JP2001146505A - Polymer compound, chemically amplified resist material and method for forming pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resist material which absorbs only a small amount of light particularly in an F2 excimer laser exposure wavelength and which is suitable for simple and easy formation of a fine pattern that is perpendicular to a substrate surface and thus is suitable for forming a fine pattern for an ultra-large scale integrated circuit. SOLUTION: This polymer has a repeating unit represented by general formula (1) (wherein R1 is H, IC or a 1-20C straight-chain, branched or cyclic alkyl group, a fluorinated alkyl group or a chlorinated alkyl group; R2 is an acid- unstable group; (o), (p), (q), (r), (s) and (t) satisfy each the relationships of 0<=o<5, 0<p<=5, 0<=q<5, 0<r<=5, 0<=s<=5, 0<=t<=5, 0<=o+q<5, 0<s+t<=5, 0<o+p+q<=5 and 0<o+q+r<=5; and (k), (m) and (n) satisfy each the relationships of 0<k<1, 0<=m<1, 0<=nL<1, and k+m+n=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. Shortening of the wavelength from KrF to ArF (193 nm) is expected to reduce the design rule to 0.13 μm or less. However, conventionally used novolak and polyvinylphenol-based resins have been reduced to around 193 nm. Since it has very strong absorption, it cannot be used as a base resin for resist. From such a point, acrylic and cycloolefin-based alicyclic resins have been studied in order to ensure transparency and required dry etching resistance (JP-A-9-73173, JP-A-10-10739).
No., JP-A-9-230595, WO97 / 33198
However, as for F ₂ (157 nm), which can be expected to have a fineness of 0.10 μm or less, it becomes more and more difficult to secure transparency, and acrylic does not transmit light at all and cycloolefin does not. Those having a carbonyl bond were found to have strong absorption.

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

[0005]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a fluorinated fluorinated compound containing a repeating unit represented by the following general formula (1) is obtained. It has been found that by using a resin based on polyvinyl phenol, a resist material having high transparency and alkali solubility can be obtained.

[0006]

Embedded image (Wherein, R ¹ is a hydrogen atom, a chlorine atom or a C 1-20
Is a linear, branched or cyclic alkyl group, a fluorinated alkyl group or a chlorinated alkyl group.
R ² is an acid labile group, and o, p, q, r, s, t are
0 ≦ o <5, 0 <p ≦ 5, 0 ≦ q <5, 0 <r ≦ 5, 0
≦ s ≦ 5, 0 ≦ t ≦ 5, and 0 ≦ o + q <
5, 0 <s + t ≦ 5, 0 <o + p + q ≦ 5, 0 <o + q
+ R ≦ 5, and k, m, and n are 0 <k <
1, 0 ≦ m <1, 0 ≦ n <1, and k + m + n =
It is a number that satisfies 1. )

According to the study by the present inventors, polyvinyl phenol has an absorption window at around 160 nm and the transmittance is slightly improved, but it is far from a practical level, and the double bond between carbonyl and carbon-carbon is high. Has been found to be a necessary condition for ensuring transmittance. However, phenol shows excellent properties in etching resistance, alkali solubility and adhesion to substrates, and furthermore, halogen-substituted, especially fluorine-substituted, phenol exhibits improved transmittance by enlarging the window. It has been found that there is an effect and a practically close transmittance can be obtained.

Accordingly, the present invention provides the following polymer compound, a chemically amplified resist material, and a pattern forming method. Claim 1: A polymer compound containing a repeating unit represented by the general formula (1). In a preferred embodiment, the resist material comprises a polymer compound represented by the general formula (1). Claim 3: (A) the polymer compound according to claim 1, (B) an organic solvent,
(C) A chemically amplified positive resist material comprising an acid generator. Claim 4: (A) the polymer compound according to claim 1, (B) an organic solvent,
A chemically amplified negative resist composition comprising (C) an acid generator and (D) a crosslinking agent. Claim 5: The resist material according to claim 3 or 4, further comprising a basic compound. Claim 6: Claim 3 or 5 further containing a dissolution inhibitor
The resist material as described. Claim 7: (1) a step of applying the resist material according to any one of claims 2 to 6 on a substrate, and (2) a high energy having a wavelength of 300 nm or less via a photomask after a heat treatment. A pattern forming method, comprising: a step of exposing to light or an electron beam; and (3) a step of performing 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 a repeating unit represented by the following general formula (1).

[0010]

Embedded image

Here, R ¹ is a hydrogen atom, a chlorine atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated or chlorinated alkyl group.

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

R ² is an acid labile group, and various groups are selected as the acid labile group.
A group represented by (3), a carbon number 4 represented by the following formula (4)
It is preferably a tertiary alkyl group having from 40 to 40, a trialkylsilyl group having from 1 to 6 carbon atoms, an oxoalkyl group having from 4 to 20 carbon atoms, or the like.

[0014]

Embedded image

In the formula (2), R ⁶ has 4 to 2 carbon atoms.
0, preferably a tertiary alkyl group having 4 to 15 carbon atoms, 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 (3)
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 (3), 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.

[0017]

Embedded image

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

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

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

[0021]

Embedded image

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

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

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

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

[0026]

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, alkoxyalkyl groups, alkoxy groups or alkoxyalkyl groups, and the like, which may be any of linear, branched and cyclic. Specifically, methyl, hydroxymethyl, ethyl, hydroxyethyl, propyl, isopropyl, n-butyl, s
ec-butyl group, n-pentyl group, n-hexyl group, methoxy group, 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 ² has 1 to 6 carbon atoms include a trimethylsilyl group, a triethylsilyl group, and a tert-butyldimethylsilyl group.

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

[0031]

Embedded image

In the equation (1), 0 ≦ o <5,0
<P ≦ 5, 0 ≦ q <5, 0 <r ≦ 5, 0 ≦ s ≦ 5, 0 ≦
t ≦ 5, 0 ≦ o + q <5, 0 <s + t ≦
5, 0 <o + p + q ≦ 5, 0 <o + q + r ≦ 5.

K, m, and n are 0 <k <1, 0 ≦ m <1,
0 ≦ n <1 and k + m + n = 1, but 0.1 ≦
k ≦ 0.9, especially 0.2 ≦ k ≦ 0.8, and 0.1 ≦
n ≦ 0.9, in particular 0.2 ≦ n ≦ 0.8, and
It is preferable that 3 ≦ k + n ≦ 1, especially 0.4 ≦ k + n ≦ 1.

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

When producing the above polymer compound, a monomer represented by the following general formula (1a) can be used.

[0036]

Embedded image ^{(Wherein, R 1, o, q,} r are as defined above .R ^o
Represents a phenol protecting group. )

As R ^o , a methyl group, a vinyl group, an allyl group, a benzyl group, and the following general formula (i):
The groups represented by (ii), (iii), (iv) and (v) can be exemplified.

[0038]

Embedded image

In the formula, Ra represents ^a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ^b, R ^c are each a hydrogen atom or a straight, branched or cyclic alkyl group that may contain a hetero atom, R ^d
Is an alkyl group, an aryl group, an aralkyl group or an oxoalkyl group which may contain a linear, branched or cyclic hetero atom having 1 to 20 carbon atoms, and R ^b and R ^c , R ^b and R ^d , R ^c and ^Rd may combine with each other to form a cyclic structure having 3 to 12 carbon atoms. R ^e, R ^f, R ^g are each a straight, include a branched or cyclic heteroatoms also an alkyl group, an aryl group, an aralkyl group or an oxoalkyl group, R ^e and R ^f , ^Re and ^Rg ,
R ^f and R ^g may combine with each other to form a cyclic structure having 3 to 12 carbon atoms. R ^h , R ⁱ , and R ^j each have 1 carbon atom
And represents a straight-chain or branched alkyl group. R ^k
Represents an alkyl group, an aryl group, an aralkyl group or an oxoalkyl group which may contain a linear, branched or cyclic heteroatom having 1 to 20 carbon atoms, and z is an integer of 0 to 10.

As a method for producing the above monomer, a method is generally used in which a benzene derivative represented by the following general formula (vi) and a vinyl derivative represented by the following general formula (vii) are obtained by cross-coupling. is there.

Embedded image (R ¹ , R ² , o, q, and r have the same meanings as described above, and X represents a halogen atom, particularly a bromo atom or an iodine atom.)

In this cross coupling, the equation (vi)
Alternatively, examples of the organometallic compound prepared from (vii) include an organic lithium compound, an organic magnesium compound, an organic zinc compound, an organic copper compound, an organic titanium compound, an organic tin compound, and the like. At the time of this cross coupling, a transition metal catalyst such as palladium, nickel, or copper is required. As the palladium catalyst, for example, tetrakis (triphenylphosphine) palladium (0), di (1,2) A zero-valent palladium compound such as -bis (diphenylphosphino) ethane) palladium (0), palladium acetate, palladium chloride,
[1,1′-bis (diphenylphosphino) ferrocene] a divalent palladium compound such as palladium (II) chloride, a complex compound comprising these and a ligand, or a combination of these divalent palladium compounds and a reducing agent Etc. can be used.

As the nickel catalyst, (1,3-bis (diphenylphosphino) propane) nickel chloride (II), (1,2-bis (diphenylphosphino))
Examples thereof include divalent nickel compounds such as ethane) nickel chloride (II) and bis (triphenylphosphine) nickel chloride (II), and zero-valent nickel compounds such as tetrakis (triphenylphosphine) nickel (0).

Examples of the copper compound include monovalent copper salts such as copper (I) chloride, copper (I) bromide, copper (I) iodide, copper (I) cyanide, copper (II) chloride, bromide Copper (II), copper iodide (I
And divalent copper salts such as I), copper (II) cyanide, and copper (II) acetate, and copper complexes such as dilithium tetraque plate.

Also, if necessary, the following equations (1b) and (1b)
It is also possible to use the monomers of c).

[0045]

Embedded image (R ¹ , p, s, and t have the same meaning as above.)

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

When the polymerization is carried out using the above formula (1a), the protecting group for R ^o is eliminated from the obtained polymer to give a polymer unit of the following formula.

[0048]

Embedded image

This polymer unit or the above formula (1)
In the following polymer unit obtained from b), an acid labile group of R ² can be introduced into these phenolic hydroxyl groups according to a conventional method.

[0050]

Embedded image

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

Accordingly, the present invention provides a chemically amplified positive resist material comprising [I] (A) the above-mentioned polymer compound, (B) an organic solvent, and (C) an acid generator.
[II] (A) the polymer compound, (B) an organic solvent,
A chemically amplified negative resist composition comprising (C) an acid generator and (D) a crosslinking agent.

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

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

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

Examples of the acid generator (C) include an onium salt of the following general formula (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.

Next, as the dissolution inhibitor of the component (F),
A compound having a molecular weight of 3,000 or less, whose solubility in an alkali developing solution is changed by the action of an acid, particularly a part or all of a phenol or carboxylic acid derivative having a low molecular weight of 2,500 or less with an acid-labile substituent. Substituted compounds can be mentioned.

Examples of 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, as The acid labile substituents are the same as those for R ^2.

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 te
tert-butyl, tert-butyl 4,4-bis (4′-tert-butoxyphenyl) valerate, 4,4-bis (4-tert-butoxycarbonyloxyphenyl)
Tert-butyl valerate, 4,4-bis (4′-ter
tert-butyl t-butoxycarbonylmethyloxyphenyl) valerate, tert-butyl 4,4-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) valerate,
Tert-Butyl 4,4-bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) valerate, tris (4-
(2′-tetrahydropyranyloxy) phenyl) methane, tris (4- (2′-tetrahydrofuranyloxy) phenyl) methane, tris (4-tert-butoxyphenyl) methane, tris (4-tert-butoxycarbonyloxyphenyl) ) Methane, Tris (4-te
rt-butoxycarbonyloxymethylphenyl) methane, tris (4- (1′-ethoxyethoxy) phenyl) methane, tris (4- (1′-ethoxypropyloxy) phenyl) methane, 1,1,2-tris (4 '-
(2 ″ -tetrahydropyranyloxy) phenyl) ethane, 1,1,2-tris (4 ′-(2 ″ -tetrahydrofuranyloxy) phenyl) ethane, 1,1,2-
Tris (4′-tert-butoxyphenyl) ethane,
1,1,2-tris (4′-tert-butoxycarbonyloxyphenyl) ethane, 1,1,2-tris (4′-tert-butoxycarbonylmethyloxyphenyl) ethane, 1,1,2-tris (4 '-(1'-
Ethoxyethoxy) phenyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxypropyloxy) phenyl) ethane and the like can be mentioned.

The addition amount of the dissolution inhibitor [component (F)] in the resist material of the present invention is 20 parts by weight or less, preferably 15 parts by weight or less based on 100 parts by weight of the solids in the resist material. . If the amount is more than 20 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 0.1 to 5%, preferably 2 to 3% of an aqueous alkali solution such as tetramethylammonium hydroxide (TMAH),
Dipping for 10 seconds to 3 minutes, preferably 30 seconds to 2 minutes (d
ip) method, paddle method, spray method (sp
(ray) method to form a target pattern on the substrate by performing development. 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, particularly an ArF having a wavelength of 193 nm, among high energy rays.
57 nm F ₂ , 146 nm Kr ₂ , 134 nm Kr
Excimer laser such as Ar, 126 nm Ar ₂ , X
Most suitable for fine patterning by electron beam and electron beam.
In addition, when the above range is out of the upper limit and the lower limit, a desired pattern may not be obtained.

[0086]

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

[0087]

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

Reference Example 1 4-tert-butoxy-
Synthesis of 2,3-difluorostyrene 4-L in a 1 L reactor
31.2 g (0.10 mol) of tert-butoxy-2,3-difluoro-1-iodobenzene and 100 ml of tetrahydrofuran (hereinafter abbreviated as THF) were charged and heated to 60 ° C. Here, 1.16 g (1 mmo) of tetrakis (triphenylphosphine) palladium (0)
l) and then 1M THF of vinyl zinc chloride
120 ml of the solution were added dropwise. After aging for 30 minutes after the completion of the dropwise addition, the reaction solution was poured into a saturated aqueous solution of ammonium chloride, and further extracted with ethyl acetate by a conventional method to obtain a crude product. This was purified by silica gel chromatography to obtain 17.6 g (yield: 83%) of the desired product. IR (ν): 2980, 1500, 1470, 136
9,1302,1161,1049,949,860
(Cm ^-1 ) ¹ H-NMR: 1.37 ppm 9H (s) 5.37 ppm 1H (d) 5.78 ppm 1H (d) 6.74-6.84 ppm 2H (m) 7.06-7.15 ppm 1H (M)

Reference Example 2 4-tert-butoxy-
Synthesis of 2,6-difluorostyrene 4-te of Reference Example 1
Using 4-tert-butoxy-2,6-difluoro-1-iodobenzene instead of rt-butoxy-2,3-difluoro-1-iodobenzene, the desired product was obtained in the same manner as in Reference Example 1. Was.

[Examples and Comparative Examples] Synthesis Examples [Synthesis Example 1] Synthesis of poly (4-hydroxystyrene) / poly (4-fluorostyrene) copolymer (1: 1) 66 g of acetoxystyrene in a 2 L flask After 50 g of 4-fluorostyrene was dissolved in 560 ml of toluene, oxygen in the system was sufficiently removed, 5.5 g of an AIBN initiator was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours.

In order to purify the obtained polymer, the reaction mixture was poured into a hexane / ether (3: 2) mixed solvent, and the obtained polymer was precipitated and separated. 97 g of a white polymer poly (4) was obtained. -Acetoxystyrene) / poly (4)
-Fluorostyrene) copolymer (1: 1) was obtained.
The polymer was transferred to a 3 L flask and methanol 50
After dissolving in 0 g and acetone 400 g, 97 g of triethylamine and 50 g of pure water were added, the temperature was raised to 60 ° C., and a hydrolysis reaction was performed for 20 hours. After the reaction solution was concentrated, the solution was poured into 20 L of pure water in which 150 g of acetic acid was dissolved to precipitate a polymer. The operation of dissolving the obtained polymer in acetone and pouring it into 20 L of pure water to precipitate the polymer was repeated twice, then the polymer was separated and dried. 85 g of the white polymer [poly (4-hydroxystyrene) / poly (4-fluorostyrene) copolymer (1: 1)] thus obtained had a weight average molecular weight of 9.8 by a light scattering method.
00g / mol, and the degree of dispersion (=
(Mw / Mn) was confirmed to be 1.60. Further, by measuring ¹ H-NMR, it was confirmed that the polymer contained 4-hydroxystyrene and 4-fluorostyrene at a ratio of about 1: 1.

[Synthesis Example 2] Poly (2,3-difluoro-
Synthesis of 4-hydroxystyrene) 2,3-difluoro-4-tert in a 2 L flask
After dissolving 100 g of butoxystyrene in 460 ml of toluene and sufficiently removing oxygen in the system, the initiator AIB
3.1 g of N was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours. In order to purify the obtained polymer,
The reaction mixture was poured into a mixed solvent of methanol / water (4: 1), and the obtained polymer was precipitated and separated. As a result, 90 g of a white polymer poly (2,3-difluoro-4-tert-) was obtained.
Butoxystyrene) was obtained. This polymer was transferred to a 2 L flask and dissolved in acetone to give a 15% solution. This solution was heated to 60 ° C., 46 ml of 12N hydrochloric acid was added dropwise little by little, and a deprotection reaction was performed for 7 hours. The reaction solution was concentrated after adding 66 g of pyridine, and poured into 5 L of pure water to precipitate a polymer. The operation of dissolving the obtained polymer in acetone and pouring it into 5 L of pure water to precipitate the polymer was repeated twice, then, the polymer was separated and dried. 81 g of the white polymer [poly (2,3-difluoro-4-hydroxystyrene)] thus obtained had a weight average molecular weight of 8,700 g / mol by a light scattering method.
From the GPC elution curve, it was confirmed that the polymer had a dispersity (= Mw / Mn) of 1.65.

Synthesis Example 3 Poly (2,6-difluoro-
Synthesis of 4-hydroxystyrene) 2,6-difluoro-4-tert in a 2 L flask
After dissolving 100 g of butoxystyrene in 460 ml of toluene and sufficiently removing oxygen in the system, the initiator AIB
3.1 g of N was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours. In order to purify the obtained polymer,
The reaction mixture was poured into a mixed solvent of methanol / water (4: 1), and the resulting polymer was precipitated and separated. 88 g of a white polymer poly (2,3-difluoro-4-tert-) was obtained.
Butoxystyrene) was obtained. This polymer was transferred to a 2 L flask and dissolved in acetone to give a 15% solution. This solution was heated to 60 ° C., and 45 ml of 12N hydrochloric acid was added dropwise little by little, followed by performing a deprotection reaction for 7 hours. After adding 65 g of pyridine to the reaction solution, the mixture was concentrated and poured into 5 L of pure water to precipitate a polymer. The operation of dissolving the obtained polymer in acetone and pouring it into 5 L of pure water to precipitate the polymer was repeated twice, then, the polymer was separated and dried. 81 g of the white polymer [poly (2,3-difluoro-4-hydroxystyrene)] thus obtained had a weight average molecular weight of 8,800 g / mol by a light scattering method.
From the GPC elution curve, it was confirmed that the polymer had a degree of dispersion (= Mw / Mn) of 1.67.

[Synthesis Example 4] Poly (4-hydroxystyrene) / poly (4-fluorostyrene) copolymer (1:
Tetrahydropyranylation of 1) In a 300 ml flask, the poly (4-
Hydroxystyrene) / poly (4-fluorostyrene)
20 g of a copolymer (1: 1), 0.6 g of trifluoromethanesulfonic acid, and 100 ml of THF were charged. While stirring at room temperature, 0.7 g of 3,4-dihydro-2H-pyran was added dropwise from a 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. From ¹ H-NMR, 15 g of the white polymer thus obtained was found to have 10% of the hydroxyl groups of 4-hydroxystyrene tetrahydropyranylated. Further, this polymer was confirmed to be a polymer having a weight average molecular weight of 11,500 g / mol by a light scattering method and a dispersity (= Mw / Mn) of 1.70 from a GPC elution curve.

[Synthesis Example 5] Poly (4-hydroxystyrene)
) / Poly (4-fluorostyrene) copolymer (1:
Ethoxyethylation of 1) In a 300 ml flask, the poly (4-
Hydroxystyrene) / poly (4-fluorostyrene)
20 g of copolymer (1: 1), trifluoromethanesulfo
0.6 g of acid and 100 ml of THF were charged. Stir at room temperature
While stirring, add 0.6 mL of ethyl vinyl ether from the dropping funnel.
0 g was added dropwise, and aging was performed at room temperature for 1 hour. To the reaction system
The reaction was quenched by adding triethylamine, and the solvent was
Distilled off under. The obtained crude polymer is added to 40 g of acetone.
Dissolve and pour into 5 L of pure water in which 20 g of acetic acid is dissolved.
The limer was allowed to settle. The obtained polymer is treated with acetone 40
g and pour into 5 L of pure water to precipitate the polymer
After repeating the operation twice, the polymer is separated, dried and dried.
Was. 15.5 g of the white polymer thus obtained was
¹According to 1 H-NMR, the hydroxyl group 1 of 4-hydroxystyrene
0% was found to be ethoxyethylated. Ma
The polymer had a weight average molecular weight of 1 according to the light scattering method.
1,000 g / mol, dispersed from GPC elution curve
Degree (Mw / Mn) 1.65
It was recognized.

[Synthesis Example 6] Poly (4-hydroxystyrene)
) / Poly (4-fluorostyrene) copolymer (1:
Ethoxypropylation of 1) In a 300 ml flask, the poly (4-
Hydroxystyrene) / poly (4-fluorostyrene)
20 g of copolymer (1: 1), trifluoromethanesulfo
0.6 g of acid and 100 ml of THF were charged. Stir at room temperature
While stirring, add ethyl propenyl ether from the dropping funnel.
0.71 g was added dropwise and aged at room temperature for 1 hour. reaction
The reaction was stopped by adding triethylamine to the system,
Was distilled off under reduced pressure. The obtained crude polymer is mixed with acetone 4
0 g and poured into 5 L of pure water in which 20 g of acetic acid was dissolved.
The polymer was then precipitated. The resulting polymer is
Dissolved in 40 g of pure water and poured into 5 L of pure water to precipitate the polymer.
After repeating the operation twice, the polymer is separated and dried.
I let it. 14.5 g of white polymer thus obtained
Body ¹From H-NMR, hydroxyl group of 4-hydroxystyrene
It was found that 10% of phenol was ethoxypropylated.
Was. In addition, this polymer is a light-
The amount is 12,000 g / mol.
Polymer having a degree of dispersion (= Mw / Mn) of 1.70.
Was confirmed.

Synthesis Example 7 Poly (4-hydroxystyrene) / poly (4-fluorostyrene) copolymer (1:
Tert-Butoxycarbonylation of 1) In a 500 ml flask, the poly (4-
Hydroxystyrene) / poly (4-fluorostyrene)
20 g of the copolymer (1: 1) and 250 ml of pyridine were charged. While stirring at room temperature, di (tert) was added through a dropping funnel.
10 ml of tetrahydrofuran in which 1.6 g of (-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. The white polymer obtained 15.0g and was found to be 8% of the hydroxyl groups of 4-hydroxystyrene from ¹ H-NMR is tert- butoxycarbonyl reduction. This polymer had a weight average molecular weight of 12,500 by a light scattering method.
g / mol, and the degree of dispersion (= Mw
/ Mn) was 1.67.

[Synthesis Example 8] Poly (2,3-difluoro-
Tetrahydropyranylation of 4-hydroxystyrene) The poly (2,2) obtained in Synthesis Example 2 was placed in a 300 ml flask.
20 g of 3-difluoro-4-hydroxystyrene)
0.6 g of trifluoromethanesulfonic acid, THF 100 m
l was charged. While stirring at room temperature,
2.48 g of 4-dihydro-2H-pyran was added dropwise, and room temperature was added.
For 1 hour. Add triethylamine to the reaction system
The reaction was stopped by addition, and the solvent was distilled off under reduced pressure. Get
Dissolve the crude polymer in 40 g of acetone, and add 20 g of vinegar.
Pour into 5 L of pure water with acid to precipitate the polymer
Was. Dissolve the obtained polymer in 40 g of acetone, and add pure water
Repeat the operation of pouring into 5 L to precipitate the polymer twice
After that, the polymer was separated and dried. Like this
14.5 g of the obtained white polymer was ¹From H-NMR
Of (2,3-difluoro-4-hydroxystyrene)
20% of the hydroxyl groups must be tetrahydropyranylated.
I understood. In addition, this polymer is superposed by light scattering method.
The weight average molecular weight is 9,500 g / mol,
According to the curve, a polymer having a degree of dispersion (= Mw / Mn) of 1.66 was obtained.
It was confirmed that it was.

Synthesis Example 9 Poly (2,3-difluoro-
Ethoxyethylation of 4-hydroxystyrene) The poly (2,2) obtained in Synthesis Example 2 was placed in a 300 ml flask.
20 g of 3-difluoro-4-hydroxystyrene)
0.6 g of trifluoromethanesulfonic acid, THF 100 m
l was charged. While stirring at room temperature, etch through the dropping funnel.
2.12 g of vinyl ether was added dropwise and ripened at room temperature for 1 hour.
Performed. Reaction by adding triethylamine to the reaction system
Was stopped and the solvent was distilled off under reduced pressure. The obtained crude poly
In 20 g of acetone and 20 g of acetic acid
The polymer was poured into 5 L of pure water to precipitate the polymer. Got
Dissolve the polymer in 40 g of acetone and pour into 5 L of pure water
After repeating the operation of precipitating the polymer twice,
The body was separated and dried. 1 obtained in this way
5.0 g of the white polymer ¹From H-NMR, poly (2,3
-Difluoro-4-hydroxystyrene)
0% was found to be ethoxyethylated. Ma
The weight average molecular weight of this polymer was determined by light scattering.
9,000 g / mol, dispersed from GPC elution curve
It is confirmed that the polymer has a degree (= Mw / Mn) of 1.66.
It was recognized.

[Synthesis Example 10] Poly (2,3-difluoro
Ethoxypropylation of 4-hydroxystyrene) The poly (2,2) obtained in Synthesis Example 2 was placed in a 300 ml flask.
20 g of 3-difluoro-4-hydroxystyrene)
0.6 g of trifluoromethanesulfonic acid, THF 100 m
l was charged. While stirring at room temperature, etch through the dropping funnel.
2.54 g of lupropenyl ether was added dropwise at room temperature for 1 hour.
Aging was performed. Add triethylamine to the reaction system
The reaction was stopped and the solvent was distilled off under reduced pressure. The crude obtained
Dissolve the polymer in 40 g of acetone and dissolve 20 g of acetic acid
The polymer was poured into 5 L of the purified water to precipitate the polymer. Get
Dissolved polymer in 40g of acetone and put in 5L of pure water
After repeating the operation of pouring and precipitating the polymer twice,
The polymer was separated and dried. Obtained in this way
14.9g of white polymer ¹From H-NMR, poly (2,
3-difluoro-4-hydroxystyrene)
It turns out that 20% is ethoxypropylated
Was. In addition, this polymer is a light-
The amount is 9,700 g / mol.
A polymer having a dispersity (= Mw / Mn) of 1.71
Was confirmed.

[Synthesis Example 11] Tert-butoxycarbonylation of poly (2,3-difluoro-4-hydroxystyrene) Poly (2,3-difluoro-4-hydroxystyrene) obtained in Synthesis Example 2 was placed in a 500 ml flask.
20 g of 3-difluoro-4-hydroxystyrene) and 250 ml of pyridine were charged. 5. While stirring at room temperature, di (tert-butyl) dicarbonate was added through a dropping funnel.
15 ml of tetrahydrofuran in which 15 g was dissolved was added dropwise, and reacted at room temperature for 1 hour. The solvent is distilled off under reduced pressure,
The obtained crude polymer was dissolved in 40 g of acetone, and purified water 5
The polymer was precipitated by pouring into L. After the obtained polymer was washed twice with 5 L of pure water, the polymer was separated and dried. From ¹ H-NMR, 14.5 g of the white polymer thus obtained was found to have 18% of the hydroxyl groups of poly (2,3-difluoro-4-hydroxystyrene) tert-butoxycarbonylated. Was. This polymer had a weight average molecular weight of 9,90 by a light scattering method.
0 g / mol, and the degree of dispersion (= M
(w / Mn) was 1.68.

[Synthesis Example 12] Poly (2,6-difluoro
Tetrahydropyranylation of -4-hydroxystyrene) The poly (2,4) obtained in Synthesis Example 3 was placed in a 300 ml flask.
6-difluoro-4-hydroxystyrene) 20 g
0.6 g of trifluoromethanesulfonic acid, THF 100 m
l was charged. While stirring at room temperature,
2.48 g of 4-dihydro-2H-pyran was added dropwise, and room temperature was added.
For 1 hour. Add triethylamine to the reaction system
The reaction was stopped by addition, and the solvent was distilled off under reduced pressure. Get
Dissolve the crude polymer in 40 g of acetone, and add 20 g of vinegar.
Pour into 5 L of pure water with acid to precipitate the polymer
Was. Dissolve the obtained polymer in 40 g of acetone, and add pure water
Repeat the operation of pouring into 5 L to precipitate the polymer twice
After that, the polymer was separated and dried. Like this
15.0 g of the obtained white polymer was ¹From H-NMR
Of (2,6-difluoro-4-hydroxystyrene)
19% of the hydroxyl groups must be tetrahydropyranylated.
I understood. In addition, this polymer is superposed by light scattering method.
GPC with a weight average molecular weight of 10,700 g / mol
Polymerization with a dispersity (= Mw / Mn) of 1.66 from the elution curve
It was confirmed that it was a body.

Synthesis Example 13 Poly (2,6-difluoro)
Ethoxyethylation of 4-hydroxystyrene) The poly (2,2) obtained in Synthesis Example 3 was placed in a 300 ml flask.
6-difluoro-4-hydroxystyrene) 20 g
0.6 g of trifluoromethanesulfonic acid, THF 100 m
l was charged. While stirring at room temperature, etch through the dropping funnel.
2.12 g of vinyl ether was added dropwise and ripened at room temperature for 1 hour.
Performed. Reaction by adding triethylamine to the reaction system
Was stopped and the solvent was distilled off under reduced pressure. The obtained crude poly
In 20 g of acetone and 20 g of acetic acid
The polymer was poured into 5 L of pure water to precipitate the polymer. Got
Dissolve the polymer in 40 g of acetone and pour into 5 L of pure water
After repeating the operation of precipitating the polymer twice,
The body was separated and dried. 1 obtained in this way
4.8 g of the white polymer ¹From H-NMR, poly (2,6
-Difluoro-4-hydroxystyrene)
It was found that 1% was ethoxyethylated. Ma
The polymer had a weight average molecular weight of 1 according to the light scattering method.
000 g / mol, dispersed from GPC elution curve
It is confirmed that the polymer has a degree (= Mw / Mn) of 1.68.
It was recognized.

[Synthesis Example 14] Poly (2,6-difluoro
Ethoxypropylation of 4-hydroxystyrene) The poly (2,2) obtained in Synthesis Example 3 was placed in a 300 ml flask.
6-difluoro-4-hydroxystyrene) 20 g
0.6 g of trifluoromethanesulfonic acid, THF 100 m
l was charged. While stirring at room temperature, etch through the dropping funnel.
2.54 g of lupropenyl ether was added dropwise at room temperature for 1 hour.
Aging was performed. Add triethylamine to the reaction system
The reaction was stopped and the solvent was distilled off under reduced pressure. The crude obtained
Dissolve the polymer in 40 g of acetone and dissolve 20 g of acetic acid
The polymer was poured into 5 L of the purified water to precipitate the polymer. Get
Dissolved polymer in 40g of acetone and put in 5L of pure water
After repeating the operation of pouring and precipitating the polymer twice,
The polymer was separated and dried. Obtained in this way
14.5 g of the white polymer ¹From H-NMR, poly (2,
6-difluoro-4-hydroxystyrene)
It turns out that 20% is ethoxypropylated
Was. In addition, this polymer is a light-
The amount is 11,000 g / mol.
Polymer having a degree of dispersion (= Mw / Mn) of 1.70.
Was confirmed.

[Synthesis Example 15] Tert-butoxycarbonylation of poly (2,6-difluoro-4-hydroxystyrene) In a 500 ml flask, the poly (2,6-difluoro-4-hydroxystyrene) obtained in Synthesis Example 3 was added.
20 g of 6-difluoro-4-hydroxystyrene) and 250 ml of pyridine were charged. 5. While stirring at room temperature, di (tert-butyl) dicarbonate was added through a dropping funnel.
15 ml of tetrahydrofuran in which 15 g was dissolved was added dropwise, and reacted at room temperature for 1 hour. The solvent is distilled off under reduced pressure,
The obtained crude polymer was dissolved in 40 g of acetone, and purified water 5
The polymer was precipitated by pouring into L. After the obtained polymer was washed twice with 5 L of pure water, the polymer was separated and dried. From ¹ H-NMR, 14.8 g of the thus obtained white polymer was found to have 19% of the hydroxyl groups of poly (2,6-difluoro-4-hydroxystyrene) tert-butoxycarbonylated. Was. The polymer had a weight average molecular weight of 12.5 by a light scattering method.
00g / mol, and the degree of dispersion (=
(Mw / Mn) was confirmed to be 1.69.

[0106]Polymer evaluation 1 g of the polymer obtained in the above synthesis example was propylene glycol
Dissolves in 10 g of monomethyl ether acetate
And filtered through a 0.2 μm filter to dissolve the polymer.
A liquid was prepared. On the other hand, the molecular weight is 10,000 and the degree of dispersion (=
(Mw / Mn) 1.10 monodisperse polyhydroxystyrene
30% of the hydroxyl groups were replaced with tetrahydropyranyl groups
A polymer was synthesized, and Comparative Example Polymer 1 was obtained. Also a minute
Polymethyl methacrylate having a molecular weight of 15,000 and a dispersity of 1.7
The rate was determined using Comparative Example Polymer 2, with a meta / para ratio of 40/60.
Novolak polymer having a molecular weight of 9,000 and a dispersity of 2.5
Was designated as Comparative Example Polymer 3. 1 g of the obtained polymer
Propylene glycol monomethyl ether acetate 10
g, and filter through a 0.2 μm filter.
Thus, a polymer solution was prepared. These polymer solutions
MgF_TwoSpin coating on substrate and hot plate
Baking at 100 ° C. for 90 seconds with a thickness of 300 nm
Polymer layer of MgF _TwoIt was created on a substrate. Vacuum ultraviolet light
248n using a densitometer (VUV200S, manufactured by JASCO Corporation)
m, polymer transmittance at 193 nm and 157 nm
Was measured. Table 1 shows the results. In addition, the above polymer solution
Spin coating the liquid on Si substrate, hot plate
Baking at 100 ° C. for 90 seconds with a thickness of 300 nm
Polymer layer on Si substrate and dry etching
Resistance was evaluated under the following two conditions. The results are shown in Table 2.
You.

(1) Etching test with CHF ₃ / CF ₄ system gas Dry etching equipment TE manufactured by Tokyo Electron Limited
Using -8500P, the difference in polymer film thickness before and after etching was determined. The etching conditions are as shown below. Chamber pressure 40.0 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 gas Nidec Anelva Co., Ltd. Dry etching equipment L-50
Using 7DL, the difference in polymer film thickness before and after etching was determined. The etching conditions are as shown below. Chamber pressure 40.0 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

[0108]

[Table 1]

[0109]

[Table 2]

Evaluation of Resist Next, a resist solution was prepared by a conventional method using the above-mentioned polymer and the components shown below in the amounts shown in Table 2. The obtained resist solution is formed into a film of DUV-30 (manufactured by Nissan Chemical Industries, Ltd.) on a silicon wafer with a thickness of 55 nm, and the film is subjected to KrF light (248).
nm), and spin-baked on a hot plate at 100 ° C. for 90 seconds to make the resist 300 nm thick. This is excimer laser stepper (Nikon, N
SR-S202A, NA-0.5, σ0.75, 2/3
Exposure at 110 ° C. immediately after exposure.
Baking was performed for 0 second, and development was performed for 60 seconds with an aqueous solution of 2.38% tetramethylammonium hydroxide to obtain a pattern having a line and space ratio of 1: 1.

The obtained resist pattern was evaluated as follows. Table 3 shows the results. Evaluation method: 0.25 μm line and space:
The exposure amount resolved at 1 was taken as the optimum exposure amount (sensitivity: 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.

[0112]

Embedded image

[0113]

Embedded image

[0114]

[Table 3] PGMEA: Propylene glycol monomethyl ether acetate

From the results of Tables 1, 2 and 3, the polymer of the present invention was
The resist material using the compound is F _TwoExcimer laser
(157 nm) and sufficient transparency
Satisfies image power and sensitivity, and the difference in film thickness after etching is small.
More excellent dry etching resistance
I understood.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Atsushi Watanabe, 28-1 Nishifukushima, Nishifukushima, Nakakushijo-gun, Niigata Prefecture Inside Synthetic Research Laboratory, Shin-Etsu Chemical Co., Ltd. 28-1 Oishi Nishifukushima Shin-Etsu Chemical Industry Co., Ltd.Synthetic Technology Laboratory (72) Inventor Mutsumi Nakajima 28-1 Nishi-Fukushima Oaza, Niigata Pref. Katsu 1-1, Sachimachi, Takatsuki-shi, Osaka (72) Inventor Shinji Kishimura 1-1-1, Sachicho, Takatsuki-shi, Osaka

Claims (7)

[Claims] 1. A polymer compound containing a repeating unit represented by the following general formula (1). Embedded image (Wherein, R ¹ is a hydrogen atom, a chlorine atom or a C 1-20
Is a linear, branched or cyclic alkyl group, a fluorinated alkyl group or a chlorinated alkyl group.
R ² is an acid labile group, and o, p, q, r, s, t are
0 ≦ o <5, 0 <p ≦ 5, 0 ≦ q <5, 0 <r ≦ 5, 0
≦ s ≦ 5, 0 ≦ t ≦ 5, and 0 ≦ o + q <
5, 0 <s + t ≦ 5, 0 <o + p + q ≦ 5, 0 <o + q
+ R ≦ 5, and k, m, and n are 0 <k <
1, 0 ≦ m <1, 0 ≦ n <1, and k + m + n =
It is a number that satisfies 1. ) 2. A resist material comprising a polymer compound represented by the general formula (1). (A) the polymer compound according to (1),
A chemically amplified positive resist composition comprising (B) an organic solvent and (C) an acid generator. 4. The polymer compound according to claim 1, wherein:
A chemically amplified negative resist material comprising (B) an organic solvent, (C) an acid generator, and (D) a crosslinking agent. 5. The method according to claim 3, further comprising a basic compound.
Or the resist material according to 4. 6. The resist material according to claim 3, further comprising a dissolution inhibitor. 7. A step of applying the resist material according to any one of claims 2 to 6 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.