ ) _h —CO
An OR ′ group (R ′ is a hydrogen atom or —R ⁵⁷ —COOH); R ⁵⁴ is — (CH ₂ ) _i — (i = 2 to 10);
-10 arylene groups, carbonyl groups, sulfonyl groups,
An oxygen atom or a sulfur atom, R ⁵⁵ is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and R ⁵⁶ is a hydrogen atom or a carbon atom having 1 to 8 carbon atoms. A linear or branched alkyl group, an alkenyl group, a phenyl group or a naphthyl group each substituted with a hydroxyl group, R ⁵⁷ is a linear or branched alkylene group having 1 to 10 carbon atoms, and R ⁵⁸ is is a hydrogen atom or a linear or branched alkyl or alkenyl group, or -R ⁵⁷ -COOH group having 1 to 8 carbon atoms. j is an integer of 0 to 5, and u and h are 0 or 1. s1, t1, s
2, t2, s3, t3, s4, and t4 are respectively s1 + t
1 = 8, s2 + t2 = 5, s3 + t3 = 4, s4 + t4
= 6 and has at least one hydroxyl group in each phenyl skeleton. β is a number that makes the compound of the formula (21) have a weight average molecular weight of 1,000 to 5,000, and γ is a number that makes the compound of the formula (22) have a weight average molecular weight of 1,000.
This is a number from 0 to 10,000. )

[0083]

Embedded image (R ⁵¹ , R ⁵² and R ⁵⁷ have the same meanings as above.
t5 is a number that s5 ≧ 0 and t5 ≧ 0, and s5 + t5 = 5. )

Specific examples of the component (E) include, but are not limited to, compounds represented by the following general formulas III-1 to IV-14 and IV-1 to IV-6.

[0085]

Embedded image

[0086]

Embedded image (However, R ″ represents a hydrogen atom or a CH ₂ COOH group,
In each compound, 10 to 100 mol% of R ″ is CH ₂ C
OOH group. α and β have the same meaning as described above. )

[0087]

Embedded image

The aromatic compound having a group represented by ≡C—COOH in the molecule can be used alone or in combination of two or more.

The amount of the aromatic compound having a group represented by ≡C—COOH in the molecule is 0.1 to 5 parts, more preferably 1 to 3 parts, per 100 parts of the base resin. If the amount is less than 0.1 part, the footing on the nitride film substrate and the effect of improving the PED may not be sufficiently obtained, and if the amount is more than 5 parts, the resolution of the resist material may decrease.

As the base resin other than the crosslinked polymer compound related to the component (A) of the component (F), particularly, the weight average molecular weight having a repeating unit represented by the following general formula is from 3,000 to 3,000. 300,000 high molecular compounds are preferably used.

Further, by blending the component (F), the dimension of the pattern and the shape of the pattern can be arbitrarily controlled, which is advantageous.

[0092]

Embedded image

In the above formula, R ² , R ³ , R ⁵ , R ⁶ , R
⁷ has the same meaning as described above, and R ¹² is an acid labile group different from the above formula (4), for example, a group represented by the above formula (5), a tertiary alkyl group having 4 to 20 carbon atoms, 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.

E and f are each 0 or a positive number.
f may be 0 at the same time, g is a positive number, and e +
f + g = 1. These composition ratios are 0 ≦ e / (e + f
+ G) ≦ 0.5, preferably 0.1 ≦ e / (e + f +
g) ≦ 0.4, 0 ≦ f / (e + f + g) ≦ 0.5, preferably 0 ≦ f / (e + f + g) ≦ 0.2, 0.4 ≦ g /
(E + f + g) ≦ 0.9, preferably 0.6 ≦ g / (e
+ F + g) ≦ 0.8. The ratio of e to the whole (e + f + g, the same applies hereinafter) exceeds 0.5, the ratio of f to the whole exceeds 0.5, and the ratio of g to the whole is 0.9
Or the ratio of g to the whole is less than 0.4, the contrast of the alkali dissolution rate becomes small and the resolution may be deteriorated. By appropriately selecting the values of e, f, and g within the above range, the dimension of the pattern and the shape of the pattern can be arbitrarily controlled.

Such a high molecular compound has a weight average molecular weight of 3,000 to 300,000, preferably 5,000.
It must be between 0 and 30,000. If the weight average molecular weight is less than 3,000, the resist material will have poor heat resistance. If it exceeds 300,000, the alkali solubility will be reduced and the resolution will be poor.

Further, in the base resin of the component (F), when the molecular weight distribution (Mw / Mn) is wide, a low molecular weight or high molecular weight polymer is present, and when a large amount of low molecular weight polymer is present, heat resistance is low. In some cases, when a high-molecular-weight polymer is present in a large amount, it may be difficult to dissolve in alkali, and may cause tailing after pattern formation. Therefore, as the pattern rule becomes finer, the influence of such molecular weight and molecular weight distribution tends to increase. Therefore, in order to obtain a resist material suitably used for fine pattern dimensions, the molecular weight distribution of the base resin must be as follows. 0
It is preferably a narrow dispersion of 2.5 to 2.5, particularly 1.0 to 1.5.

The compounding ratio of the base resin (F) to the base resin (crosslinked high molecular compound) of the component (A) is preferably 0: 100 to 90:10 by weight. In particular, 0: 100 to 50:50 is preferable. If the amount of the base resin (F) is greater than the above weight ratio, the desired effect of the base resin (crosslinked polymer compound) of the component (A) may not be obtained.

The resist composition of the present invention may further comprise a dissolution inhibitor as a component (G), thereby improving the contrast. As the dissolution inhibitor, a compound having an average molecular weight of 100 to 1,000, preferably 150 to 800, and having two or more phenolic hydroxyl groups in the molecule is obtained by converting the hydrogen atom of the phenolic hydroxyl group into an acid labile group. 0-100 mol% on average
The substituted compound is blended at the ratio of

The substitution rate of the hydrogen atom of the phenolic hydroxyl group by the acid labile group is 0 mol% or more, preferably 30 mol% or more, of the total phenolic hydroxyl group on average.
The upper limit is 100 mol%, more preferably 80 mol%.

In this case, the phenolic hydroxyl group is 2
Compounds having one or more of the following formulas (i) to (xi)
Are preferred.

[0101]

Embedded image

[0102]

Embedded image

[0103]

Embedded image (Wherein, R ²¹ and R ²² each represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, and R ²³ represents a hydrogen atom or a linear chain having 1 to 8 carbon atoms. Or branched alkyl or alkenyl group, or-
(R ²⁷ ) _h —COOH, and R ²⁴ is — (CH ₂ ) _i —
(I = 2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, R
²⁵ is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and R ²⁶ is a hydrogen atom or a linear or branched chain having 1 to 8 carbon atoms. An alkyl group, an alkenyl group, a phenyl group or a naphthyl group each substituted with a hydroxyl group,
²⁷ is a linear or branched alkylene group having 1 to 10 carbon atoms. J is an integer of 0 to 5, and u and h are 0 or 1. s, t, s ′, t ′, s ″, and t ″ satisfy s + t = 8, s ′ + t ′ = 5, s ″ + t ″ = 4, respectively, and have at least one hydroxyl group in each phenyl skeleton. Such a number. α is the equation (viii), (ix)
Is a number with a molecular weight of 100 to 1,000. )

In the above formula, R ²¹ and R ²² include, for example, hydrogen atom, methyl group, ethyl group, butyl group, propyl group, ethynyl group, cyclohexyl group, and R ²³ include, for example, R
²¹ and R ²² , or -COOH, -CH ₂
COOH and R ²⁴ include, for example, an ethylene group, a phenylene group, a carbonyl group, a sulfonyl group, an oxygen atom and a sulfur atom, and R ²⁵ includes, for example, a methylene group or R ²⁴
Materials similar to those in, for example hydrogen atom R ^26, a methyl group, an ethyl group, butyl group, propyl group, an ethynyl group, a cyclohexyl group, each phenyl group substituted with a hydroxyl group, a naphthyl group and the like.

Here, as the acid labile group of the dissolution inhibitor, groups represented by the above general formulas (5) and (6), tertiary alkyl groups having 4 to 20 carbon atoms, and each alkyl group can be used. Trialkylsilyl group having 1 to 6 carbon atoms, 4 to 2 carbon atoms
And an oxoalkyl group of 0.

The compound (dissolution inhibitor) in which the phenolic hydroxyl group is partially substituted with an acid labile group is 0 to 50 parts, preferably 5 to 50 parts, per 100 parts of the base resin.
Parts, more preferably 10 to 30 parts, and they can be used alone or in combination of two or more. If the amount is less than 5 parts, the resolution may not be improved. If the amount is more than 50 parts, the pattern may be reduced in film thickness and the resolution may be reduced.

The dissolution inhibitor as described above can be synthesized by chemically reacting a compound having a phenolic hydroxyl group with an acid labile group as in the case of the base resin.

The resist composition of the present invention may have a weight average molecular weight of more than 1,000 and 3,000 or less as a dissolution inhibitor instead of or in addition to the above dissolution inhibitor, and a phenolic hydroxyl group in the molecule. And a compound in which the hydrogen atom of the phenolic hydroxyl group is partially substituted by an acid labile group at an average rate of 0% or more and 60% or less as a whole.

In this case, the compound in which the hydrogen atom of the phenolic hydroxyl group is partially substituted with such an acid labile group includes:
One or more compounds selected from compounds having a repeating unit represented by the following general formula (28) and having a weight average molecular weight of more than 1,000 and not more than 3,000 are preferred.

[0110]

Embedded image (Where R ⁴ represents an acid labile group, and v and w are numbers satisfying 0 ≦ v / (v + w) ≦ 0.6, respectively)

Here, as the acid labile group of the dissolution inhibitor, groups represented by the above general formulas (4) and (5), tertiary alkyl groups having 4 to 20 carbon atoms, and each alkyl group can be used. Trialkylsilyl group having 1 to 6 carbon atoms, 4 to 2 carbon atoms
And an oxoalkyl group of 0.

The mixing amount of the another dissolution inhibitor is such that the dissolution inhibitor combined with the dissolution inhibitor as a whole dissolves in the base resin 10.
0 to 50 parts, especially 0 to 30 parts, preferably 1 to 0 parts
It is preferable that the amount be in a range such that at least one part is used.

The other dissolution inhibitor as described above can be synthesized by chemically reacting a compound having a phenolic hydroxyl group with an acid labile group as in the case of the base resin.

The resist composition of the present invention further comprises (H)
A compound having a molar absorbance at a wavelength of 248 nm of 10,000 or less can be blended as a component ultraviolet absorber. This makes it possible to design and control a resist having an appropriate transmittance for substrates having different reflectivities.

Specifically, pentalene, indene, naphthalene, azulene, peptalene, biphenylene, indacene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, acephenanthrylene, aceanthrylene, triphenylene, pyrene, chrysene,
Naphthalene, preiaden, picene, perylene, pentaphen, pentacene, benzophenanthrene, anthraquinone, anthrone benzanthrone, 2,7-dimethoxynaphthalene, 2-ethyl-9,10-dimethoxyanthoselan, 9,10-dimethylanthracene, 9- Ethoxyanthracene, 1,2-naphthoquinone, 9-fluorene, condensed polycyclic hydrocarbon derivatives such as the following general formulas (29) and (30), condensed heterocyclic derivatives such as thioxanthen-9-one, thianthrene and dibenzothiophene; 2,
3,4-tribitroxybenzophenone, 2,3,4
4′-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 3,5-dihydroxybenzophenone, 4,4′-dihydroxybenzophenone,
Benzophenone derivatives such as 4,4'-bis (dimethylamino) benzophenone; squaric acid derivatives such as squaric acid and dimethyl squarate;

[0116]

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

More specifically, the above formulas (29) and (30)
Wherein R ^{61 to} R ⁶³ each independently represent a hydrogen atom, a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched alkoxyalkyl group, a linear or branched Linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, ter
Those having 1 to 10 carbon atoms such as a t-butyl group, a hexyl group, a cyclohexyl group and an adamantyl group are preferred, and among them, a methyl group, an ethyl group, an isopropyl group and a tert-butyl group are more preferably used. Examples of the linear or branched alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, hexyloxy, and cyclohexyloxy. Those having formulas 1 to 8 are preferred, and among them, methoxy, ethoxy, isopropoxy and tert-butoxy groups are more preferably used. Examples of the linear or branched alkoxyalkyl group include those having 2 to 10 carbon atoms such as a methoxymethyl group, a 1-ethoxyethyl group, a 1-ethoxypropyl group, a 1-propoxyethyl group, and a tert-butoxyethyl group. Are preferable, and among them, a methoxymethyl group, a 1-ethoxyethyl group, a 1-ethoxypropyl group, a 1-propoxyethyl group and the like are preferable. As the linear or branched alkenyl group, those having 2 to 4 carbon atoms such as a vinyl group, a propenyl group, an allyl group and a butenyl group are preferred. As the aryl group, those having 6 to 14 carbon atoms such as a phenyl group, a xylyl group, a toluyl group, and a cumenyl group are preferable.

R ⁶⁴ is a substituted or unsubstituted divalent aliphatic hydrocarbon group which may contain an oxygen atom, or a substituted or unsubstituted divalent alicyclic hydrocarbon group which may contain an oxygen atom. A substituted or unsubstituted divalent aromatic hydrocarbon group or an oxygen atom which may contain an oxygen atom. In the formula, J is 0 or 1, and when J is 0, -R ⁶⁴
The bond is a single bond;

Examples of the substituted or unsubstituted divalent aliphatic hydrocarbon group which may contain an oxygen atom include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group and a sec- Butylene group, -CH ₂
O- group, -CH ₂ CH ₂ O- group, -CH ₂ OCH ₂ - is preferred has 1 to 10 carbon atoms, such as radicals, among them methylene group, an ethylene group, -CH ₂ O- group, - CH ₂ CH ₂ O-
Groups are more preferably used.

Examples of the substituted or unsubstituted divalent alicyclic hydrocarbon group which may contain an oxygen atom include, for example,
4-cyclohexylene group, 2-oxacyclohexane-
1,4-ylene group, 2-thiacyclohexane-1,4-
Examples thereof include those having 5 to 10 carbon atoms such as an ylene group.

The substituted or unsubstituted divalent aromatic hydrocarbon group which may contain an oxygen atom includes, for example, o-
Phenylene group, p-phenylene group, 1,2-xylene-
3,6-ylene group, toluene-2,5-ylene group, 1-
Those having 6 to 14 carbon atoms, such as cumene-2,5-ylene group, or -CH ₂ Ph- group, -CH ₂ PhCH ₂ -
Groups, -OCH ₂ Ph- group, -OCH ₂ PhCH ₂ O- group (Ph is a phenylene group) allyl alkylene group having 6 to 14 carbon atoms such as.

R ⁶⁵ is an acid labile group, and the acid labile group referred to herein means a group obtained by substituting a carboxyl group with one or more functional groups capable of decomposing in the presence of an acid. It is not particularly limited as long as it decomposes in the presence of an acid to release a functional group exhibiting alkali solubility. In particular, groups represented by the following general formulas (31a), (31b), and (31c) are preferred. preferable.

[0123]

Embedded image (Wherein, R ^{66 to} R ⁶⁹ each independently represent a hydrogen atom, a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched alkoxyalkyl group, Alternatively, it is a branched alkenyl group or an aryl group, and these groups may contain a carbonyl group in the chain, but all of R ^{66 to} R ⁶⁹ must not be hydrogen atoms. ⁶⁶ and R ⁶⁷ may be bonded to each other to form a ring, and R ⁶⁹ is a linear or branched alkyl group, a linear or branched alkoxyalkyl group, a linear or branched alkenyl A group or an aryl group, and these groups may contain a carbonyl group in the chain, and R ⁶⁹ may combine with R ⁶⁶ to form a ring.)

In this case, the above-mentioned linear or branched alkyl group, linear or branched alkoxy group, linear or branched alkoxyalkyl group, linear or branched alkenyl group, aryl group Examples thereof include the same as those described above for R ^{61 to} R ⁶³ .

In the formula (31a), the ring formed by bonding R ⁶⁶ and R ⁶⁷ to each other includes, for example, cyclohexylidene, cyclopentylidene, 3-oxocyclohexylidene, 3-oxo- Examples thereof include those having 4 to 10 carbon atoms such as a 4-oxacyclohexylidene group and a 4-methylcyclohexylidene group.

In the formula (31b), examples of the ring formed by combining R ⁶⁶ and R ⁶⁷ with each other include 1-silacyclohexylidene group, 1-silacyclopentylidene group and 3-oxo-1- Silacyclopentylidene group, 4-
C3-C3 such as methyl-1-silacyclopentylidene group
9 are mentioned.

In the formula (31c), examples of the ring formed by bonding R ⁶⁹ and R ⁶⁶ to each other include, for example, a 2-oxacyclohexylidene group, a 2-oxacyclopentylidene group, a 2-oxa-4- Those having 4 to 10 carbon atoms such as a methylcyclohexylidene group are exemplified.

Here, as the group represented by the above formula (31a), for example, tert-amyl group, 1,1-dimethylethyl group, 1,1-dimethylbutyl group, 1-ethyl-
In addition to tertiary alkyl groups having 4 to 10 carbon atoms such as 1-methylpropyl group and 1,1-diethylpropyl group, 1,1-dimethyl-3-oxobutyl group, 3-oxocyclohexyl group, 1-methyl-3 A 3-oxoalkyl group such as -oxo-4-oxacyclohexyl group is preferred.

The group represented by the above formula (31b) includes, for example, trimethylsilyl, ethyldimethylsilyl, dimethylpropylsilyl, diethylmethylsilyl, triethylsilyl, tert-butyldimethylsilyl, etc. Ten trialkylsilyl groups are preferred.

Examples of the group represented by the above formula (31c) include 1-methoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-ethoxypropyl group,
1-ethoxyisobutyl group, 1-n-propoxyethyl group, 1-tert-butoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert
-Pentoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2′-n-butoxyethoxy) ethyl group,
1- (2-ethylhexyloxy) ethyl group, 1- {4
-(Acetoxymethyl) cyclohexylmethyloxy}
Ethyl group, 1- {4- (tert-butoxycarbonyloxymethyl) cyclohexylmethyloxy} ethyl group, 1-methoxy-1-methylethyl group, 1-ethoxypropyl group, dimethoxymethyl group, diethoxymethyl group, 2- Those having 2 to 8 carbon atoms, such as a tetrahydrofuranyl group and a 2-tetrahydropyranyl group, are preferred.

In the above formulas (29) and (30), E, F and G are each 0 or a positive integer of 1 to 9;
Is a positive integer of 1 to 10 and satisfies E + F + G + H ≦ 10.

Preferred specific examples of the compounds of the above formulas (29) and (30) include compounds represented by the following (32a) to (32j).

[0133]

Embedded image

[0134]

Embedded image (In the formula, R ⁷⁰ is an acid labile group.)

As the ultraviolet absorber, bis (4-
Hydroxyphenyl) sulfoxide, bis (4-ter
t-butoxyphenyl) sulfoxide, bis (4-te
diarylsulfoxide derivatives such as rt-butoxycarbonyloxyphenyl) sulfoxide, bis [4- (1-ethoxyethoxy) phenyl] sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-te
rt-butoxyphenyl) sulfone, bis (4-ter
t-butoxycarbonyloxyphenyl) sulfone, bis [4- (1-ethoxyethoxy) phenyl] sulfone, bis [4- (1-ethoxypropoxy) phenyl]
Diarylsulfone derivatives such as sulfone, benzoquinonediazide, naphthoquinonediazide, anthraquinonediazide, diazo compounds such as diazofluorene, diazotetralone and diazophenanthrone, naphthoquinone-1,2
-Complete or partial ester compound of diazide-5-sulfonic acid chloride and 2,3,4-trihydroxybenzophenone, naphthoquinone-1,2-diazide-4-sulfonic acid chloride and 2,4,4'-trihydroxybenzophenone And quinonediazide group-containing compounds such as complete or partial ester compounds.

Preferred as the ultraviolet absorber are tert-butyl 9-anthracenecarboxylate, tert-amyl 9-anthracenecarboxylate, tert-methoxymethyl 9-anthracenecarboxylate, tert-ethoxyethyl 9-anthracenecarboxylate, Tert-tetrahydropyranyl anthracenecarboxylate, tert-tetrahydrofuranyl 9-anthracenecarboxylate,
A partial ester compound of naphthoquinone-1,2-diazide-5-sulfonic acid chloride and 2,3,4-trihydroxybenzophenone can be exemplified.

The compounding amount of the ultraviolet absorber (H) is preferably 0 to 10 parts, more preferably 0.5 to 10 parts, and still more preferably 1 to 5 parts with respect to 100 parts of the base resin. preferable.

Further, the resist material of the present invention includes (I)
An acetylene alcohol derivative can be blended as a component, which can improve the storage stability.

As the acetylene alcohol derivative, those represented by the following formulas (33) and (34) can be suitably used.

[0140]

Embedded image (Wherein, R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , and R ⁷⁵ are each a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, and X and Y are 0 or Indicates a positive number and satisfies the following values: 0 ≦ X ≦ 30, 0 ≦ Y ≦ 30, 0 ≦ X + Y ≦
40. )

As acetylene alcohol derivatives, Surfynol 61, Surfynol 82, Surfynol 104, Surfynol 104E, Surfynol 104H, Surfynol 104A, Surfynol TG, Surfynol PC, Surfynol 44 are preferred.
0, Surfynol 465, Surfynol 485 (A
ir Products and Chemicals
Inc. Olfin E1004 (manufactured by Nissin Chemical Industry Co., Ltd.).

The acetylene alcohol derivative is added in an amount of 0.01 to 2% by weight, more preferably 0.02 to 1% by weight, based on 100% by weight of the resist composition. 0.0
If the amount is less than 1% by weight, the effect of improving coating properties and storage stability may not be sufficiently obtained, and if the amount is more than 2% by weight, the resolution of the resist material may decrease.

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

The surfactant is preferably a nonionic surfactant, and examples thereof include perfluoroalkylpolyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, and fluorine-containing organosiloxane compounds. For example, Florard "F
C-430 "," FC-431 "(all manufactured by Sumitomo 3M Limited), Surflon" S-141 "," S-1 "
45, S-381, S-383 (all manufactured by Asahi Glass Co., Ltd.), Unidyne DS-401, DS
-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), MegaFac" F-8151 "," F-1
71 "," F-172 "," F-173 "," F-17 "
7 (manufactured by Dainippon Ink Industries, Ltd.), “X-70-09”
2 "," X-70-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Preferably, Florado “FC-430” (manufactured by Sumitomo 3M Limited),
"X-70-093" (manufactured by Shin-Etsu Chemical Co., Ltd.).

A pattern can be formed using the resist material of the present invention by employing a known lithography technique. For example, a film having a thickness of 0 is formed on a substrate such as a silicon wafer by a method such as spin coating. 0.5-2.0μ
m on a hot plate.
１５０150 ° C., 1〜１０10 minutes, preferably 80〜120
Pre-bake at 1 ° C for 1-5 minutes. Next, a mask for forming a target pattern is held over the above resist film, and a high energy ray such as a deep ultraviolet ray having a wavelength of 300 nm or less, an excimer laser, an X-ray or the like or an electron beam is exposed at a dose of 1
About 200 mJ / cm ² , preferably 10 to 100 m
After irradiating to about J / cm ² , on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably 80 to 150 ° C.
Post-exposure bake at 120 ° C for 1 to 3 minutes (P
EB). Further, 0.1-5%, preferably 2-3%
Tetramethylammonium hydroxide (TMA
H) using a developing solution of an aqueous alkali solution for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, by a conventional method such as a dip method, a paddle method, or a spray method. By developing, a target pattern is formed on the substrate. The material of the present invention is particularly suitable for fine patterning using 254 to 193 nm far ultraviolet rays or excimer lasers, X-rays and electron beams among high energy rays. Further, when the above range is out of the upper limit and the lower limit, a desired pattern may not be obtained.

[0146]

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. Further, the pattern is unlikely to be overhanging, and has excellent dimensional controllability. Further, the storage stability is improved by blending the acetylene alcohol derivative. Therefore, the resist material of the present invention can be a resist material having a small absorption at the exposure wavelength of the KrF excimer laser due to these characteristics, and can easily form a fine and perpendicular pattern to the substrate. Super LSI
It is suitable as a fine pattern forming material for manufacturing.

[0147]

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] The monomer components shown in Table 1 were charged into a 2 L flask, and 1.5 L of THF was added as a solvent. The reaction vessel was cooled to -70 ° C under a nitrogen atmosphere, and degassing under reduced pressure and nitrogen flow were repeated three times. After the temperature was raised to room temperature, 13.1 g of AIBN was added as a polymerization initiator,
After the temperature was raised to 60 ° C., the reaction was carried out for 15 hours. The reaction solution was concentrated to １ ／, precipitated in 10 L of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain a white polymer 12
0 g was obtained. The obtained polymer was subjected to ¹³ C-NMR, ¹ H-N
The following analysis results were obtained by measuring MR and GPC.

[0149]

[Table 1]

[0150]

Embedded image

[0151]

Embedded image

[0152]

Embedded image

[0153]

Embedded image

[0154]

Embedded image

[Examples and Comparative Examples] The above Polymer 1
-8, the acid generators represented by the following PAGs 1-4, and the dissolution inhibitors represented by the following DRIs 1 and 2 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) having a weight 6 times the solid content, A resist composition was prepared, and each composition was filtered through a 0.2 μm Teflon filter to prepare a resist solution.

[0156]

Embedded image

[0157]

Embedded image

Next, the obtained resist solution was formed into a film of DUV-30 (manufactured by Nissan Chemical Industries, Ltd.) with a thickness of 55 nm on a silicon wafer, and the reflectance was suppressed to 1% or less with KrF light (248 nm). The resist was spin-coated on the substrate and baked at 100 ° C. for 90 seconds using a hot plate to make the resist thickness 550 nm.

This was exposed using an excimer laser stepper (Nikon Corporation, NSR-2005EX8A, NA-0.5). Immediately after the exposure, the film was baked at 110 ° C. for 90 seconds, and 2.38% tetramethylammonium hydroxide was added. Development was carried out with the aqueous solution for 60 seconds to obtain a positive pattern.

The obtained resist pattern was evaluated as follows. The results are shown in Tables 2 and 3. Evaluation method: 0.30 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 resist was spin-coated was evaluated under two conditions. (1) Etching test with CHF ₃ / CF ₄ system gas Dry etching equipment TE-85 manufactured by Tokyo Electron Limited
Using 00P, the difference in the thickness of the resist before and after etching was determined.

The etching conditions are as shown below. Chamber pressure 300 mmTorr RF power 1300 W Gap 9 mm CHF ₃ gas flow rate 30 sccm CF ₄ gas flow rate 30 sccm Ar gas flow rate 100 sccm Time 60 sec (2) Etching test with Cl ₂ / BCl ₃ system gas Dry etching apparatus L-50 manufactured by Nidec Anelva Co., Ltd.
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 300MmTorr RF power 300W Giyappu 9 mm Cl ₂ gas flow rate 30 sccm BCl ₃ gas flow rate 30 sccm CHF ₃ gas flow rate 100 sccm O ₂ gas flow rate 2sccm time 360sec

[0163]

[Table 2]

[0164]

[Table 3]

From the results shown in Tables 2 and 3, the resist material using the polymer compound of the present invention satisfies sufficient resolution and sensitivity, and has excellent dry etching resistance due to the small difference in film thickness after etching. It was found to have.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 246/00 C08F 246/00 G03F 7/039 601 G03F 7/039 601 (72) Inventor Takanobu Takeda Niigata 28-1 Nishifukushima, Kushiro-mura, Nakakukujo-gun, Japan Shin-Etsu Chemical Industry Co., Ltd.Synthetic Technology Research Laboratory (72) Inventor Jun Watanabe 28-1, Nishi-Fukushima, Oku-ku, Nakakushiro-gun, Niigata Pref. 72) Inventor Yoichi Osawa 28-1 Nishifukushima, Nippon-mura, Nakakushijo-gun, Niigata Prefecture Inside the Synthetic Technology Research Laboratory, Shin-Etsu Chemical Co., Ltd. F-term (reference) in Synthetic Technology Laboratory, Industrial Co., Ltd. 2H025 AA09 AB16 AC04 AC06 AC08 BE00 CB14 CB17 CB55 CC03 CC20 FA01 FA12

Claims (6)

[Claims] The following general formulas (1a), (1b) and (1)
A polymer compound crosslinked intramolecularly or intermolecularly, having any of the repeating units represented by c). Embedded image (Wherein, R ¹ is an oxygen atom, a nitrogen atom, a sulfur atom, a linear, branched or cyclic unsubstituted or aryl-substituted alkylene or alkylidene group having 1 to 20 carbon atoms, An unsubstituted or alkyl group-substituted arylene group or arylidine group, or a divalent or trivalent group in which an alkylene group or an alkylidine group is bonded to an arylene group or an arylidine group, the alkylene group, an alkylidine group, an arylene group, The divalent or trivalent group in which the arylidine group and the alkylene group or the alkylidine group are bonded to the arylene group or the arylidine group may include a heteroatom, wherein R ² is a hydrogen atom or a carbon atom having 1 to 10 carbon atoms.
Is a linear, branched or cyclic alkyl group. R
³ is a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. m is an integer of 0-4. ) 2. The general formulas (1a), (1b), and (1)
An intramolecular or intermolecular crosslinked polymer compound having any of the repeating units represented by c) further comprises any of the repeating units represented by the following general formulas (2a), (2b) and (2c) , The following general formulas (3a), (3b), (3
The polymer compound according to claim 1, which has any of the repeating units represented by c), and has a weight average molecular weight of 1,000 to 500,000. Embedded image (Wherein, R ² and R ³ have the same meanings as above, and R ⁴ is an acid labile group. M is an integer of 0 to 4, n is an integer of 1 to 5, p is 1 to 5) It is an integer, but m + n ≦ 5, m + p ≦
5 ) 3. A chemically amplified resist material comprising: (A) the polymer compound according to claim 1 or 2; (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 chemically amplified resist material according to any one of claims 3, 4, and 5 onto a substrate; and (2) subsequently applying a wavelength through a photomask after a heat treatment. A pattern forming method comprising: a step of exposing with a high energy beam or an electron beam of 300 nm or less; and (3) a step of performing a heat treatment as necessary and then developing with a developing solution.