JP2002055456A - Polymer compound, resist material and pattern forming method - Google Patents

Abstract

(57) Abstract: A polymer compound having a repeating unit represented by the following general formula (1). Embedded image (Wherein, R ¹ is a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and may be a bridged cyclic hydrocarbon group. R is a hydrogen atom or an acid Is an unstable group,
0 ≦ m ≦ 3, 0 ≦ n ≦ 3, 1 ≦ m + n ≦ 6. 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.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art LSI
With the high integration and high speed of the pattern, the miniaturization of the pattern rule is rapidly progressing. Background of the rapid progress of miniaturization include higher NA of the projection lens, improved resist performance, and shorter wavelength. Especially from i-line (365 nm) to KrF
The shortening of the wavelength to excimer laser (248 nm) has brought about a major change, and it has become possible to mass-produce devices of the 0.18 μm rule. In order to increase the resolution and sensitivity of the resist, a chemically amplified positive resist material using an acid as a catalyst (Japanese Patent Publication No. 2-27660, JP-A-63-27882)
No. 9) has excellent characteristics and has become a mainstream resist material particularly in 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 the wavelength from a KrF excimer laser to an ArF excimer laser (193 nm) is expected to reduce the design rule to 0.13 μm or less. However, novolak or polyvinylphenol resins which have been conventionally used have been used. Has a very strong light absorption band near the wavelength of 193 nm and cannot be used as a base resin for resist. Acrylic resins and cycloolefin-based alicyclic resins have been studied to ensure light transmittance and required dry etching resistance (Japanese Patent Application Laid-Open No. 9-73).
No. 173, JP-A-10-10739, JP-A-9-23
0595, WO97 / 33198).

Further, with respect to an F ₂ excimer laser (157 nm), which can be expected to be finer than 0.10 μm, it becomes more and more difficult to secure light transmittance. It was also found that those having a carbonyl bond had extremely low light transmittance. Furthermore, siloxane polymers and silsesquioxane polymers are more advantageous for improving light transmittance (Cr
italical issues in 157nm li
thography: T.T. M. Bloomstein
et al. J. Vac. Sci. Technol.
B 16 (6), Nov / Dec 1998), which can be used as a resist base resin for forming a multi-layer resist pattern using oxygen plasma. It is considered that the load on the light transmittance is considerably reduced because the film can be made thinner than the resist.

[0005] However, those in which a phenol group is introduced in order to increase the dissolution contrast with alkali have a window of light absorption near a wavelength of 160 nm, and the light transmittance is slightly improved, but the carboxylic acid is far from a practical level. Introduced ones had strong light absorption based on carbonyl groups, and further reduced light transmittance. It has been found that reducing the carbon-carbon unsaturated bond represented by a benzene ring and the carbon-oxygen double bond represented by a carbonyl group in a single-layer resist are necessary conditions for ensuring light transmittance (International). Work Sh
op157nm Lithography MIT-
LL Boston, MA May 5, 1999).
The silicone-containing polymer is certainly advantageous in terms of light transmittance as compared with a single-layer resist because it can be made thinner, but it was still necessary to fundamentally increase the light transmittance in order to increase the resolution.

The present invention has been made in view of the above circumstances,
Wavelength of 300 nm or less, especially F ₂ (157 nm), Kr ₂
(146 nm), KrAr (134 nm), Ar ₂ (1
26) A resist material having excellent transparency to excimer laser and EUV (8 to 13 nm) in a vacuum ultraviolet region such as nm, particularly a novel polymer compound useful as a base polymer of a chemically amplified resist material, and a resist material containing the same. An object of the present invention is to provide a pattern forming method using a resist material.

[0007]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies in order to achieve the above object, and have considered that fluorinated alcohols can achieve both light transmittance and etching resistance. Attempts to introduce it into the containing polymer resulted in light transmission and etching by using a polysilsesquioxane-based resin containing a fluorinated alcohol partially substituted with acid labile groups. The present inventors have found that a resist material having a high resistance can be obtained, and have accomplished the present invention.

That is, the present invention provides the following polymer compound, resist material and pattern forming method. [1] A polymer compound having a repeating unit represented by the following general formula (1).

Embedded image (Wherein, R ¹ is a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and may be a bridged cyclic hydrocarbon group. R is a hydrogen atom or an acid Is an unstable group,
0 ≦ m ≦ 3, 0 ≦ n ≦ 3, 1 ≦ m + n ≦ 6. [2] A polymer compound having a repeating unit represented by the following general formula (2).

Embedded image (Wherein, R ¹ is a linear, branched, cyclic or bridged cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, R ² is an acid labile group, and R ³ is 1 carbon atom. To 20 linear, branched or cyclic, substituted or unsubstituted monovalent hydrocarbon groups, 0 ≦ m ≦ 3, 0 ≦ n ≦ 3, 0 <p <1, 0 <q <
1, 0 ≦ r <1, 0 ≦ s <1, 0 ≦ t <1, 0 ≦ u <
1, 1 ≦ m + n ≦ 6, and p + q + r + s + t
+ U = 1. [3] A photoresist material comprising the polymer compound of [1] or [2]. [4] (A) the polymer compound of the above [1] or [2],
A chemically amplified positive resist material comprising (B) an organic solvent and (C) an acid generator. [5] The resist material according to [4], further comprising (D) a basic compound. [6] The resist material according to [4] or [5], further comprising (E) a dissolution inhibitor. [7] (1) a step of applying the resist material according to any one of [3] to [6] on a substrate, and (2) a step of applying a resist having a wavelength of 300 nm or less via a photomask after a heat treatment. Exposing with an energy beam or an electron beam;
(3) a step of performing heat treatment as necessary, and then developing with a developer. [8] The method for forming a multilayer resist pattern according to [7], wherein after the pattern is formed, the underlying layer is processed by oxygen plasma etching.

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

[0010]

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[0011]

Embedded image (Wherein, R ¹ is a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and may be a divalent bridged cyclic hydrocarbon group. R is hydrogen Atom or acid labile group,
R ² is an acid labile group; R ³ is a linear, branched or cyclic, substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and 0 ≦ m ≦ 3, 0 ≦ n ≦ 3. , 0 <p <1, 0 <q <
1, 0 ≦ r <1, 0 ≦ s <1, 0 ≦ t <1, 0 ≦ u <
1, 1 ≦ m + n ≦ 6, and p + q + r + s + t
+ U = 1. )

Here, R ¹ is a divalent hydrocarbon group having 1 to 20, preferably 2 to 16 carbon atoms, such as a linear, branched, cyclic or bridged cyclic alkylene group. Specific examples of R ¹ include a methylene group, an ethylene group, a propylene group, a butylene group, a cyclopentylene group, a cyclohexylene group,
Or the following groups are mentioned.

[0013]

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In the polymer compound of the present invention, the acid labile groups represented by R and R ² are variously selected, and in particular, groups represented by the following formulas (3) and (4), It is preferably a tertiary alkyl group having 4 to 40 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms, or an oxoalkyl group having 4 to 20 carbon atoms, which is represented by 5).

[0015]

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In the formula (3), R ⁶ has 4 to 20 carbon atoms;
Preferably, a tertiary alkyl group of 4 to 15, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or a group represented by the general formula (4), Specific examples of the tertiary alkyl group include t
tert-butyl group, tert-amyl group, 1,1-diethylpropyl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group,
1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group,
2-methyl-2-adamantyl group and the like. Specific examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a dimethyl-tert-butylsilyl group and the like, and specific examples of the oxoalkyl group include 3-oxocyclohexyl group, 4-methyl-2-
Oxooxan-4-yl group, 5-methyl-2-oxooxolan-5-yl group and the like. a1 is 0-6
Is an integer.

R ⁷ and R ⁸ in the formula (4) 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.

[0018]

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

Specific examples of the acid labile group of the above formula (3) include a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a tert-amyloxycarbonyl group, a tert-amyloxycarbonylmethyl group,
1,1-diethylpropyloxycarbonyl group, 1,1
-Diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-
2-cyclopentenyloxycarbonyl group, 1-ethyl-2-cyclopentenyloxycarbonylmethyl group, 1
-Ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

Specific examples of the linear or branched acid labile group represented by the above formula (4) include the following groups.

[0022]

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As the cyclic group among the acid labile groups represented by the above formula (4), specifically, tetrahydrofuran-
Examples thereof include a 2-yl group, a 2-methyltetrahydrofuran-2-yl group, a tetrahydropyran-2-yl group, and a 2-methyltetrahydropyran-2-yl group. Equation (4)
Preferred are an ethoxyethyl group, a butoxyethyl group and an ethoxypropyl group.

Next, in the formula (5), R ¹⁰ , R ¹¹ ,
R ¹² is a monovalent hydrocarbon group such as a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and includes oxygen, sulfur,
It may contain a hetero atom such as nitrogen or fluorine, and R ¹⁰
And R ¹¹ , R ¹⁰ and R ¹² , and R ¹¹ and R ¹² may combine with each other to form a ring.

The tertiary alkyl group represented by the formula (5) includes a tert-butyl group, a triethylcarbyl group,
Ethylnorbonyl group, 1-methylcyclohexyl group, 1
-Ethylcyclopentyl group, 2- (2-methyl) adamantyl group, 2- (2-ethyl) adamantyl group, ter
A t-amyl group and the like can be mentioned.

Further, specific examples of the tertiary alkyl group of the formula (5) include the following formulas (5) -1 to (5) -16.

[0027]

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

R ¹⁶ is a hydrogen atom or a carbon atom
-20, especially 1-16 alkyl, hydroxyalkyl, alkoxyalkyl, alkoxy or alkoxyalkoxy groups, which may be linear, branched or 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.

[0032]

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The acid labile groups of R and R ² include
It may be an acid labile group (crosslinking group) represented by the following general formula (6a) or (6b). In this case, the polymer compound is crosslinked between or within molecules by the crosslinking group. It is.

[0034]

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In the formula, R ¹⁹ and R ^{20 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ¹⁹ and R ²⁰ may combine to form a ring, and when forming a ring, R ¹⁹ and R ^{20 each} have 1 to 1 carbon atoms.
8 represents a linear or branched alkylene group. R ²¹ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, b and d are 0 or 1 to 10, preferably 0 or 1 to 5;
Is an integer. A represents a c-valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a hetero atom interposed, or A part of the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom. B is -CO-O-, -N
HCO-O- or -NHCONH- is shown. c is 2
8, c ′ is an integer of 1 to 7.

In this case, A is preferably a straight-chain, branched or cyclic C1-C20 alkylene group, alkyltriyl group, alkyltetrayl group having 1 to 20 carbon atoms, or a C6-C30 alkylene group. These are arylene groups, and these groups may have a hetero atom interposed, and a part of the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group, a carboxyl group, an acyl group or a halogen atom. Further, c ′ is preferably an integer of 1 to 3.

As is clear from the value of c ′ in the above formulas (6a) and (6b), the crosslinkable group is not limited to divalent but trivalent to trivalent.
It may be an octavalent group. For example, as the divalent crosslinking group, the following formulas (6a ′) and (6b ′)
Examples represented by the following formulas (6a ″) and (6b ″) are given.

[0038]

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Here, A in the above-mentioned cross-linking group will be described. Specifically, the c + 1 valent organic group of A is preferably a hydrocarbon group having 1 to 50 carbon atoms, particularly 1 to 40 carbon atoms such as O and NH. , N (CH ₃ ), S, SO ₂ or other unsubstituted or hydroxyl-, carboxyl-, acyl- or fluorine-substituted alkylene groups which may be intervened with a heteroatom, preferably 6 to 50, particularly 6 to 6 carbon atoms. An arylene group of 40, a group in which the alkylene group and the arylene group are bonded, and an a ′ valence (a ′) in which a hydrogen atom bonded to a carbon atom of each of the above groups is eliminated.
Is an integer of 3 to 8), and further includes an a + 1-valent heterocyclic group, and a group in which the heterocyclic group is bonded to the above hydrocarbon group. To be specific, A includes the following.

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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Preferably, in the formula (6a), R ¹⁹ is a methyl group, R ²⁰ is a hydrogen atom, b is 0, A is ethylene,
1,4-butylene or 1,4-cyclohexylene.

In order to obtain a polymer compound which is cross-linked between molecules and / or intramolecularly by the cross-linking group having a C—O—C group, the corresponding non-cross-linked polymer compound and alkenyl ether are converted to an acid. It can be synthesized by reacting in a conventional manner under catalytic conditions.

When the decomposition of another acid labile group proceeds under acid catalyst conditions, the alkenyl ether is reacted with hydrochloric acid or the like to form a halogenated alkyl ether. The desired product can be obtained by reacting with a molecular compound.

Here, specific examples of the alkenyl ether include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,3-propanediol divinyl ether, and 1,3-butanediol divinyl ether. Vinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, 1,4
-Cyclohexanediol divinyl ether, 1,4-
Divinyloxymethylcyclohexane, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene Vinyl ether, triethylene glycol diethylene vinyl ether, trimethylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythritol diethylene vinyl ether,
Examples thereof include pentaerythritol triethylene vinyl ether, pentaerythritol tetraethylene vinyl ether, and compounds represented by the following formulas (I-1) to (I-31).

[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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Also, diethylene vinyl ether terephthalate, diethylene vinyl ether phthalate, diethylene vinyl ether isophthalate, dipropylene vinyl ether phthalate, dipropylene vinyl ether terephthalate, dipropylene vinyl ether isophthalate, diethylene vinyl ether maleate, diethylene vinyl ether fumarate, itaconic acid Examples thereof include diethylene vinyl ether, and the following formulas (II-1) to (I)
Compounds represented by I-11) can be exemplified, but are not limited to the compounds exemplified above.

[0057]

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[0058]

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R ³ is a linear group having 1 to 20 carbon atoms;
A branched or cyclic substituted or unsubstituted monovalent hydrocarbon group, wherein an alkyl group, an aryl group, an aralkyl group, or the like, or a part or all of the hydrogen atoms of these groups is a halogen atom, particularly a fluorine atom or an OR ² group And the like.

Specific examples of R ³ include methyl, chloromethyl, ethyl, 2,2,2-trifluoroethyl, n-propyl, and 3,3,3-trifluoropropyl. A chain alkyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a branched alkyl group such as a tert-butyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 2-norbornyl group, a 1-adamantyl group, Examples include a cyclic alkyl group such as a 2-adamantyl group.

In the equation (1), the following equation (1a)

Embedded image Examples of the group represented by are the following groups.

[0062]

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In the above formulas (1) and (2), m and n are 0 ≦ m ≦ 3 and 0 ≦ n ≦ 3, preferably m = 3 and n
= 3.

In the above equation (2), p, q, r, s,
t and u are 0 <p <1, preferably 0.05 ≦ p ≦ 0.
95, more preferably 0.1 ≦ p ≦ 0.9, even more preferably 0.15 ≦ p ≦ 0.85, 0 <q <1, preferably 0.05 ≦ q ≦ 0.95, more preferably 0 .1 ≦ q ≦
0.9, more preferably 0.15 ≦ q ≦ 0.85, and 0 ≦ r <1, 0 ≦ s <1, 0 ≦ t <1, 0 ≦ u
<1, but preferably 0 ≦ r ≦ 0.6, 0 ≦ s ≦
0.6, 0 ≦ t ≦ 0.6, 0 ≦ u ≦ 0.6, more preferably 0 ≦ r ≦ 0.4, 0 ≦ s ≦ 0.4, 0 ≦ t ≦ 0.
4, 0 ≦ u ≦ 0.4, more preferably 0 ≦ r ≦ 0.2,
0 ≦ s ≦ 0.2, 0 ≦ t ≦ 0.2, and 0 ≦ u ≦ 0.2. Note that p + q + r + s + t + u = 1.

The weight average molecular weight of the polymer compound of the present invention is from 1,000 to 100,000, particularly from 1,500 to 5,
Preferably it is 000.

When the above-mentioned polymer compound is produced, generally, for example, a trichlorosilane or trialkoxysilane monomer is synthesized by the following synthesis method, and is polymerized by hydrolysis and dehydration-condensation polymerization in a conventional manner.
At the time of polycondensation, the hydroxy group of the fluorinated alcohol is protected with an acetyl group or an alkyl group, and is deprotected after the polycondensation. Thereafter, by protecting the hydroxy group with an acid labile group, that is, by partially introducing the acid labile group to the OH group, a polymer having a repeating unit of the formula (1) can be obtained. it can.

[0067]

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[0068]

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In the above general formula (2), p + q
Is close to 1 and the values of r, s, t, and u are 0 or 0
In this case, depending on the type of the group represented by R ¹ and the type of the group represented by the above formula (1a), the compound has desired physical properties such as molecular weight and thermodynamic properties. It may be impossible or difficult to obtain a polymer compound. As means for solving this problem, r, s, t,
It is effective to set u to an appropriate value. As one example, it is difficult to keep the molecular weight of the polymer compound (III) in Synthesis Example 5 described below to 4,000 or more with the same charge composition, whereas in Synthesis Example 7, t is set to an appropriate value. By setting, the high molecular compound (V) having a molecular weight of more than 6,000 can be easily obtained.

The resist material of the present invention comprises the above polymer compound as a base resin, and is particularly effectively used as a chemically amplified type, and is particularly preferably used as a chemically amplified positive type.

In this case, the resist material of the present invention comprises:
(A) the polymer compound, (B) an organic solvent, and (C) an acid generator as essential components, preferably (D) a basic compound,
And / or (E) a dissolution inhibitor.

The organic solvent (B) used in the present invention may be any organic solvent capable of dissolving an acid generator, a base resin, a dissolution inhibitor and the like. Examples of such an organic solvent include ketones such as cyclohexanone, 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 (7), a diazomethane derivative of the formula (8), a glyoxime derivative of the formula (9), a β-ketosulfone derivative, a disulfone derivative, and nitrobenzyl. Sulfonate derivatives, sulfonic acid ester derivatives, imido-yl sulfonate derivatives, and the like.

(R ³⁰ ) _b M ⁺ K ⁻ (7) (where R ³⁰ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a carbon atom having 6 to 12 carbon atoms) Represents an aralkyl group of 7 to 12, M ⁺ represents iodonium or sulfonium, K ⁻ represents a non-nucleophilic counter ion, and b is 2 or 3.)

The alkyl group for R ³⁰ includes a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group,
-Oxocyclohexyl, norbornyl, adamantyl and the like. Aryl groups include phenyl, p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p
-Tert-butoxyphenyl group, alkoxyphenyl group such as m-tert-butoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 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. Examples of the non-nucleophilic counter ion of K ⁻ include halide ions such as chloride ions and bromide ions, fluoroalkyl sulfonates such as triflate, 1,1,1-trifluoroethanesulfonate and nonafluorobutane sulfonate, tosylate, and benzene sulfonate. , 4-fluorobenzenesulfonate, arylsulfonates such as 1,2,3,4,5-pentafluorobenzenesulfonate, and alkylsulfonates such as mesylate and butanesulfonate.

[0076]

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

Examples of the alkyl group for 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,
An adamantyl group and the like can be mentioned. 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.

[0078]

Embedded image (However, R ³³ , R ³⁴ , and R ³⁵ are linear, branched or cyclic alkyl groups or halogenated alkyl groups having 1 to 12 carbon atoms, aryl groups or halogenated aryl groups having 6 to 12 carbon atoms or carbon atoms. an aralkyl group having 7 to 12. ^Moreover, R ^{34, R 3 5} may be bonded to each other to form a cyclic structure, to form a cyclic ^{structure, R} 3 ^{4, R 35} are each a carbon number 1 Represents a linear or branched alkylene group of 1 to 6)

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 those described for R ³¹ and R ³² can be mentioned. In addition, as an alkylene group of R ³⁴ and R ^35, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and the like can be mentioned.

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, 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, 5-norbornene-2,3-dicarboximido-yl-n-butylsulfonate, etc., and triphenylsulfonium trifluoromethanesulfonate; Trifluoromethanesulfonic 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 based on 100 parts of the base resin.
Parts (parts by weight, hereinafter the same) is preferably 0.2 to 15 parts, particularly 0.5 to 8 parts. If less than 0.2 parts, the amount of acid generated during exposure is small, and sensitivity and The resolution may be inferior. If it exceeds 15 parts, the transmittance of the resist may decrease, and the resolving power may deteriorate.

As the basic compound as the component (D), a compound capable of suppressing the diffusion rate when the acid generated from the acid generator diffuses into the resist film is suitable. The composition improves the resolution by suppressing the diffusion rate of acid in the resist film, suppresses the change in sensitivity after exposure, reduces the dependence on the substrate and environment, and improves the exposure margin and pattern profile. (JP-A-5-232706 and JP-A-5-249683).
Nos. 5-158239, 5-249662, 5-257282, 5-289322, and 5-2
No. 89340).

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), 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.

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, etc.). , 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 amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamido, N-methylacetamido,
Examples include N-dimethylacetamide, propionamide, benzamide and the like. Examples of the imide derivative include phthalimide, succinimide, and maleimide.

Further, basic compounds represented by the following general formulas (10) and (11) can be blended.

[0088]

Embedded image (Wherein, R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁷ , and R ⁴⁸ each independently represent a linear, branched, or cyclic C 1 -C 1)
20 alkylene groups, R ⁴⁴ , R ⁴⁵ , R ⁴⁶ ,
R ⁴⁹ and R ^{50 each} represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an amino group, and R ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R
⁴⁶ , R ⁴⁴ and R ⁴⁶ , R ⁴⁴ and R ⁴⁵ and R ⁴⁶ , R
⁴⁹ and R ⁵⁰ may be combined 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, R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R
⁴⁹ and R ⁵⁰ do not contain a hydrogen atom. )

Here, R ⁴¹ , R ⁴² , R ⁴³ ,
As the alkylene group for R ⁴⁷ and R ⁴⁸ , C 1 to C 2
0, preferably 1 to 10, more preferably 1 to 8, and specifically, methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene Group, isopentylene group, hexylene group, nonylene group, decylene group, cyclopentylene group, cyclohexylene group and the like.

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

Further, R ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ ,
R ⁴⁴ and R ⁴⁶ , R ⁴⁴ and R ⁴⁵ and R ⁴⁶ , R ⁴⁹ and R
^{When 50} forms a ring, the ring has 1 to 20 carbon atoms;
More preferably 1 to 8, still more preferably 1 to 6,
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 (10) and (11) 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-mentioned basic compounds can be used alone or in combination of two or more. The compounding amount is 0.01 to 2 parts, especially 0.01 to 2 parts, based on 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.

Next, as a dissolution inhibitor as the component (E), a compound having a molecular weight of 3,000 or less, whose solubility in an alkaline developer changes by the action of an acid, particularly a low molecular weight phenol of 2,500 or less, or Compounds in which part or all of the carboxylic acid derivative has been substituted with an acid-labile substituent can be mentioned.

Examples of phenol or carboxylic acid derivatives having a molecular weight of 2,500 or less include 4,4 '-(1-methylethylidene) bisphenol and [1,1'-biphenyl-4,4'-diol] 2,2'-diol. Methylene bis [4-
Methylphenol], 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, 3,3′difluoro [(1 , 1'-biphenyl) 4,4'-diol], 3,3 ', 5,5'-tetrafluoro [(1,1'-biphenyl) -4,4'-diol], 4,4'-[ 2,2,2-trifluoro-1
-(Trifluoromethyl) ethylidene] bisphenol, 4,4'-methylenebis [2-fluorophenol], 2,2'-methylenebis [4-fluorophenol], 4,4'isopropylidenebis [2-fluorophenol], Cyclohexylidenebis [2-fluorophenol], 4,4 '-[(4-fluorophenyl) methylene] bis [2-fluorophenol], 4,4'-
Methylenebis [2,6-difluorophenol], 4,
4 '-(4-fluorophenyl) methylenebis [2,6
-Difluorophenol], 2,6-bis [(2-hydroxy-5-fluorophenyl) methyl] -4-fluorophenol, 2,6-bis [(4-hydroxy-3-
Fluorophenyl) methyl] -4-fluorophenol, 2,4-bis [(3-hydroxy-4-hydroxyphenyl) methyl] -6-methylphenol, and the like. ² and the like.

Examples of suitable dissolution inhibitors include 3,3 ′, 5,5′-tetrafluoro [(1,1 ′
-Biphenyl) -4,4'-di-t-butoxycarbonyl], 4,4 '-[2,2,2-trifluoro-1-
(Trifluoromethyl) ethylidene] bisphenol-
4,4'-di-t-butoxycarbonyl, bis (4-
(2′-tetrahydropyranyloxy) phenyl) methane, bis (4- (2′-tetrahydrofuranyloxy)
Phenyl) methane, bis (4-tert-butoxyphenyloxy) 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'-tert-butoxycarbonyloxyphenyl) propane, 2,2-
Bis (4-tert-butoxycarbonylmethyloxyphenyl) propane, 2,2-bis (4 ′-(1 ″-
Ethoxyethoxy) phenyl) propane, 2,2-bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) propane, 4,4-bis (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) Tert-butyl valerate, tert-butyl 4,4-bis (4 ′-(2 ″ -tetrahydrofuranyloxy) phenyl) valerate,
Tert-butyl 4,4-bis (4′-tert-butoxyphenyl) valerate, 4,4-bis (4-tert-butyl)
Butoxycarbonyloxyphenyl) valeric acid tert-
Butyl, tert-butyl 4,4-bis (4′-tert-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-butoxycarbonyloxyphenyl) methane, tris (4-tert-butoxycarbonyloxyphenyl) methane, tris (4-tert-butoxycarbonyloxymethylphenyl) methane, tris (4 -(1′-ethoxyethoxy) phenyl) methane, tris (4- (1′-ethoxypropyl) ) Phenyl) methane, 1,1,2-tris (4 '- (2''
-Tetrahydropyranyloxy) phenyl) ethane,
1,1,2-tris (4 ′-(2 ″ -tetrahydrofuranyloxy) phenyl) ethane, 1,1,2-tris (4′-tert-butoxyphenyl) ethane,
1,2-tris (4′-tert-butoxycarbonyloxyphenyl) ethane, 1,1,2-tris (4′-
tert-butoxycarbonylmethyloxyphenyl)
Ethane, 1,1,2-tris (4 '-(1'-ethoxyethoxy) phenyl) ethane, 1,1,2-tris (4'-(1'-ethoxypropyloxy) phenyl)
Ethane, 2-trifluoromethylbenzenecarboxylic acid 1,1-t-butyl ester, 2-trifluoromethylcyclohexanecarboxylic acid-t-butyl ester, decahydronaphthalene-2,6-dicarboxylic acid-t-butyl ester, coal Acid-t-butyl ester, deoxycholic acid-t-butyl ester, adamantanecarboxylic acid-t-butyl ester, adamantaneacetic acid-t-butyl ester, [1,1′-bicyclohexyl-3,3 ′,
4,4'-tetracarboxylic acid tetra-t-butyl ester] and the like.

The addition amount of the dissolution inhibitor in the resist material of the present invention is 20 parts or less, preferably 15 parts or less based on 100 parts of solids in the resist material. 2
If the amount is more than 0 parts, the monomer component increases, so that the heat resistance of the resist material decreases.

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 hindered.

The surfactant is preferably a nonionic surfactant, and examples thereof include perfluoroalkylpolyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, and fluorine-containing organosiloxane compounds. For example, Florard "F
C-430 "," FC-431 "(all manufactured by Sumitomo 3M Limited), Surflon" S-141 "," S-1 "
45, S-381, S-383 (all manufactured by Asahi Glass Co., Ltd.), Unidyne DS-401, DS
-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), MegaFac" F-8151 "," F-1
71 "," F-172 "," F-173 "," F-17 "
7 "(all manufactured by Dainippon Ink and Chemicals, Inc.)," X-7
0-092 "and" X-70-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.). Preferably, Florard "FC-430" (manufactured by Sumitomo 3M Limited) and "X-70-093" (manufactured by Shin-Etsu Chemical Co., Ltd.) are exemplified.

Pattern using the resist material of the present invention
In order to form a
Can be performed, for example, on a substrate such as a silicon wafer.
Thickness of 0.1-1.0μ by spin coating etc.
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 turns is formed on the above resist film.
Shades, deep ultraviolet rays with a wavelength of 300 nm or less, excimer
Exposure to high energy rays such as lasers, X-rays or electron beams
1 to 200 mJ / cm²Degree, preferably 10-100
mJ / cm²Irradiation to the extent
60 to 150 ° C. for 10 seconds to 5 minutes, preferably
80 ~ 130 ℃, 30 seconds ~ 3 minutes post exposure
Bake (PEB). Further, 0.1 to 5%, preferably
Is 2-3% tetramethyl ammonium hydroxide
Using a developing solution of an alkaline aqueous solution such as
Dipping for 10 seconds to 3 minutes, preferably 30 seconds to 2 minutes (d
ip) method, paddle method, spray method (sp
ray) on the substrate by developing with a conventional method such as
The desired pattern is formed. The material of the present invention
254 to 120 nm far ultraviolet rays among high energy rays
Line or excimer laser, especially ArF of 193 nm, 1
57nm F ₂Kr of 146 nm₂, 134 nm K
rAr, 126 nm Ar₂Excimer lasers, such as
Ideal for fine patterning with X-rays and electron beams
You. In addition, when the above range is out of the upper limit and the lower limit,
Sometimes the desired pattern cannot be obtained. That
Then, if necessary, use an oxygen plasma etch
The base can be processed.

[0102]

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.

[0103]

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

[Synthesis Example 1] 5- (2-acetoxy-2,
2-bistrifluoromethyl) ethyl-2-norbornene In a 200 ml autoclave, cyclopentadiene (14.9 g) and 1,1-bistrifluoromethyl-3 were added.
-Buten-1-ol (43.8 g) was charged, and 180
Stirred at C for 2 hours. 19. The reaction mixture was distilled under reduced pressure.
6 g of 5- (2-hydroxy-2,2-bistrifluoromethyl) ethyl-2-norbornene were obtained (boiling point 84
８８88 ° C./3.33 kPa). Sodium hydride (1.9 g) and tetrahydrofuran (90 ml) were charged into a 200 ml three-necked flask, and a solution of the above norbornene derivative (18.0 g) in tetrahydrofuran (90 ml) was added dropwise while paying attention to the generation of hydrogen. After stirring at room temperature for 30 minutes, acetyl chloride (8.0 g) was added dropwise over 1 hour under ice cooling, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was poured into an ice-cooled aqueous sodium hydrogen carbonate solution, and the aqueous layer was extracted with diethyl ether. The organic layer was washed with a saturated saline solution, dried over anhydrous sodium sulfate, filtered, concentrated, and distilled under reduced pressure (boiling point: 90 to 94 ° C./3.33 kPa) to obtain the desired compound.
-(2-Acetoxy-2,2-bistrifluoromethyl) ethyl-2-norbornene (16.6 g) was obtained.
Its formation was confirmed by mass spectrum.

[Synthesis Example 2] (2-acetoxy-2,2-
Bistrifluoromethyl) ethyl-trichlorosilylnorbornane 100 equipped with stirrer, reflux, dropping funnel and thermometer
ml of 3- (2-acetoxy-2,
2-bistrifluoromethyl) ethyl-2-norbornene (9.0 g), 20% by weight chloroplatinic acid-isopropanol solution (0.009 g), isooctane (15 ml)
And heated to 80 ° C. After the internal temperature was stabilized, trichlorosilane (4.3 g) was added dropwise over 30 minutes. After completion of the dropwise addition, the reaction solution was stirred at 80 ° C. for 5 hours. The reaction solution was distilled under reduced pressure to obtain (2-acetoxy-2,2-bistrifluoromethyl) ethyl-trichlorosilylnorbornane (8.2 g) as a fraction having a boiling point of 98 to 102 ° C./10 Pa.

Synthesis Example 3 Polymer (I) Triethylamine (8.5 g), toluene (5 ml), methyl isobutyl ketone (5 ml) and water (10 ml) were charged into a 200 ml three-necked flask, and cooled under ice-cooling.
The norbornane derivative (5.0 g) obtained in Synthesis Example 2 was added dropwise, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was diluted with methyl isobutyl ketone, washed repeatedly with a mixed aqueous solution of sodium chloride and ammonium chloride until the pH was 8 or less, and concentrated. This is dissolved in toluene and filtered, and 200 ml
Was stirred at 200 ° C. for 12 hours to obtain a polymer (4.1 g) having a weight average molecular weight of 3,200.
After cooling, potassium carbonate (7.7 g), methanol (45 g)
ml), tetrahydrofuran (55 ml), water (10 m
l) was added and the mixture was stirred at room temperature for 12 hours. A saturated aqueous ammonium chloride solution (50 ml) and water (10 ml) were added thereto, the aqueous layer was extracted with ether, and the organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, filtered and concentrated. This is dissolved in tetrahydrofuran (50 ml),
After adding methanesulfonic acid (0.3 g), ethyl vinyl ether (1.3 g) was added at 30 ° C., and the mixture was stirred for 3 hours, and neutralized by adding concentrated aqueous ammonia. This reaction solution was solvent-exchanged to ethyl acetate, washed six times with a mixed solution of pure water and acetone, then solvent-exchanged to acetone, and added dropwise to pure water.
The crystallized product is collected by filtration, washed with pure water, and dried under vacuum.
9 g of a white powder was obtained. As a result of NMR and GPC analysis, it was confirmed that this was the polymer (I) represented by the following formula and having a weight average molecular weight of 3,300.

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[Synthesis Example 4] Polymer (II) 3,4-dihydro-2 instead of ethyl vinyl ether
Except for using H-pyran, exactly the same as in Synthesis Example 3,
A polymer (II) (4.0 g) having a weight average molecular weight of 3,400 represented by the following formula was obtained.

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Synthesis Example 5 Polymer (III) A 200 ml three-necked flask was charged with triethylamine (8.5 g), toluene (5 ml), methyl isobutyl ketone (5 ml), and water (10 ml).
A mixture of the norbornane derivative (5.93 g) obtained in Synthesis Example 2 and trichloromethylsilane (0.35 g) was added dropwise, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was diluted with methyl isobutyl ketone, washed repeatedly with a mixed aqueous solution of sodium chloride and ammonium chloride until the pH was 8 or less, and concentrated. This is dissolved in toluene and filtered, and 200 ml
Was stirred at 200 ° C. for 12 hours to obtain a polymer (3.91 g) having a weight average molecular weight of 3,600. After cooling, potassium carbonate (7.5 g), methanol (40 ml), tetrahydrofuran (50 ml) and water (10 ml) were added, and the mixture was stirred at room temperature for 12 hours. A saturated aqueous ammonium chloride solution (50 ml) and water (10 m
l) was added, the aqueous layer was extracted with ether, the organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, filtered,
Concentrated. This was dissolved in tetrahydrofuran (50 ml), and methanesulfonic acid (0.30 g) was added.
At 0 ° C., ethyl vinyl ether (1.30 g) was added and 3
After stirring for an hour, concentrated aqueous ammonia was added for neutralization. This reaction solution was solvent-exchanged to ethyl acetate, washed six times with a mixed solution of pure water and acetone, then solvent-exchanged to acetone, and added dropwise to pure water. The crystallized product was collected by filtration, washed with pure water, and dried under vacuum to obtain 3.72 g of a white powder. As a result of NMR and GPC analysis, it was confirmed that this was a polymer (III) represented by the following formula and having a weight average molecular weight of 3,800.

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[Synthesis Example 6] Polymer (IV) 3,4-dihydro-2 instead of ethyl vinyl ether
Except for using H-pyran, exactly the same as in Synthesis Example 5,
A polymer (IV) (3.79 g) represented by the following formula and having a weight average molecular weight of 3,900 was obtained.

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Synthesis Example 7 Polymer (V) As raw materials for the hydrolysis reaction, the norbornane derivative (5.81 g) obtained in Synthesis Example 2, trichloromethylsilane (0.43 g), 1,2-bis (chloro A polymer (V) having a weight average molecular weight of 6,400 (3.89 g) represented by the following formula was obtained in the same manner as in Synthesis Example 5 except that a mixture of dimethylsilyl) ethane (0.07 g) was used.

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[Comparative Synthesis Example] 1,200 ml of water was charged into a reactor, and a mixed solution of 487.2 g (2.0 mol) of trichloro-p-methoxybenzylsilane and 600 ml of toluene was stirred for 2 hours at 30 ° C. And dripping,
Hydrolysis was performed. Thereafter, the aqueous layer was removed by a liquid separation operation, and the organic layer was washed with water until the aqueous layer became neutral. 80 g of hexamethyldisilazane was added to the organic layer, and the mixture was refluxed for 5 hours. After cooling, toluene and unreacted hexamethyldisilazane were distilled off by an evaporator, and then dissolved in 400 g of acetonitrile. 60 in this solution
480 g of trimethylsilyl iodide was dropped at a temperature of not higher than
The reaction was performed at 60 ° C. for 10 hours. After completion of the reaction, 200 g of water
Was added to carry out hydrolysis, and then a polymer layer was obtained by decanting. After the solvent was removed by an evaporator, the polymer was dried under vacuum to obtain 330 g of poly (p-hydroxybenzylsilsesquioxane). When the molecular weight of this polymer was measured by GPC, Mw =
3,500.

After dissolving 160 g of the above poly (p-hydroxybenzylsilsesquioxane) in 1,000 ml of dimethylformamide in a 2 L flask, a catalytic amount of p-toluenesulfonic acid was added, and the mixture was stirred at 20 ° C. While adding 19.0 g of ethyl vinyl ether. After reacting for 1 hour, neutralize with concentrated aqueous ammonia and add 10 L of water.
When the neutralization reaction solution was added dropwise to the mixture, a white solid was obtained.
After filtration, this was dissolved in 500 ml of acetone, and water 10
L, filtered, and dried in vacuum. As a result of NMR and GPC analysis, it was confirmed that this was a polymer (VI) having a weight average molecular weight of 3,800 represented by the following formula.

[0118]

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Next, the light transmittance of the polymer obtained above was evaluated by the following method. Table 1 shows the results. Measurement of light transmittance of polymer: 1 g of the obtained polymer was mixed with propylene glycol monomethyl ether acetate (PG
MEA) sufficiently dissolved in 10 g, and a pore size of 0.2 μm
The resulting solution was filtered through a filter of m to prepare a polymer solution.
The polymer solution was spin-coated on a MgF ₂ substrate and baked at 100 ° C. for 90 seconds using a hot plate to form a polymer layer having a thickness of 100 nm on the MgF ₂ substrate. The light transmittance at wavelengths of 248 nm, 193 nm, and 157 nm was measured using a vacuum ultraviolet photometer (VUV200S, manufactured by JASCO Corporation).

[0120]

[Table 1]

Dry etching resistance test: 2 g of the above polymer was sufficiently dissolved in 10 g of propylene glycol monomethyl ether acetate and filtered with a 0.2 μm filter to prepare a polymer solution. This polymer solution was spin-coated on a Si substrate and baked at 100 ° C. for 90 seconds using a hot plate to form a 300 nm-thick polymer layer on the Si substrate. Dry etching was performed under the following conditions, and the etching resistance of the polymer was evaluated. Etching test with O ₂ gas: Using a dry etching device TE-8500P manufactured by Tokyo Electron Limited, the difference in polymer film thickness before and after etching was determined. Table 2 shows the results
Shown in

The etching conditions are as shown below. Press 60Pa Power 600W Ar 40ml / min O ₂ 60ml / min Gap 9mm Time 60sec

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[Table 2]

Examples and Comparative Examples A resist solution having the composition shown in Table 3 was prepared. On the other hand, DUV-
30 (manufactured by Nissan Chemical Industries, Ltd.) with a film thickness of 55 nm, and KrF
A substrate having a reflectance of 1% or less for an excimer laser (wavelength: 248 nm) was prepared. Next, the above-mentioned resist solution was spin-coated on this substrate, and baked at 100 ° C. for 90 seconds using a hot plate to make the thickness of the resist film 100 nm. An excimer laser stepper (Nikon Corporation, NSR-S202A, NA-0.
6, σ 0.75, 2/3 annular illumination), and immediately after the exposure, baking at 110 ° C. for 90 seconds and 30% with a 2.38% aqueous solution of tetramethylammonium hydroxide.
Development was performed for 2 seconds to obtain a positive pattern. The obtained resist pattern was evaluated as follows. Table 3 shows the results. Evaluation method: 0.20 μm line and space:
Exposure amount to be resolved at 1 is optimal exposure amount (Eop) = sensitivity (m
J / cm ² ), the minimum line width of the line and space separated at this exposure amount was taken as the resolution (μm) of the evaluation resist.

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[Table 3]

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From the results shown in Tables 1 to 3, the resist material using the polymer compound of the present invention satisfies the same resolution and sensitivity as the conventionally proposed benzylsilsesquioxane type, and the film thickness after etching. Since the difference was small, it was found that it had excellent dry etching resistance.
Furthermore very high light transmittance in the VUV region, it was found that F ₂ lithography, or even in the ArF lithography is a promising material.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) G03F 7/075 511 G03F 7/075 511 7/40 521 7/40 521 H01L 21/027 H01L 21/30 502R (72) Inventor Toshinobu Ishihara 28-1 Nishifukushima, Kazagusuku-mura, Nakakubijo-gun, Niigata Prefecture Inside the Synthetic Technology Research Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inventor: Toru Kubota 28-1, Nishifukushima, Oaza, Kushiro-mura, Nakakushiro-gun, Niigata Prefecture Shin-Etsu Chemical Co., Ltd. 28-1 Fukushima Shin-Etsu Chemical Co., Ltd. Synthetic Technology Laboratory F term (reference) 2H025 AA01 AA02 AA09 AB16 AC04 AC06 AC08 AD03 BE00 BE10 BG00 CC03 CC20 FA03 FA12 FA17 FA41 2H096 AA00 AA25 BA11 BA20 EA03 EA05 EA06 FA01 GA08 HA23 HA24 4J CP081 CP191 EB116 EJ028 EJ038 EN 017 EN057 EU047 EU077 EU117 EU137 EV216 EV246 EV296 FD206 FD207 FD208 GP03 4J035 BA01 BA12 CA071 CA082 CA151 CA161 HA01 LB16

Claims (8)

[Claims] 1. A polymer compound having a repeating unit represented by the following general formula (1). Embedded image (Wherein, R ¹ is a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and may be a bridged cyclic hydrocarbon group. R is a hydrogen atom or an acid Is an unstable group,
0 ≦ m ≦ 3, 0 ≦ n ≦ 3, 1 ≦ m + n ≦ 6. ) 2. A polymer compound having a repeating unit represented by the following general formula (2). Embedded image (Wherein, R ¹ is a linear, branched, cyclic or bridged cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, R ² is an acid labile group, and R ³ is 1 carbon atom. To 20 linear, branched or cyclic, substituted or unsubstituted monovalent hydrocarbon groups, 0 ≦ m ≦ 3, 0 ≦ n ≦ 3, 0 <p <1, 0 <q <
1, 0 ≦ r <1, 0 ≦ s <1, 0 ≦ t <1, 0 ≦ u <
1, 1 ≦ m + n ≦ 6, and p + q + r + s + t
+ U = 1. ) 3. A resist material comprising the polymer compound according to claim 1 or 2. 4. A chemically amplified positive resist material comprising (A) the polymer compound according to claim 1 or 2, (B) an organic solvent, and (C) an acid generator. 5. The resist material according to claim 4, further comprising (D) a basic compound. 6. The resist material according to claim 4, further comprising (E) a dissolution inhibitor. 7. A step of (1) applying the resist material according to any one of claims 3 to 6 onto a substrate; and (2)
Next, after the heat treatment, a wavelength of 300 n is passed through a photomask.
A pattern forming method comprising: exposing with a high-energy ray or an electron beam of m or less; and (3) performing a heat treatment as necessary and then developing with a developer. 8. The method for forming a multilayer resist pattern according to claim 7, wherein after forming the pattern, the base is processed by oxygen plasma etching.