JP2002268225A - High molecular compound, resist material and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist material having small absorption at the wavelength of F2 excimer laser light for exposure and capable of easily forming a fine pattern perpendicular to a substrate. SOLUTION: The high molecular compound has repeating units of formula (1) (where A is a divalent organic group and forms a 4-20C cyclic hydrocarbon group together with C atoms which bond at both ends of A, the cyclic hydrocarbon group may be a bridged cyclic group and may contain a heteroatom; R<1> -R<3> are each H, F, a 1-4C alkyl or a 1-4C fluorinated alkyl, at least one of R<1> -R<3> contains F; and R<4> is an acid labile group). The resist material is sensitive to high energy beams and is excellent in sensitivity and resolution at <=200 nm, particularly <=170 nm wavelength and in plasma etching resistance.

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 containing the same, and a pattern forming method using the same.

[0002]

2. Description of the Related Art LSI
With the increase in integration and speed of devices, pattern rules are rapidly becoming finer. Background of the rapid progress of miniaturization include higher NA of the projection lens, improved resist performance, and shorter wavelength.

In particular, from the i-line (365 nm) to KrF (24
8 nm) has brought about a major change, with 0.1
Mass production of 8 μm rule devices is becoming possible. In order to improve the resolution and sensitivity of resist, a chemically amplified positive resist material using an acid as a catalyst (Japanese Patent Publication No. 2-27)
660 and JP-A-63-27829) have excellent characteristics and have become a mainstream resist material particularly in deep ultraviolet lithography.

[0004] Resist materials for KrF excimer lasers have generally begun to be used in 0.3 micron processes,
After the 0.25 micron rule, the 0.18 micron rule is now being applied to mass production, and the 0.15 micron rule has begun trial production, and the 0.13 micron rule is being studied. It is being accelerated. Kr
Shortening the wavelength from F to ArF (193 nm) is expected to reduce the design rule to 0.13 μm or less. However, novolak or polyvinylphenol-based resins which have been conventionally used have been reduced to around 193 nm. Since it has very strong absorption, it cannot be used as a base resin for resist. In order to ensure transparency and required dry etching resistance, acrylic and cycloolefin-based alicyclic resins have been studied (JP-A-9-73173, JP-A-10-10739, and JP-A-9-10739). −230
595, WO 97/33198). 0.10
For F ₂ (157 nm), which can be expected to be finer than μm, it is increasingly difficult to ensure transparency. Acrylics do not transmit light at all, and cycloolefins having a carbonyl bond have strong absorption. I found it to have. A polymer having a benzene ring slightly improves transmittance at a wavelength of about 160 nm, but is far from a practical value, and is represented by a carbon-carbon double bond represented by a benzene ring and a carbonyl group in a single-layer resist. Carbon oxygen 2
It has been found that reducing heavy coupling is a necessary condition for ensuring transmittance (International W
ork Shop 157nm Lithograph
y MIT-LL Boston, MA May
5, 1999). It has been shown that the introduction of fluorine is effective for improving the transmittance (J. Vac. S.
ci. Technol. B 17 (6), Nov
/ Dec 1999), many fluorine-containing polymers for resists have been proposed (J. Photopolyme).
r Sci. and Technol. Vol.
13 No. 4 (2000) p657-664 an
d Vol. 13 No. 4 (2000) p451
-458) is polyhydroxystyrene and its derivative in KrF exposure, and poly (meth) in ArF exposure.
It does not reach the transmittance of acrylic derivatives or polycycloolefin derivatives.

On the other hand, it has been known that a two-layer resist method is excellent for forming a pattern having a high aspect ratio on a stepped substrate. Further, the two-layer resist film is developed with a general alkali developing solution. To do so, a high molecular silicone compound having a hydrophilic group such as a hydroxy group or a carboxyl group is required.

As a silicone-based chemically amplified positive resist material, a base resin obtained by protecting a part of phenolic hydroxyl groups of polyhydroxybenzylsilsesquioxane, which is a stable alkali-soluble silicone polymer, with t-Boc groups is used. , A silicone-based chemically amplified positive resist material for KrF combining this with an acid generator has been proposed (Japanese Patent Application Laid-Open No. Hei 7-118651, SPIE).
vol. 1925 (1993) p377). Ar
For F, a positive resist based on silsesquioxane in which cyclohexylcarboxylic acid is substituted with an acid labile group has been proposed (JP-A-10-324).
748, JP-A-11-302382, SP
IE vol. 3333-07 (1998) p6
2). Further, a silicone-containing polymer using a silicon-containing acrylic monomer has also been proposed (JP-A-9-110).
No. 938, J.C. Photopolymer Sc
i. and Technol. Vol. 9 N
o. 3 (1996) p435-446).

A disadvantage of the acrylic pendant silicon-containing polymer is that its dry etching resistance in oxygen plasma is weaker than that of silsesquioxane-based polymers. This is due to the low silicon content and
The difference in the polymer main skeleton is cited as a reason. Also,
The siloxane pendant type has the disadvantage that the developer is easily repelled and the wettability of the developer is poor. In view of this, there has been proposed a polymer of a trisilane or tetrasilane pendant type which has a higher silicon content and further contains a repeating unit in which a silicon-containing group has acid elimination property (SPIEv).
ol. 3678 p214, p241, p562). However, at a wavelength of 200 nm or less, a silane compound of disilane or more has a strong absorption, and thus has a disadvantage in that the transmittance is reduced when the introduction rate is increased. Attempts have also been made to incorporate an acid labile group silicon in addition to the above (SPIE vol. 3678).
p420), and the acid desorption performance is low, so that there are drawbacks such as low environmental stability and easy formation of a T-top profile.

On the other hand, the present applicant has proposed an acid labile group in which silicon has been introduced into a cyclic hydrocarbon group (Japanese Patent Application No. Hei 11-1999).
342380). This is excellent in acid elimination property,
It has the advantage of preventing the occurrence of top profiles. In addition, silicon is contained in one cyclic hydrocarbon group.
It is possible to increase the dry etching resistance by introducing more than one. In addition, it also has a feature that carbon atoms are present between silicon atoms, and there is no fear of lowering the transmittance in ArF without generating a disilane bond.

[0009] However, the silicone-containing polymer is certainly advantageous in terms of transmittance as compared with a single-layer resist because it can be made thinner. Needed.

The present invention has been made in order to meet the above-mentioned demands, and has been made to have a thickness of 300 nm or less, particularly ArF (193 nm),
F ₂ (157 nm), Kr ₂ (146 nm), KrAr
(134 nm), resist material excellent in vacuum ultraviolet light transmittance such as Ar ₂ (126 nm) and dry etching resistance, especially a novel polymer compound useful as a base polymer of a chemically amplified resist material, and a resist material containing the same An object is to provide a pattern forming method using a resist material.

[0011]

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 cycloolefin carboxyl group having a fluorine atom substituted by an acid labile group has been obtained. The present inventors have found that the use of a pendant silsesquioxane as a base resin can provide a resist material having both transparency and dry etching resistance, and have accomplished the present invention.

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

Embedded image (Wherein A is a divalent organic group, and may be a bridged cyclic group having 4 to 20 carbon atoms which may contain a hetero atom together with carbon atoms bonded at both ends of A) R ¹ , R ² , and R ^{3 each} represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl group having 1 to 4 carbon atoms; ¹ , R
^At least one of R ² and R ³ contains a fluorine atom. R ⁴
Is an acid labile group. Claim 2: A resist material comprising the polymer compound according to claim 1. Claim 3: (A) the polymer compound according to claim 1, (B) an organic solvent,
(C) A chemically amplified resist material comprising an acid generator. In a preferred embodiment, the resist composition further comprises (D) a basic compound. Claim 5: Claim 3 further comprising (E) a dissolution inhibitor.
Or the resist material according to 4. Claim 6: (1) a step of applying the resist material according to any one of claims 2 to 5 on a substrate; and (2) a high energy ray having a wavelength of 300 nm or less via a photomask after a heat treatment. Alternatively, a pattern forming method comprising: a step of exposing to an electron beam; and (3) a step of performing a heat treatment as necessary and then developing with a developer. In a preferred embodiment, the resist pattern is formed by processing the base by etching including oxygen plasma etching after forming the pattern. In a preferred embodiment, after forming the pattern, the resist pattern is formed by etching the base by etching with a halogen gas containing chlorine or bromine.

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).

[0014]

Embedded image (Wherein A is a divalent organic group, and may be a bridged cyclic group together with carbon atoms bonded at both ends of A and may contain a heteroatom such as oxygen or sulfur. Forming a cyclic hydrocarbon group having a number of 4 to 20, preferably 4 to 16. R ¹ , R ² , and R ³ are a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms; Wherein at least one of R ¹ , R ² and R ³ contains a fluorine atom, and R ⁴ is an acid labile group.)

Here, as the repeating unit in the general formula (1), specifically, the following formulas (1) -1 to (1) -20
Can be mentioned.

[0016]

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[0017]

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The acid labile group of R ⁴ may be variously selected. In particular, the groups represented by the following formulas (A-1) and (A-2) and the carbon represented by the following formula (A-3) A tertiary alkyl group having 4 to 40 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms,
It is preferably an oxoalkyl group having 4 to 20 carbon atoms.

[0019]

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In the formula (A-1), R ³⁰ has 4 carbon atoms.
To 20, 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 formula (A-3) Tert-butyl group, tert-amyl group, 1,1-diethylpropyl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group A 1-butylcyclohexyl group, a 1-ethyl-2-cyclopentenyl group, a 1-ethyl-2-cyclohexenyl group, a 2-methyl-2-adamantyl group, and the like. Specific examples of the trialkylsilyl group include: Trimethylsilyl group, triethylsilyl group, dimethyl-t
tert-butylsilyl group and the like. Specific examples of the oxoalkyl group include a 3-oxocyclohexyl group,
-Methyl-2-oxooxan-4-yl group, 5-methyl-2-oxooxolan-5-yl group and the like. a1 is an integer of 0 to 6.

In the formula (A-2), R ³¹ and R ^{32 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. Methyl group, ethyl group, propyl group, isopropyl group, n
-Butyl group, sec-butyl group, tert-butyl group,
Examples thereof include a cyclopentyl group, a cyclohexyl group, a 2-ethylhexyl group, and an n-octyl group. R ³³ represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms, and preferably 1 to 10 carbon atoms;
A branched or cyclic alkyl group, and those in which a part of these hydrogen atoms are substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group, and the like, and specifically, the following substituted alkyl And the like.

[0022]

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R ³¹ and R ³² , R ³¹ and R ³³ , R ³²
And R ³³ may form a ring, and when forming a ring, R ³¹ , R ³² and R ³³ each have 1 to 18 carbon atoms;
It preferably represents 1 to 10 linear or branched alkylene groups.

The acid labile group of the above formula (A-1) includes
Specifically, a 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-
Examples thereof include an ethyl-2-cyclopentenyloxycarbonylmethyl group, a 1-ethoxyethoxycarbonylmethyl group, a 2-tetrahydropyranyloxycarbonylmethyl group, and a 2-tetrahydrofuranyloxycarbonylmethyl group.

Further, the following formulas (A-1) -1 to (A-1)
A substituent represented by -9 can also be mentioned.

[0026]

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Here, R ³⁷ is the same or different and is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ³⁸ is a hydrogen atom or a carbon atom. It is a linear, branched or cyclic alkyl group of the formulas 1 to 10.

^{Further, R 39} are each the same or different number 2-10 straight, branched or cyclic alkyl group, or an aryl group having 6 to 20 carbon atoms.

Among the acid labile groups represented by the above formula (A-2), those having a linear or branched structure are represented by the following formula (A-
2) -1 to (A-2) -23 can be exemplified.

[0030]

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[0031]

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Among the acid labile groups represented by the above formula (A-2), cyclic groups include tetrahydrofuran-2-
An yl group, a 2-methyltetrahydrofuran-2-yl group,
Examples include a tetrahydropyran-2-yl group and a 2-methyltetrahydropyran-2-yl group.

The formula (A-2a) or (A-
The base resin may be cross-linked intramolecularly or intramolecularly by the acid labile group represented by 2b).

[0034]

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In the formula, R ⁴⁰ and R ⁴¹ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁴⁰ and R ⁴¹ may combine to form a ring, and when forming a ring, R ⁴⁰ and R ^{41 each} have 1 to 1 carbon atoms.
8 represents a linear or branched alkylene group. R ⁴² is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and b and d are 0 or 1 to 10, preferably 0 or 1 to 5;
And c is an integer of 1 to 7. A represents a (c + 1) -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; Alternatively, part of a hydrogen atom bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, a carbonyl group, or a fluorine atom. B is -CO-O-, -NHCO-O- or -NHC
ONH- is shown.

In this case, A is preferably a divalent, tetravalent, branched or cyclic alkylene group having 1 to 20 carbon atoms, an alkyltriyl group, an alkyltetrayl group, and a C6 to C30 carbon atom. 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 with a hydroxyl group, a carboxyl group, an acyl group or a halogen atom. C is preferably an integer of 1 to 3.

The crosslinked acetal groups represented by the general formulas (A-2a) and (A-2b) are specifically represented by the following formula (A-
2) -24 to (A-2) -31.

[0038]

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Next, in formula ^{(A-3) R 34,} R
³⁵ and R ³⁶ are monovalent hydrocarbon groups such as linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, and include oxygen,
Sulfur, nitrogen, may contain a hetero atom such as fluorine,
The R ³⁴ and ^{R 35, R 34} and ^{R 3 6, R 35} and ^{R 36} combine with each other together with the carbon atoms to which they are attached, may form a ring having 3 to 20 carbon atoms.

The tertiary alkyl group represented by the formula (A-3) includes a tert-butyl group, a triethylcarbyl group,
1-ethylnorbonyl group, 1-methylcyclohexyl group, 1-ethylcyclopentyl group, 2- (2-methyl)
An adamantyl group, a 2- (2-ethyl) adamantyl group,
A tert-amyl group and the like can be mentioned.

Further, specific examples of the tertiary alkyl group include the following formulas (A-3) -1 to (A-3) -18.

[0042]

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In the formulas (A-3) -1 to (A-3) -18,
R ⁴³ represents the same or different linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or an aryl group such as a phenyl group having 6 to 20 carbon atoms. R ⁴⁴ and R ⁴⁶ are a hydrogen atom,
Or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ⁴⁵ represents an aryl group such as a phenyl group having 6 to 20 carbon atoms.

Further, the following formulas (A-3) -19 and (A-3)
As shown in -20, divalent or higher alkylene group, include R ⁴⁷ is an arylene group, within the molecule or between molecules of the polymer may be crosslinked. Formula (A-3) -1
9, in ^{(A-3) -20, R} 4 3 is similar to the ^{above, R 47}
Represents a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group such as a phenylene group;
It may contain a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom. b1 is an integer of 1 to 3.

[0045]

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Further, R ³⁴ , R ³⁵ and R ³⁵ in the formula (A-3)
R ³⁶ can be mentioned oxygen, nitrogen, may have a hetero atom such as sulfur, in particular those of the following formula (A) -1~ (A) -7 .

R ³⁰ , R ³³ and R ³⁶ in the formulas (A-1), (A-2) and (A-3) each represent a phenyl group, a p-methylphenyl group, a p-ethylphenyl group or a p-ethylphenyl group. An unsubstituted or substituted aryl group such as an alkoxy-substituted phenyl group such as a methoxyphenyl group, an aralkyl group such as a benzyl group or a phenethyl group, or a hydrogen atom having an oxygen atom in these groups or a hydrogen atom bonded to a carbon atom is a hydroxyl group. Replaced or 2
Alkyl groups represented by the following formulas (A) -1 to (A) -7 in which hydrogen atoms are replaced by oxygen atoms to form a carbonyl group, or formula (A) -8, (A) -9 And an oxoalkyl group represented by

[0048]

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The trialkylsilyl groups having 1 to 6 carbon atoms as the alkyl groups used as the acid labile groups include trimethylsilyl group, triethylsilyl group,
a tert-butyldimethylsilyl group;

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

[0051]

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The polymer compound of the present invention may have a repeating unit represented by the following general formula (1 ′) in addition to the unit represented by the above formula (1).

[0053]

Embedded image (In the formula, R ¹ , R ² , and R ³ are the same as described above.)

In the polymer compound of the present invention, the substitution rate by the acid labile group is preferably partial substitution from the viewpoints of alkali solubility and developer wettability, and is preferably 10 to 90 mol%, more preferably. Is from 20 to 70 mol%.

In the case of producing the above-mentioned polymer compound, as an example, generally, a method of synthesizing a trichlorosilane or trialkoxysilane monomer by the following synthesis method and polymerizing it by a hydrolysis reaction can be mentioned. The acid labile group may be introduced by substituting the hydroxy group of the carboxylic acid of the monomer before polymerization, or may substitute the hydroxy group of the carboxylic acid of the polymer after polymerization.

[0056]

Embedded image Here, X is a single bond, a methylene group, an ethylene group, an oxygen atom, or a sulfur atom.

The polymer compound of the present invention is represented by the following formulas (2) -1 to (2) -24 in addition to the units of the formula (1) in order to improve alkali solubility, transparency, adhesion and the like. The repeating unit containing the fluorinated alcohol can also be copolymerized.

[0058]

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[0059]

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[0060]

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Further, in order to improve the adhesion and the alkali solubility, a repeating unit containing a hydrophilic group represented by the following formulas (3) -1 to (3) -84 can be introduced.

[0062]

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[0063]

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[0064]

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[0065]

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Further, in order to improve transparency or optimize the molecular weight, a repeating unit having a pendant alkyl group or fluorinated alkyl represented by the following formulas (4) -1 to (4) -4 may be contained. it can.

[0067]

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(Wherein R ³ is a straight-chain having 1 to 20 carbon atoms;
Branched or cyclic unsubstituted or substituted C 1-10
And the substituted alkyl group includes a fluorinated alkyl group. c to f are 0 ≦ c
<1, 0 ≦ d <1, 0 ≦ e <1, 0 ≦ f <1. )

The polymer compound of the present invention has a weight average molecular weight of 1,000 to 100,000, preferably 1,
500-50,000.

The polymer compound of the present invention comprises a resist material,
Particularly, it is suitably used as a base resin of a chemically amplified resist material, especially a chemically amplified positive resist material. In this case, the chemically amplified positive resist material of the present invention comprises (A)
It may contain a base resin composed of the above polymer compound, (B) an acid generator, and (C) an organic solvent, and more preferably contain (D) a dissolution inhibitor and (E) a basic compound.

Here, the acid generator used in the resist composition of the present invention includes an onium salt represented by the following general formula (6):
Examples include a diazomethane derivative of the formula (7), a glyoxime derivative of the formula (8), a β-ketosulfone derivative, a disulfone derivative, a nitrobenzylsulfonate derivative, a sulfonate derivative, and an imido-ylsulfonate derivative.

(R ⁵¹ ) _c M ⁺ K ⁻ (6) (provided that R ⁵¹ may be the same or different and has 1 carbon atom)
Represents a linear, branched or cyclic alkyl group having from 12 to 12, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, M ⁺ represents iodonium or sulfonium,
K ^- is a non-nucleophilic counter-ion, c is 2 or 3. )

The alkyl group for R ⁵¹ 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 2,3,4,5,6-pentafluorobenzenesulfonate, and alkylsulfonates such as mesylate and butanesulfonate.

[0074]

Embedded image (However, R ⁵² and R ⁵³ may be the same or different and each may be 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 alkyl group. Represents an aryl group or an aralkyl group having 7 to 12 carbon atoms.)

The alkyl group for R ⁵² and R ⁵³ includes 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 adamantyl groups. Examples of the halogenated alkyl group include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,2-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 fluorophenyl group, a chlorophenyl group, a 2,3,4,5,6-pentafluorophenyl group, and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0076]

Embedded image (However, R ⁵⁴ , R ⁵⁵ and R ⁵⁶ 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 an aralkyl group having 7 to 12. ^Moreover, R ^{55, R 5 6} may be bonded together to form a ring structure together, when they form a ^{ring, R} 5 ^{5, R 56} each having a carbon number of 1 Represents a linear or branched alkylene group of 1 to 6)

The alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group represented by R ⁵⁴ , R ⁵⁵ and R ⁵⁶ include the same groups as those described for R ⁵² and R ⁵³ . In addition, as an alkylene group of R ⁵⁵ and R ^56, 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-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, 5-norbornene-2,3-dicarboximido-yl-n-butylsulfonate, etc., 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, and naphthoquinonediazidosulfonic acid ester derivatives 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, the fine adjustment of the profile can be performed by combining the two.

The compounding amount of the acid generator is 100
Parts (parts by weight, hereinafter the same) is preferably from 0.2 to 50 parts, particularly from 0.5 to 40 parts. The resolution may be inferior. If it exceeds 50 parts, the transmittance of the resist may decrease, and the resolving power may deteriorate.

The organic solvent used in the resist composition of the present invention may be any organic solvent capable of dissolving an acid generator, a base resin, a dissolution inhibitor and the like. Such organic solvents include, for example, cyclohexanone, methyl-
Ketones such as 2-n-amyl ketone, alcohols such as 3-methoxybutanol, 3-methyl-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, 3
Esters such as ethyl ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol-mono-tert-butyl ether acetate; one of these being used 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, And a mixed solvent thereof are preferably used.

As the dissolution inhibitor used in the resist composition of the present invention, compounds having a molecular weight of 3,000 or less, whose solubility in an alkali developing solution is changed by the action of an acid, and especially compounds having a molecular weight of 2,000 or less,
Compounds in which part or all of a low-molecular-weight phenol or carboxylic acid derivative having a molecular weight of 500 or less are substituted with an acid-labile substituent are exemplified. The acid labile group is (A-
Those similar to 1) to (A-8) can be used.

Examples of the phenol or carboxylic acid derivative 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 ′
-Methylene bis [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, and examples of the acid-labile substituent include those similar to the above.

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 determined by the amount of base resin 10 in the resist material.
It is 20 parts or less, preferably 15 parts or less with respect to 0 parts. If the amount is more than 20 parts, the monomer component increases and the heat resistance of the resist material decreases.

As the basic compound used in the resist composition of the present invention, a compound capable of suppressing the rate of diffusion of the acid generated from the acid generator into the resist film is suitable. By blending of basic compounds,
The diffusion rate of the acid in the resist film is suppressed, the resolution is improved, the sensitivity change after exposure can be suppressed, the dependency on the substrate and the environment can be reduced, and the exposure margin and pattern profile can be improved. (JP-A-5-232706, JP-A-5-249683, JP-A-5-158239, and JP-A-5-239.
49662, 5-257282, 5-2893
No. 22, No. 5-289340, etc.).

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, 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.

Examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (eg, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine,
Histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine), and the like. Pyridinium p-toluenesulfonate and the like are exemplified. Examples of the nitrogen-containing compound having a hydroxy group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, and 2,4-quinolinediol. , 3-indolemethanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-imino Diethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1
-Butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2
-Hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine,
1- (2-hydroxyethyl) -2-pyrrolidinone, 3
-Piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyurolidine, 3-quinuclidinol, 3-tropanol,
Examples thereof include 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, and N- (2-hydroxyethyl) isonicotinamide. Examples of the amide derivative include formamide, N-methylformamide, N, N-dimethylformamide, acetamido, N-methylacetamido,
Examples include N-dimethylacetamide, propionamide, benzamide and the like. Examples of the imide derivative include phthalimide, succinimide, and maleimide.

Further, one or more kinds of basic compounds represented by the following general formula (B) -1 can be added. N (X) _n (Y) _3-n (B) -1 wherein n = 1, 2 or 3. The side chains X may be the same or different and can be represented by the following general formulas (X) -1 to (X) -3. The side chain Y is the same or different and represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may include an ether group or a hydroxyl group. Further, Xs may be bonded to each other to form a ring.

Here, R ³⁰⁰ , R ³⁰² and R ³⁰⁵ are linear or branched alkylene groups having 1 to 4 carbon atoms.
R ³⁰¹ and R ³⁰⁴ are a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may include one or more hydroxy groups, ether groups, ester groups, and lactone rings.

R³⁰³Is a single bond, a straight chain having 1 to 4 carbon atoms
And branched alkylene groups; ³⁰⁶Is 1 carbon
From 20 to 20 linear, branched or cyclic alkyl groups
, Hydroxy group, ether group, ester group, lactone
One or more rings may be included.

[0093]

Embedded image

The compound represented by formula (B) -1 is specifically exemplified below. Tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl {Amine, Tris} 2- (1-
Ethoxyethoxy) ethyl} amine, tris {2- (1
-Ethoxypropoxy) ethyl} amine, tris [2-
{2- (2-hydroxyethoxy) ethoxy} ethyl]
Amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.88] 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, tris (2-formyloxyethyl) amine, tris (2-formyloxyethyl) amine, tris (2
-Acetoxyethyl) amine, tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, Tris (2-pivaloyloxyxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-te
rt-butoxycarbonyloxyethyl) amine, tris [2- (2-oxopropoxy) ethyl] amine, tris [2- (methoxycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycarbonylmethyloxy) ethyl] Amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl]
Amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine,
N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2 -(Ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2
-Methoxyethoxycarbonyl) ethylamine, N, N
-Bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-
(Hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2
-[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-
[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2-
(2-oxopropoxycarbonyl) ethylamine,
N, N-bis (2-acetoxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis ( 2
-Acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N,
N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2
-(4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(2-formyloxyethoxycarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N -(2-acetoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2 -(Ethoxycarbonyl) ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl)
Ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2-
(Methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl]
Amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine,
N-methylbis (2-pivaloyloxyxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert
-Butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, β- (diethylamino) Examples thereof include, but are not limited to, -δ-valerolactone.

Further, one or more basic compounds having a cyclic structure represented by the following general formula (B) -2 may be added.

[0096]

Embedded image (Wherein, X is as described above, R ³⁰⁷ is a linear or branched alkylene group having 2 to 20 carbon atoms, and a carbonyl group;
It may contain one or more ether groups, ester groups and sulfides. )

Formula (B) -2 specifically, 1- [2
-(Methoxymethoxy) ethyl] pyrrolidine, 1- [2
-(Methoxymethoxy) ethyl] piperidine, 4- [2
-(Methoxymethoxy) ethyl] morpholine, 1- [2
-[(2-methoxyethoxy) methoxy] ethyl] pyrrolidine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] piperidine, 4- [2-[(2-methoxyethoxy) methoxy] ethyl] morpholine, Acetic acid 2-
(1-pyrrolidinyl) ethyl, 2-piperidinoethyl acetate, 2-morpholinoethyl acetate, 2- (1-pyrrolidinyl) ethyl formate, 2-piperidinoethyl propionate,
2-morpholinoethyl acetoxyacetate, methoxyacetic acid 2
-(1-pyrrolidinyl) ethyl, 4- [2- (methoxycarbonyloxy) ethyl] morpholine, 1- [2-
(T-butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, methyl 3-piperidinopropionate, 3- Methyl morpholinopropionate, methyl 3- (thiomorpholino) propionate, 2-methyl-3- (1
Methyl-pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, methoxycarbonylmethyl 3-piperidinopropionate, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 3 -(1-Pyrrolidinyl) propionic acid 2-oxotetrahydrofuran-3-
Yl, tetrahydrofurfuryl 3-morpholinopropionate, glycidyl 3-piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate, 3- (1-
2- (2-methoxyethoxy) ethyl pyrrolidinyl) propionate, butyl 3-morpholinopropionate, 3-
Cyclohexyl piperidinopropionate, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate , Methyl thiomorpholinoacetate, ethyl 1-pyrrolidinyl acetate, and 2-methoxyethyl morpholinoacetate.

Further, basic compounds containing a cyano group represented by formulas (B) -3 to (B) -6 can be added.

[0099]

Embedded image ( ^Where X, R ³⁰⁷ , and n are R ³⁰⁸ , R
³⁰⁹ is the same or different linear or branched alkylene group having 1 to 4 carbon atoms. )

The base containing a cyano group is specifically
(Diethylamino) propiononitrile, N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile, N, N-bis (2-acetoxyethyl) -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N,
N-bis (2-methoxyethyl) -3-aminopropiononitrile, N, N-bis [2- (methoxymethoxy)
Ethyl] -3-aminopropiononitrile, N- (2-
Methyl cyanoethyl) -N- (2-methoxyethyl) -3-aminopropionate, N- (2-cyanoethyl)-
Methyl N- (2-hydroxyethyl) -3-aminopropionate, N- (2-acetoxyethyl) -N- (2-
Methyl cyanoethyl) -3-aminopropionate, N-
(2-cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-
Hydroxyethyl) -3-aminopropiononitrile,
N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-
Aminopropiononitrile, N- (2-cyanoethyl)
-N- (2-methoxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- (2-cyanoethyl ) -N- (3-hydroxy-1-propyl) -3-aminopropiononitrile;
N- (3-acetoxy-1-propyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N-
(2-cyanoethyl) -N- (3-formyloxy-1
-Propyl) -3-aminopropiononitrile, N-
(2-cyanoethyl) -N-tetrahydrofurfuryl-
3-aminopropiononitrile, N, N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N, N-bis (2-hydroxyethyl) aminoacetonitrile, N, N-bis (2-
(Acetoxyethyl) aminoacetonitrile, N, N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2-methoxyethyl) aminoacetonitrile, N, N-bis [2- (methoxymethoxy) ethyl] amino Acetonitrile, N-cyanomethyl-N-
Methyl (2-methoxyethyl) -3-aminopropionate, N-cyanomethyl-N- (2-hydroxyethyl)
Methyl-3-aminopropionate, N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate, N-cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile, N- (2-acetoxyethyl ) -N- (cyanomethyl) aminoacetonitrile;
N-cyanomethyl-N- (2-formyloxyethyl)
Aminoacetonitrile, N-cyanomethyl-N- (2-
Methoxyethyl) aminoacetonitrile, N-cyanomethyl-N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N- (3-hydroxy-1-propyl) aminoacetonitrile, N-
(3-acetoxy-1-propyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N-
(3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidinepropiononitrile, 1-piperidinepropiononitrile, 4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidine acetonitrile, 4-morpholine acetonitrile,
Cyanomethyl 3-diethylaminopropionate, N, N
Cyanomethyl-bis (2-hydroxyethyl) -3-aminopropionate, cyanomethyl N, N-bis (2-acetoxyethyl) -3-aminopropionate, N, N-
Cyanomethyl bis (2-formyloxyethyl) -3-aminopropionate, cyanomethyl N, N-bis (2-methoxyethyl) -3-aminopropionate, N, N-
Cyanomethyl bis [2- (methoxymethoxy) ethyl] -3-aminopropionate, 2-diethylaminopropionic acid (2-cyanoethyl), N, N-bis (2-hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl) ), N, N-bis (2-acetoxyethyl) -3
-Aminopropionic acid (2-cyanoethyl), N, N-
Bis (2-formyloxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis [2 -(Methoxymethoxy) ethyl] -3-aminopropionic acid (2-cyanoethyl),
Cyanomethyl 1-pyrrolidinepropionate, cyanomethyl 1-piperidinepropionate, cyanomethyl 4-morpholinepropionate, 1-pyrrolidinepropionate (2
-Cyanoethyl), 1-piperidinepropionic acid (2-
Cyanoethyl) and 4-morpholinepropionic acid (2-cyanoethyl).

The basic compound of the present invention is compounded in an amount of 0.001 to 2 parts, especially 0.1 to 2 parts, based on 100 parts of the total base resin.
01 to 1 part is preferred. If the amount is less than 0.001 part, the compounding effect is not obtained, and if the amount is more than 2 parts, the sensitivity may be excessively lowered.

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

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

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.

FIG. 1 shows a method of forming a silicon-containing resist pattern by exposure, PEB, and development, forming an underlying organic film pattern by oxygen gas etching, and processing the film to be processed by dry etching. here,
In FIG. 1A, 1 is a base substrate, 2 is a substrate to be processed (SiO ₂ , SiN, etc.), 3 is an organic film (novolak, polyhydroxystyrene, etc.), 4 is a silicon-containing polymer compound according to the present invention. As shown in FIG. 1B, a required portion of the resist layer is exposed to light 5 and further, as shown in FIG.
B, development is performed to remove the exposed region, and further, oxygen plasma etching is performed as shown in FIG. 1 (D), and the substrate to be processed is etched (CF-based gas) as shown in FIG. 1 (E). It can be patterned.

Here, oxygen gas etching uses oxygen gas.
Reactive plasma etching, the main component of which
The underlying organic film can be processed at the spect ratio. acid
T-top shape by over etching in addition to raw gas
SO to protect sidewalls₂And
N₂, CO₂, CO gas may be added. Also, development
Removes resist scum afterwards and smoothes line edges
Oxygen gas etching to prevent roughness
Etching with a short time CFC-based gas before
Both are possible. Next, dry etching of the film to be processed is performed.
In the process, the film to be processed is SiO₂And Si₃N₄Then
The etching is mainly performed by using an etching gas. Freon system
The gas is CF₄, CHF₃, CF₂F₂, C₂F₆, C₃
F₈, C₄F ₁₀, C₅F₁₂And the like. this
At the same time, the silicon-containing layer
It is possible to remove the dist film. The film to be processed is poly
Silicon, tungsten silicide, TiN / Al, etc.
In the case of, etching with chlorine and bromine gas as main components
Do.

The silicon-containing resist of the present invention has excellent resistance to etching mainly containing chlorine and bromine gas, and the same processing method as that for a single-layer resist can be used.

FIG. 2 shows this. In FIG. 2 (A), reference numeral 1 denotes an undersubstrate, 6 denotes a substrate to be processed, 4 denotes the above-described resist layer, and FIGS. As shown, after exposure 5, PEB, and development are performed, the substrate to be processed (Cl-based gas) can be performed as shown in FIG. 2 (D). The silicon-containing resist film of the present invention is formed into a pattern, and the film to be processed can be processed by etching mainly containing chlorine and bromine gas.

[0109]

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.

[0110]

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 2-tert-butoxycarbonyl-2-trifluoromethyl-5 (6) -trichlorosilylnorbornane 30 equipped with a stirrer, reflux condenser, dropping funnel and thermometer.
In a 0 ml flask, fresh cyclopentadiene (14.5 g) obtained as a pyrolysis fraction of dicyclopentadiene
And benzene (75 ml) were charged, and tert-butyl 2-trifluoromethylacrylate (39.2 g) was added dropwise while paying attention to heat generation. After the temperature rise was no longer observed, the mixture was heated under reflux for 4 hours, the solvent was distilled off, and the residue was distilled under reduced pressure.
-Trifluoromethyl-2-tert-butoxycarbonyl-5-norbornene (28.9 g) was obtained. 300 m with stirrer, reflux condenser, dropping funnel and thermometer
of the above norbornene derivative (28.0)
g), a 20% by weight chloroplatinic acid-isopropanol solution (0.1 g) and isooctane (150 ml) were charged,
Heated to 80 ° C. After the internal temperature was stabilized, trichlorosilane (15.9 g) was added dropwise over 1 hour. 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 give 2-trifluoromethyl-2- represented by the following formula.
tert-butoxycarbonyl-5 (6) -trichlorosilylnorbornane (boiling point 110-114 ° C / 0.1 m
mHg, 34.0 g).

[0112]

Embedded image

[Synthesis Example 2] Triethylamine (2-ethyloxy-2-trifluoromethyl-5 (6) -trichlorosilylnorbornane) was placed in a 2000 ml flask equipped with a chiller-type reflux condenser, a dropping funnel equipped with a cold jacket, and a thermometer. 161.9 g), acetyl chloride (113.
0g) and 1,2-dichlorobenzene (500 ml) were charged at 80 ° C. in 1,1,1-trifluoroacetone (8
9.6 g) was added dropwise over 4 hours, and the mixture was heated and aged for 2 hours. After cooling, the mixture was poured into ice water (1,000 g), and the organic layer was washed with water (200 ml × 2), dried over sodium sulfate, filtered and distilled to give 1,1,1-trifluoromethyl-2-propenyl acetate. (Boiling point 75-77 ° C, 96.
2g). In a 1,000 ml autoclave, the above 1,1,1-trifluoromethyl-2-propenyl acetate (9
5.0 g) and dicyclopentadiene (48.9 g) were charged and stirred at 180 ° C. for 15 hours. The reaction mixture was distilled under reduced pressure to give 5-acetoxy-5-trifluoromethyl-2.
To obtain norbornene (boiling point 90 to 94 ° C./30 mmH
g, 47.5 g). In a 1,000 ml flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, the norbornene derivative (47.0 g), a 20 wt% chloroplatinic acid-isopropanol solution (0.2 g), and isooctane (250 ml) were placed. ) And heated to 80 ° C. After the internal temperature was stabilized, trichlorosilane (31.8 g) was added dropwise over 1 hour. 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 give 2-acetoxy-2-trifluoromethyl-5 (6) -trichlorosilylnorbornane (boiling point: 76 to 80 ° C / 0.1 mmHg, 63.8).
g) was obtained.

[Synthesis Example 3] (2-acetoxy-2,2-
Bistrifluoromethyl) ethyl-5 (6) -trichlorosilylnorbornane In a 200 ml autoclave, dicyclopentadiene (13.2 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). A 200 ml flask was charged with sodium hydride (1.9 g) and tetrahydrofuran (90 ml), and the above norbornene derivative (1) was added.
A solution of 8.0 g) in tetrahydrofuran (90 ml) was added dropwise, 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 ice-cooled aqueous sodium hydrogen carbonate solution, and the aqueous layer was extracted with diethyl ether. The organic layer was washed with saturated saline, 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 5-
(2-acetoxy-2,2-bistrifluoromethyl)
Ethyl-2-norbornene (16.6 g) was obtained. 100 ml with stirrer, reflux unit, dropping funnel and thermometer
In the three-necked flask, the above norbornene derivative (9.
0 g), a 20 wt% chloroplatinic acid-isopropanol solution (0.009 g), and isooctane (15 ml) were charged 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-5 (6) -trichlorosilylnorbornane (8.2 g) as a fraction having a boiling point of 98 to 102 ° C./10 Pa.

Synthesis Example 4 Polymer (I) Triethylamine (60.7 g), toluene (40.7 g) were placed in a 500 ml flask equipped with a stirrer, a dropping funnel and a thermometer.
0 ml), methyl isobutyl ketone (40 ml) and water (80 ml), and the 2-t obtained in Synthesis Example 1 under ice-cooling.
tert-butoxycarbonyl-2-trifluoromethyl-5 (6) -trichlorosilylnorbornane (19.8
9 g) and a mixture of 2-acetoxy-2-trifluoromethyl-5 (6) -trichlorosilylnorbornane (17.78 g) obtained in Synthesis Example 2 were 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 became 8 or less, concentrated, and then diluted with toluene (150%).
ml) and filtered into a 1,000 ml flask. The temperature was gradually raised on a heating bath to distill off toluene, and 20
The mixture was stirred at 0 ° C. for 12 hours to obtain a polymer having a weight average molecular weight of 4,200 (28.84 g). After cooling, potassium carbonate (27.1 g), methanol (300 ml), tetrahydrofuran (300 ml), and water (120 ml) were added.
Stirred at room temperature for 15 hours. The organic solvent was distilled off, and ethyl acetate (500 ml) and a saturated aqueous ammonium chloride solution (10
0 ml) and water (100 ml) were added and shaken, and the organic layer was washed with water (50 ml × 5). The solvent was distilled off and 40
Vacuum dried at 15 ° C. for 15 hours to obtain 26.24 g of a solid. As a result of GPC, NMR and IR analysis, it was confirmed that this product was a polymer compound having a weight average molecular weight of 4,100 and a molecular weight dispersity of 1.10, and had a structure of the following formula (I).

[0116]

Embedded image

[Synthesis Example 5] Polymer (II) 2-acetoxy-2-trifluoromethyl-5 (6)-
The following formula was prepared in the same manner as in Synthesis Example 4 except that (2-acetoxy-2,2-bistrifluoromethyl) ethyl-5 (6) -trichlorosilylnorbornane obtained in Synthesis Example 3 was used instead of trichlorosilylnorbornane. Was synthesized. As a result of GPC analysis, the weight average molecular weight was 4,000, and the molecular weight dispersion was 1.1.
It was 2.

[0118]

Embedded image

Comparative Example Synthesis 1 Polymer (III) Using 4-hydroxybenzylsilsesquioxane represented by the following formula, the hydroxy group was ethoxyethoxylated with ethyl vinyl ether to obtain a polymer (III) represented by the following formula: ) Was performed. As a result of GPC analysis, the weight average molecular weight was 4,600, and the molecular weight dispersity was 1.
08.

[0120]

Embedded image

Evaluation Example [Measurement of polymer transmittance] 1 g of the obtained polymer was sufficiently dissolved in 10 g of propylene glycol monomethyl ether acetate, and filtered with a 0.2 μm filter.
A polymer solution was prepared. The polymer solution was spin-coated on a MgF ₂ substrate, and 10
Baking was performed at 0 ° C. for 90 seconds to form a polymer layer having a thickness of 100 nm on the MgF ₂ substrate. 248 nm, 193 n using a vacuum ultraviolet photometer (VUV200S, manufactured by JASCO Corporation)
m, the transmittance at 157 nm was measured. Table 1 shows the results
Shown in

[0122]

[Table 1]

[Dry Etching Resistance Test] 2 g of the polymer obtained above was sufficiently dissolved in 10 g of propylene glycol monomethyl ether acetate, and filtered with a 0.2 μm filter to prepare a polymer solution. The polymer solution was applied to a silicon wafer by spin coating, and baked at 100 ° C. for 90 seconds to form a polymer film having a thickness of 300 nm. Next, the wafer on which the polymer film was formed was dry-etched under the following two conditions, and the difference in thickness of the polymer film before and after etching was determined.

(1) Etching test with O ₂ gas Dry etching equipment TE manufactured by Tokyo Electron Limited
Using -8500P, the difference in thickness of the resist before and after etching was determined. The etching conditions are as shown below.

[0125]

[Table 2]

(2) Etching test with Cl ₂ / BCl ₃ -based gas Dry etching apparatus L-50 manufactured by Nidec Anelva Co., Ltd.
Using 7DL, the difference in polymer film thickness before and after etching was determined. The etching conditions are as shown below.

[0127]

[Table 3]

Table 4 shows the results of the etching test.

[Table 4]

[Resist preparation example] The polymer obtained in the synthesis example, the acid generators represented by PAGs 1 and 2, the bases shown in Table 5, and the dissolution inhibitor represented by DRI were prepared using FC-430 (manufactured by Sumitomo 3M Limited). Propylene glycol monomethyl ether acetate containing 0.01% by weight (PGME
A) A resist solution was prepared by dissolving sufficiently in 1,000 parts by weight of a solvent with the composition shown in Table 5 and filtering through a 0.1 μm Teflon (registered trademark) filter. Next, a DUV-30 (manufactured by Nissan Chemical Industries, Ltd.) film is formed to a thickness of 55 nm on a silicon wafer using the obtained resist solution, and the reflectance is reduced to 1% or less with KrF light (248 nm) on a substrate. The substrate was spin-coated and baked at 100 ° C. for 90 seconds using a hot plate to make the thickness of the resist 100 nm. This is a KrF excimer laser stepper (Nikon Corporation, NSR-S202A, NA-
0.6, σ0.75, 2/3 annular illumination), and immediately after exposure, baked at 110 ° C. for 90 seconds, 2.3
Development was carried out for 30 seconds with an aqueous solution of 8% tetramethylammonium hydroxide to obtain a positive pattern.

The obtained resist pattern was evaluated as follows. Table 5 shows the results. Evaluation method: 0.25 μm line and space:
The exposure amount resolved at 1 was taken as the optimum exposure amount (Eop), and the minimum line width of the line and space separated at this exposure amount was taken as the resolution of the evaluation resist.

[0131]

[Table 5]

[0132]

Embedded image

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

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of a processing process using oxygen etching.

FIG. 2 is an explanatory diagram of a processing process using chlorine-based etching.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 base substrate 2 substrate to be processed 3 organic film 4 resist layer 5 exposure 6 substrate to be processed

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/027 H01L 21/30 502R (72) Inventor Jun Hatakeyama 28, Nishifukushima, Nishifukushima, Nakakushijo-gun, Niigata Prefecture -1 Synthetic Technology Research Laboratories, Shin-Etsu Chemical Co., Ltd. 28-1 Nishifukushima, Kushiro-mura, Kushiro-gun, Japan Shin-Etsu Chemical Industry Co., Ltd. ) Inventor Masaru Sasako 1-1, Yukicho, Takatsuki-shi, Osaka (72) Inventor Masataka Endo 1-1, Yukicho, Takatsuki-shi, Osaka (72) Inventor Kishimura (72) Inventor, Mitsutaka Otani 2805, Imafukunakadai, Kawagoe-shi, Saitama Prefecture Central Glass Co., Ltd.Chemical Research Laboratories (72) Inventor Satoru Miyazawa 2805, Imafukunakadai, Kawagoe-shi, Saitama Prefecture Address Central Glass Co., Ltd., Chemical Research Laboratory (72) Inventor Kentaro Tsutsumi 2805 Imafukunakadai, Kawagoe-shi, Saitama Prefecture Central Glass Co., Ltd. Chemical Research Laboratory (72) Inventor Kazuhiko Maeda 3-7-7 Kandanishikicho, Chiyoda-ku, Tokyo 1 F-term in Central Glass Co., Ltd. (reference) 2H025 AA01 AA09 AB16 AC04 AC06 AC08 BE00 BE10 BG00 CB33 CB41 CC20 FA17 2H096 AA25 BA11 EA04 EA06 FA01 HA24 4J002 CP081 CP091 CP101 DF008 ED057 EH007 EH037E67EH37E037EH37EH37EH37EH37EEJEH EL087 EN028 EN038 EN048 EN068 EN078 EN098 EN108 EN118 EN128 EN138 EP018 ES008 ET008 EU018 EU028 EU048 EU058 EU078 EU118 EU128 EU138 EU148 EU218 EU228 EU238 EV216 EV246 EV256 EV266 EV296 EV318 EV328 FD206 FD207 GP03 4J035 BA11 BA12 BA14 C A062 CA072 CA082 CA092 CA101 CA16N CA161 CA192 CA202 CA222 CA262 LA03 LB16

Claims (8)

[Claims] 1. A polymer compound having a repeating unit represented by the following general formula (1). Embedded image (Wherein A is a divalent organic group, and may be a bridged cyclic group having 4 to 20 carbon atoms which may contain a hetero atom together with carbon atoms bonded at both ends of A) R ¹ , R ² , and R ^{3 each} represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl group having 1 to 4 carbon atoms; ¹ , R
^At least one of R ² and R ³ contains a fluorine atom. R ⁴
Is an acid labile group. ) 2. A resist material comprising the polymer compound according to claim 1. (A) the polymer compound according to (1),
A chemically amplified resist material comprising (B) an organic solvent and (C) an acid generator. 4. The resist material according to claim 3, further comprising (D) a basic compound. 5. The resist material according to claim 3, further comprising (E) a dissolution inhibitor. 6. A step of applying the resist material according to any one of claims 2 to 5 on a substrate; and (2) a step of applying heat through a photomask after the heat treatment to a wavelength of 300 nm.
A pattern forming method, comprising the following steps of exposing with a high energy beam or an electron beam, and (3) a step of performing a heat treatment as necessary and then developing with a developer. 7. The method according to claim 6, wherein after forming the pattern, the underlayer is processed by etching including oxygen plasma etching. 8. The resist pattern forming method according to claim 6, wherein after forming the pattern, the base is processed by etching with a halogen gas containing chlorine or bromine.