JP2002131897A - Positive resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive resist composition which is enhanced in resolving power, reduced in residue on development and improved in process admissibility such as a margin for exposure and a focal depth in lithography using a short- wavelength light source for exposure capable of ultra-microfabrication and a positive chemical amplification resist. SOLUTION: The positive resist composition contains (A) at least one of compound which generates a specific sulfonic acid by the irradiation of active light and (B) a resin having a group which is decomposed by the action of an acid to increase solubility in an alkali developing solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a lithographic printing plate or an IC.
The present invention relates to a positive photosensitive composition used in a semiconductor manufacturing process such as the above, a circuit substrate such as a liquid crystal and a thermal head, and other photofabrication processes.

[0002]

2. Description of the Related Art Semiconductor manufacturing processes for lithographic printing plates and ICs,
Liquid crystal, the manufacture of circuit boards such as thermal heads, as well as other photosensitive compositions used in the photofabrication process, there are various compositions, generally a photoresist photosensitive composition is used, it is Broadly speaking, there are two types: positive and negative. As one of the positive photoresist photosensitive compositions, there is a chemically amplified resist composition described in US Pat. No. 4,491,628, European Patent 249,139 and the like. Chemically amplified positive resist compositions are
Irradiation with radiation such as deep ultraviolet light generates an acid in the exposed area, and a reaction using this acid as a catalyst changes the solubility of the active radiation-irradiated area and the non-irradiated area in the developing solution to form a pattern on the substrate. It is a pattern forming material to be made.

Examples of such a combination include a combination of a compound capable of generating an acid by photolysis with an acetal or an O, N-acetal compound (Japanese Patent Application Laid-Open No. 48-89003), a combination of an orthoester or an amide acetal compound ( Combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-172014).
3429), a combination with an enol ether compound (JP-A-55-12995), a combination with an N-acyliminocarbonate compound (JP-A-55-126236),
Combination with a polymer having an orthoester group in the main chain (JP-A-56-17345), combination with a tertiary alkyl ester compound (JP-A-60-3625), combination with a silyl ester compound (JP-A-60-3625) Showa 60-10247
No.) and a combination with a silyl ether compound (Japanese Unexamined Patent Publication No.
0-37549, JP-A-60-112446) and the like. These have high photosensitivity because the quantum yield exceeds 1 in principle.

Similarly, systems which are stable under aging at room temperature, but are decomposed by heating in the presence of an acid and solubilized in alkali are disclosed in, for example, JP-A-59-45439, JP-A-60-3625, JP-A-62-2229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250542, Polym.Eng.Sce., Vol. 23, 101
2 (1983); ACS.Sym. 242, 11 (1984); Semicond
uctor World 1987, November, p. 91; Macromolecules, 2
Vol. 1, p. 1475 (1988); SPIE, vol. 920, p. 42 (1988);
Combination systems with esters or carbonate compounds of primary or secondary carbons (eg t-butyl, 2-cyclohexenyl). Since these systems also have high sensitivity and low absorption in the far ultraviolet region, they can be effective systems for shortening the light source wavelength capable of ultrafine processing.

The positive chemically amplified resist comprises an alkali-soluble resin, a compound which generates an acid upon exposure to radiation (photoacid generator), and a compound having an acid-decomposable group and inhibiting the dissolution of the alkali-soluble resin. It can be roughly classified into a two-component system comprising a component system, a resin having a group which is decomposed by the reaction with an acid and becomes alkali-soluble, and a photoacid generator. These two
In a three-component or three-component positive chemically amplified resist, the acid from the photoacid generator is interposed by exposure,
After the heat treatment, development is performed to obtain a resist pattern.

As described above, these positive-type chemically amplified resists can be effective systems for shortening the wavelength of a light source capable of ultra-fine processing. However, such resists further improve resolution, exposure margin and depth of focus. There is a need for improved process tolerance. As the photoacid generator, those which generate perfluoroalkanesulfonic acid such as triphenylsulfonium triflate and bis (t-butylphenyl) iodonium perfluorobutanesulfonate are well known. Generally, perfluoroalkyl compounds have high hydrophobicity,
It is used for water repellent treatment of clothes. Therefore, a resist using an acid generator that generates perfluoroalkyl sulfonic acid upon irradiation with the actinic ray has a low affinity for an aqueous developing solution, and a decrease in sensitivity due to deterioration in developability or a residue of development (scum) occurs. There was a problem that occurred.

Furthermore, the above-mentioned technology cannot sufficiently cope with the current fine processing, and there is room for improvement in the improvement of the resolving power and the process tolerance such as the exposure margin and the depth of focus.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a lithography technique using a short-wavelength exposure light source capable of ultrafine processing and a positive-type chemically amplified resist. An object of the present invention is to provide a positive resist composition having reduced processability and improved process tolerance such as exposure margin and depth of focus.

[0009]

According to the present invention, a positive resist composition having the following constitution is provided to achieve the above object of the present invention.

(1) (A) At least one compound (B) which generates a sulfonic acid represented by the following general formula (X) upon irradiation with actinic light is decomposed by the action of an acid, and A positive resist composition comprising a resin having a group that increases solubility.

[0011]

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[0012] In the general formula _{(X), R 1 a~R 13} a is a hydrogen atom, an alkyl group, an alkyl group substituted with a halogen atom, a halogen atom, a hydroxyl group. A represents a divalent linking group having a hetero atom or a single bond. However, when A is a single bond, all of R ₁ a to R ₁₃ a do not simultaneously represent a fluorine atom, and all of R ₁ a to R ₁₃ a do not simultaneously represent a hydrogen atom. m represents an integer of 0 to 12. n
Represents an integer of 0 to 12. q represents an integer of 1 to 3.

(2) (C) A low-molecular-weight dissolution inhibiting compound having a molecular weight of 3000 or less, which has a group decomposable by an acid and whose dissolution rate in an alkaline developer is increased by the action of an acid. The positive resist composition according to the above (1), which is characterized in that:

(3) (A) A compound capable of decomposing at least one compound (C) capable of generating a sulfonic acid represented by the general formula (X) described in the above (1) upon irradiation with actinic rays, Having a molecular weight of 300, wherein the dissolution rate in an alkali developer is increased by the action of an acid.
0 or less low molecular dissolution inhibiting compound (E) A positive resist composition comprising a resin which is insoluble in water and soluble in an alkali developing solution.

(4) The general formula (X) described in the above (1)
In sulfonic acid CF ₃ shown _{CF 2 -O-CF 2 CF 2} S
The positive resist composition according to any one of (1) to (3), wherein the positive resist composition is O ₃ H.

(5) Iodonium salt or sulfonium salt compounds represented by the following general formulas (I) to (III).

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In the above general formulas (I) to (III), R ₁ ~ R
₃₇ is each independently a hydrogen atom, a linear chain having 1 to 4 carbon atoms,
Branched alkyl group, C 3 -C 8 cyclic alkyl group having a carbon 1-4 alkoxy group carbon atoms, a hydroxyalkyl group, a halogen atom or -S-R ₃₈ group,. Here, R ₃₈ is a linear or branched alkyl group having 1 to 12 carbon atoms, 3 to 8 carbon atoms.
Represents a cyclic alkyl group or an aryl group having 6 to 14 carbon atoms. X ⁻ is an anion of a sulfonic acid represented by the general formula (X) described in the above (1).

In the present invention, excellent performance can be exhibited even with an electron beam as an energy beam for irradiation. When irradiating with an electron beam, the incident electrons have electric charges and interact with the nuclei and electrons of the substances that make up the resist. There was a problem of deterioration. Further, there is also a problem that even if the beam diameter is reduced to irradiate a fine pattern for resolving the fine pattern, the scattering increases the irradiation area and deteriorates the resolving power. The composition of the present invention successfully solved these problems caused by electron beam irradiation.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides: (A) at least one compound capable of generating a sulfonic acid represented by the following general formula (X) upon irradiation with actinic light;
A positive resist composition (hereinafter, also referred to as a "first composition") containing, as an essential component, a seed and (B) a resin having a group that is decomposed by the action of an acid and increases the solubility in an alkaline developer. , 2. (A) at least one compound that generates a sulfonic acid represented by the following general formula (X) upon irradiation with actinic rays is decomposed by the action of an acid (C) to increase the solubility in an alkali developer to a molecular weight of 3,000. The following compounds and (E) a positive resist composition containing an alkali-soluble resin as an essential component (hereinafter, also referred to as “second composition”) are included. Hereinafter, when simply referred to as a positive resist composition or a composition, it includes both the first composition and the second composition. In the present invention, the actinic ray refers to far ultraviolet rays (KrF excimer laser, ArF excimer laser), electron beam, X-ray, and ion beam.

First, components such as a compound and a resin contained in the positive resist composition will be described in detail.

[Explanation of each component contained in the composition] [1] (A) Irradiation with actinic rays causes the following general formula (X)
At least one compound that generates a sulfonic acid represented by
In the seed ((A) also referred to as a component or a sulfonic acid generator) the general formula _{(X), R 1 a~R 13} a is a hydrogen atom, an alkyl group, an alkyl group substituted with a halogen atom, a halogen atom, a hydroxyl group Represents A represents a divalent linking group having a hetero atom or a single bond. However, when A is a single bond, R
₁ a to R ₁₃ all of a is not simultaneously represent a fluorine atom, and R ₁ a to R ₁₃ all a do not simultaneously represent hydrogen atoms. m represents an integer of 0 to 12. n represents the integer of 0-12. q represents an integer of 1 to 3.

[0022] The alkyl group of R ₁ a to R ₁₃ a, which may have a substituent, a methyl group, an ethyl group, a propyl group,
Those having 1 to 12 carbon atoms such as n-butyl group, sec-butyl group and t-butyl group are exemplified. R ₁ a to R ₁₃ a
Examples of the halogen atom include a fluorine atom, a chlorine atom and an iodine atom. As the substituent, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, and an iodine atom), an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, Examples include a cyano group, a hydroxy group, a carboxy group, an alkoxycarbonyl group, and a nitro group.

Examples of the divalent linking group having a hetero atom in A include an oxygen atom, a sulfur atom, -CO- and -COO.
-, - CONR -, - SO 2 NR -, - CONRCO
_{-, - SO 2 NRCO -,} - SO 2 NRSO 2 -, - OC
ONR- and the like. Here, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

Examples of the sulfonic acid represented by the general formula (X), preferably represents at least one of a halogen atom R ₁ a to R ₁₃ a, more preferably R ₁ a to R ₁₃ a
Preferably, at least one of the above represents a fluorine atom.
Among the above, more preferably, CF ₈ (CF ₂ ) _k [A
(CF ₂ ) _{k '} ] _q SO ₃ H, CF ₃ (CF ₂ ) _k (CH ₂ ) _k' SO
Compounds represented by ₃ H and CH ₃ (CH ₂ ) _k (CF ₂ ) _{k ′} SO ₃ H are preferred, and CF ₃ CF ₂ —O—CF ₂ CF ₂ SO ₃ H is particularly preferred. Here, k represents an integer of 0 to 12. k '
Represents an integer of 1 to 12. q has the same meaning as described above.

As the component (A) of the present invention, a sulfonium salt or an iodonium salt of sulfonic acid represented by the above general formula (X) is preferable in terms of sensitivity and resolution. More preferred is a sulfonium salt, which further improves the storage stability.

Further, the component (A) is preferably a compound having a structure represented by any one of the following general formulas (I) to (III).

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(In the above formula, R ₁ To R ₃₇ are each independently
Hydrogen atom, straight chain, branched or cyclic alkyl group, straight chain,
Represents a branched or cyclic alkoxy group, a hydroxy group, a halogen atom, or a —S—R ₃₈ group. Here, R ₃₈ represents a linear, branched, or cyclic alkyl group or an aryl group. X
^- is an anion of sulfonic acid represented by the general formula (X). )

In the general formulas (I) to (III), R _{1 to} R
The straight-chain or branched alkyl group of ₃₈ may have a substituent and has 1 carbon atom such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and t-butyl group.
To four. As the cyclic alkyl group,
What has a C3-C8 group which may have a substituent, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, is mentioned. As the alkoxy group for R _{1 to} R ₃₇ ,
Methoxy, ethoxy, hydroxyethoxy, propoxy, n-butoxy, isobutoxy, sec-
Those having 1 to 4 carbon atoms such as a butoxy group and a t-butoxy group are exemplified.

Examples of the halogen atom for R _{1 to} R ₃₇ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. _Examples of the aryl group represented by R ₃₈ include a phenyl group, a tolyl group, a methoxyphenyl group, a naphthyl group and the like.
Fourteen are included. The aryl group may have a substituent.

As these substituents, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom,
A chlorine atom, an iodine atom), an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cyano group, a hydroxy group, a carboxy group, an alkoxycarbonyl group, and a nitro group.

The general formulas (I) to (II) which can be used in the present invention
The iodonium compound or sulfonium compound represented by I) has a sulfonic acid anion represented by the general formula (X) as a counter anion X ⁻ . These anions are anions (—SO ₃ ⁻ ) from which a hydrogen atom of the sulfonic acid (—SO ₃ H) has been eliminated.

Hereinafter, specific examples of the component (A) (including specific examples of the compounds represented by the above general formulas (I) to (III)) are shown, but the present invention is not limited thereto. .

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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The above (I-14), (I-15), (I
-19), (I-20), (II-27), (II-2)
8) The compounds of (II-29) use sulfonic acid synthesized via the telomer method as a raw material, and are a mixture containing 60% or more of the described compound and a sulfonate having a different fluoroalkyl chain length. is there.

The compounds of the above (A) may be used alone or in combination of two or more.
More than one species can be used in combination.

The compound represented by the general formula (I), which is the component (A), is obtained by reacting an aromatic compound with a periodate and subjecting the obtained iodonium salt to salt exchange with a corresponding sulfonic acid. Can be synthesized. General formula (I
I), the compound represented by the general formula (III) is obtained, for example, by reacting an aryl Grignard reagent such as arylmagnesium bromide with a substituted or unsubstituted phenylsulfoxide, and converting the obtained triarylsulfonium halide with a corresponding sulfonic acid. It can be synthesized by salt exchange. Also,
A method in which substituted or unsubstituted phenyl sulfoxide and the corresponding aromatic compound are condensed and salt-exchanged using an acid catalyst such as methanesulfonic acid / diphosphorus pentoxide or aluminum chloride, and a diaryliodonium salt and a diarylsulfide are converted to copper acetate or the like. It can be synthesized by a method such as condensation and salt exchange using a catalyst. The salt exchange can be performed by a method of once converting to a halide salt and then converting it to a sulfonate using a silver reagent such as silver oxide, or by using an ion exchange resin. The sulfonic acid or sulfonic acid salt used for the salt exchange may be a commercially available one, or may be obtained by hydrolysis of a commercially available sulfonic acid halide.

The content of the component (A) in the positive resist composition of the present invention is based on the solid content of the composition.
0.1-20% by weight is preferred, more preferably 0.5%
10 to 10% by weight, more preferably 1 to 7% by weight.

Acid-generating compound other than component (A) which can be used in combination In the present invention, a compound which decomposes by irradiation with actinic rays or radiation to generate an acid may be used in addition to component (A). The amount of the photoacid generator that can be used in combination with the component (A) of the present invention is a molar ratio (component (a) / other acid generator).
And usually 100/0 to 20/80, preferably 100/0
0/40/60, more preferably 100/0 to 50/5
0. Such photoacid generators that can be used together include:
Photo-initiators of photo-cationic polymerization, photo-initiators of photo-radical polymerization, photo-decolorants of dyes, photo-discolorants, or known acids that generate an acid by irradiation with actinic rays or radiation used in micro resists and the like Compounds and mixtures thereof can be appropriately selected and used.

For example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts and arsonium salts;
Organic halogen compound, organic metal / organic halide, o
-Photoacid generators having a nitrobenzyl-type protecting group, compounds that generate sulfonic acid upon photolysis, such as iminosulfonate, and disulfone compounds.

Further, a compound in which a group or a compound capable of generating an acid upon irradiation with an actinic ray or radiation is introduced into a main chain or a side chain of a polymer, for example, US Pat.
No. 849,137, German Patent No. 3914407, JP-A-63-26653,
JP-A-55-164824, JP-A-62-69263, JP-A-63-1460
Compounds described in JP-A-38-163452, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029 and the like can be used.

Further, the compounds capable of generating an acid by light described in US Pat. No. 3,779,778 and European Patent 126,712 can also be used.

Among the compounds which can be used together and decompose upon irradiation with actinic rays or radiation to generate an acid, those which are particularly effectively used are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PAG)
An S-triazine derivative represented by 2).

[0052]

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In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C (Y) ₃
Show Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0054]

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[0055]

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(2) An iodonium salt represented by the following formula (PAG3) or a sulfonium salt represented by the following formula (PAG4).

[0057]

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The formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom.

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, it is an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or a substituted derivative thereof. Preferred substituents are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom with respect to the aryl group,
Examples of the alkyl group include an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, and an alkoxycarbonyl group.

[0060] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^-, etc. perfluoroalkane sulfonate anion, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes Examples include, but are not limited to:

Further, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded through a single bond or a substituent.

Specific examples include the following compounds, but are not limited thereto.

[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, and are described, for example, in US Pat.
It can be synthesized by the methods described in 807,648 and 4,247,473, JP-A-53-101,331 and the like.

(3) Disulfone derivatives represented by the following formula (PAG5) or iminosulfonate derivatives represented by the following formula (PAG6).

[0076]

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In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group. Specific examples include the following compounds, but are not limited thereto.

[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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(4) A diazodisulfone derivative represented by the following general formula (PAG7).

[0084]

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Here, R represents a linear, branched or cyclic alkyl group or an optionally substituted aryl group. Specific examples include the following compounds,
It is not limited to these.

[0086]

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Next, the general formulas (I) to (III) of the present invention
The novel compound represented by is described.

[1-1] Iodonium Salt Compound Represented by the General Formula (I) In the general formula (I), R _{28 to} R _{37 each} represent a hydrogen atom, a straight chain having 1 to 4 carbon atoms, branched alkyl group, C 3 -C 8 cyclic alkyl group having a carbon 1-4 alkoxy group carbon atoms, a hydroxyalkyl group, a halogen atom or -S-R ₃₈ group,. Wherein R ₃₈ represents a linear or branched alkyl group having 1 to 12 carbon atoms, 6 to number of 3 to 8 cyclic alkyl group or the number of carbon-carbon
Represents 14 aryl groups.

R _{28 to} R ₃₇ are linear or branched alkyl groups having 1 to 4 carbon atoms, cyclic alkyl groups having 3 to 8 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, and aryl groups having R ₃₈ are The same ones as the specific examples exemplified above are given. X ^- is an anion of the sulfonic acid represented by the general formula (X).

[0090] Examples of the sulfonic acid represented by the general formula (X), preferably represents at least one of a halogen atom R ₁ a to R ₁₃ a, more preferably R ₁ a to R ₁₃ a
Preferably, at least one of the above represents a fluorine atom.
Among the above, more preferably, CF ₈ (CF ₂ ) _k [A
(CF ₂ ) _{k '} ] _q SO ₃ H, CF ₃ (CF ₂ ) _k (CH ₂ ) _k' SO
Compounds represented by ₃ H and CH ₃ (CH ₂ ) _k (CF ₂ ) _{k ′} SO ₃ H are preferred, and CF ₃ CF ₂ —O—CF ₂ CF ₂ SO ₃ H is particularly preferred. Here, k represents an integer of 0 to 12. k '
Represents an integer of 1 to 12. q has the same meaning as described above.

[1-2] The above general formula (II) of the present invention
During in sulfonium salt compound the general formula represented (II), R ₁ To R ₁₅ are a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, a halogen atom, or -SR ₃₈ represents a group. Wherein R ₃₈ represents a linear or branched alkyl group having 1 to 12 carbon atoms, 6 to number of 3 to 8 cyclic alkyl group or the number of carbon-carbon
Represents 14 aryl groups.

R ₁ C1-4 straight-chain carbon atoms of to R _15, branched alkyl group, C 3 -C 8 cyclic alkyl group having a carbon alkoxy group having 1 to 4 carbon atoms, an aryl group of R ₃₈ are previously exemplified specifically Examples are the same as in the example. X ^- is an anion of the sulfonic acid represented by the general formula (X).

[0093] Examples of the sulfonic acid represented by the general formula (X), preferably represents at least one of a halogen atom R ₁ a to R ₁₃ a, more preferably R ₁ a to R ₁₃ a
Preferably, at least one of the above represents a fluorine atom.
Among the above, more preferably, CF ₈ (CF ₂ ) _k [A
(CF ₂ ) _{k '} ] _q SO ₃ H, CF ₃ (CF ₂ ) _k (CH ₂ ) _k' SO
Compounds represented by ₃ H, CH ₃ (CH ₂ ) _k (CF ₂ ) _{k ′} SO ₃ H are preferred, and CF ₃ CF ₂ —O—CF ₂ CF ₂ SO ₃ H is particularly preferred. Here, k represents an integer of 0 to 12. k '
Represents an integer of 1 to 12. q has the same meaning as described above.

[1-3] Sulfonium salt compound represented by the above general formula (III) In the above general formula (III), R _{16 to} R ₂₇ represent a hydrogen atom, a straight chain having 1 to 4 carbon atoms, branched alkyl group, C 3 -C 8 cyclic alkyl group having a carbon 1-4 alkoxy group carbon atoms, a hydroxyalkyl group, a halogen atom or -S-R ₃₈ group,.
Here, R ₃₈ is a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, or a carbon atom having 6 carbon atoms.
Represents up to 14 aryl groups.

R _{16 to} R ₂₇ represented by a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an aryl group represented by R ₃₈ are The same ones as the specific examples exemplified above are given. X ^- is an anion of the sulfonic acid represented by the general formula (X).

[0096] Examples of the sulfonic acid represented by the general formula (X), preferably represents at least one of a halogen atom R ₁ a to R ₁₃ a, more preferably R ₁ a to R ₁₃ a
Preferably, at least one of the above represents a fluorine atom.
Among the above, more preferably, CF ₈ (CF ₂ ) _k [A
(CF ₂ ) _{k '} ] _q SO ₃ H, CF ₃ (CF ₂ ) _k (CH ₂ ) _k' SO
Compounds represented by ₃ H and CH ₃ (CH ₂ ) _k (CF ₂ ) _{k ′} SO ₃ H are preferred, and CF ₃ CF ₂ —O—CF ₂ CF ₂ SO ₃ H is particularly preferred. Here, k represents an integer of 0 to 12. k '
Represents an integer of 1 to 12. q has the same meaning as described above.

In the present invention, the compounds represented by the above general formulas (I) to (II)
Specific examples of the novel compound represented by I) include those corresponding to the novel compound among the specific examples of the component (A).

[2] (B) Resin having a group which is decomposed by the action of an acid and increases the solubility in an alkali developer (component (B)) The component (B) is used in the first composition of the present invention. Used as an essential component. Component (B) is a resin having a group that decomposes with an acid and increases solubility in an alkali developer (also referred to as a group that can be decomposed with an acid), such as a main chain or a side chain of the resin,
Alternatively, it is a resin having an acid-decomposable group in both the main chain and the side chain. Among them, a resin having a group which can be decomposed by an acid in a side chain is more preferable.

A preferred group capable of being decomposed by an acid is-
COOA ⁰ and —O—B ⁰ groups. Examples of the groups containing these include the groups represented by —R ⁰ —COOA ⁰ and —Ar—O—B ⁰ . Here, A ⁰ is -C (R ⁰¹ )
^{(R 02) (R 03)} , - showing the ^{Si (R 01) (R 02} ) (R 0 3) or ^{-C (R 04) (R 05} ) -O-R 06 group. B ⁰
Shows A ⁰ or -CO-O-A ⁰ group (R ^0, R ⁰¹ ~R
⁰⁶ and Ar are the same as those described below).

The acid-decomposable group is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a tertiary alkyl ether group, or a tertiary alkyl ester. And tertiary alkyl carbonate groups. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, an acetal group, and a tetrahydropyranyl ether group. Particularly preferred is an acetal group.

Next, when the group decomposable by these acids is bonded as a side chain, the base resin has -OH or -COOH, preferably -R ⁰ -COOH or -Ar-OH group on the side chain. It is an alkali-soluble resin. For example, an alkali-soluble resin described below can be used.

The alkali dissolution rate of these alkali-soluble resins was measured with a 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.) and measured at 170 ° C.
A / sec or more is preferable. Particularly preferably 330A
Per second or more (where A is Angstroms). From the viewpoint of achieving a rectangular profile, an alkali-soluble resin having a high transmittance to far ultraviolet light or excimer laser light is preferable. Preferably, a 1 μm film thickness of 24
The transmittance at 8 nm is 20 to 90%. From such a viewpoint, particularly preferred alkali-soluble resins are o-, m
-, P-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen or alkyl-substituted poly (hydroxystyrene), part of poly (hydroxystyrene), O-alkylated or O- An acylated product, a styrene-hydroxystyrene copolymer, an α-methylstyrene-hydroxystyrene copolymer, and a hydrogenated novolak resin.

The resin having a group decomposable with an acid used in the present invention is disclosed in European Patent No. 2,485,853, JP-A No. 2-25 / 1990.
No. 850, No. 3-223860, No. 4-251259
As disclosed in US Pat. No. 6,086,098, an alkali-soluble resin is reacted with a precursor of an acid-decomposable group, or an alkali-soluble resin monomer having an acid-decomposable group bonded thereto is copolymerized with various monomers. Can be obtained.

The acid-decomposable resin is preferably one in which all or a part of the phenolic hydroxyl group of polyhydroxystyrene is protected by an acid-decomposable group. The acid-decomposable group is preferably an acetal group. As a result, performance fluctuation due to aging from irradiation to post-heating is reduced. As the acetal group, a 1-alkoxyethyl acetal group is preferable. More preferably, it is a 1-alkoxyethyl acetal group having a cyclic hydrocarbon group or an aromatic group.
By using this, dry etching resistance is improved.

Specific examples of the resin having a group decomposable by an acid used in the present invention are shown below, but the present invention is not limited to these.

Pt-butoxystyrene / p-hydroxystyrene copolymer, p- (t-butoxycarbonyloxy) styrene / p-hydroxystyrene copolymer, p
-(T-butoxycarbonylmethyloxy) styrene /
p-hydroxystyrene copolymer, 4- (t-butoxycarbonylmethyloxy) -3-methylstyrene / 4
Hydroxy-3-methylstyrene copolymer, p- (t-
(Butoxycarbonylmethyloxy) styrene / p-hydroxystyrene (10% hydrogenated) copolymer, m-
(T-butoxycarbonylmethyloxy) styrene / m
-Hydroxystyrene copolymer, o- (t-butoxycarbonylmethyloxy) styrene / o-hydroxystyrene copolymer, p- (cumyloxycarbonylmethyloxy) styrene / p-hydroxystyrene copolymer, cumyl methacrylate / Methyl methacrylate copolymer,
4-t-butoxycarbonylstyrene / dimethyl maleate copolymer, benzyl methacrylate / tetrahydropyranyl methacrylate,

P- (t-butoxycarbonylmethyloxy) styrene / p-hydroxystyrene / styrene copolymer, pt-butoxystyrene / p-hydroxystyrene / fumaronitrile copolymer, t-butoxystyrene / hydroxyethyl methacrylate Copolymer, styrene / N- (4-hydroxyphenyl) maleimide / N-
(4-t-butoxycarbonyloxyphenyl) maleimide copolymer, p-hydroxystyrene / t-butyl methacrylate copolymer, styrene / p-hydroxystyrene / t-butyl methacrylate copolymer p-hydroxystyrene / t-butyl Acrylate copolymer, styrene / p-hydroxystyrene / t-butyl acrylate copolymer p- (t-butoxycarbonylmethyloxy)
Styrene / p-hydroxystyrene / N-methylmaleimide copolymer, t-butyl methacrylate / 1-adamantyl methyl methacrylate copolymer, p-hydroxystyrene / t-butyl acrylate / p-acetoxystyrene copolymer, p-hydroxy Styrene / t-butyl acrylate / p- (t-butoxycarbonyloxy)
Styrene copolymer, p-hydroxystyrene / t-butyl acrylate / p- (t-butoxycarbonylmethyloxy) styrene copolymer,

In the present invention, as the resin having an acid-decomposable group (component (B)), a resin containing a repeating structural unit represented by the following general formulas (IV) and (V) is preferable. Thereby, it has a high resolution and the performance change over time from irradiation to heating becomes smaller.

[0109]

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(In the above formula (IV), L is a hydrogen atom,
It represents a linear, branched or cyclic alkyl group which may be substituted, or an aralkyl group which may be substituted. Z represents a linear, branched or cyclic alkyl group which may be substituted, or an aralkyl group which may be substituted. Further, Z and L may combine to form a 5- or 6-membered ring. )

Examples of the alkyl group in L and Z in the general formula (IV) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, a cyclopentyl group and a hexyl group. Group, cyclohexyl group, octyl group, dodecyl group, etc.
Straight-chain, branched or cyclic ones.

Preferred substituents on the alkyl group include an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acylamino group, a sulfonylamino group,
Examples include an alkylthio group, an arylthio group, and an aralkylthio group.Examples include a cyclohexylethyl group, an alkylcarbonyloxymethyl group, an alkylcarbonyloxyethyl group, an arylcarbonyloxyethyl group, an aralkylcarbonyloxyethyl group, an alkyloxymethyl group, and an aryloxy group. Methyl group, aralkyloxymethyl group, alkyloxyethyl group, aryloxyethyl group, aralkyloxyethyl group, alkylthiomethyl group, arylthiomethyl group, aralkylthiomethyl group,
Examples thereof include an alkylthioethyl group, an arylthioethyl group, and an aralkylthioethyl group. The alkyl in this case is not particularly limited, but may be any of a chain, a ring, and a branch, and examples thereof include a group such as a cyclohexylcarbonyloxyethyl group, a t-butylcyclohexylcarbonyloxyethyl group, and an n-butylcyclohexylcarbonyloxyethyl group. Can be mentioned. Also, the aryl is not limited, but includes, for example, a phenyloxyethyl group and the like, and may be further substituted, for example, a cyclohexylphenyloxyethyl group. The aralkyl is not particularly limited, but examples thereof include a benzylcarbonyloxyethyl group.

Examples of the aralkyl group in L and Z include those having 7 to 15 carbon atoms, such as a substituted or unsubstituted benzyl group and a substituted or unsubstituted phenethyl group. Preferred substituents of the aralkyl group include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, an aralkylthio group, and the like. Examples include a benzyl group and a phenylthiophenethyl group. It is preferred that Z is a substituted alkyl group or a substituted aralkyl group, since further improvement in edge roughness is recognized. Here, the substituent of the alkyl group is preferably a cyclic alkyl group, an aryloxy group, an alkylcarboxy group, an arylcarboxy group, or an aralkylcarboxy group, and the substituent of the aralkyl group is an alkyl group, a cyclic alkyl group, or a hydroxyl group. preferable.

5 or 6 formed by combining L and Z with each other
Examples of the member ring include a tetrahydropyran ring and a tetrahydrofuran ring.

The ratio of the repeating structural unit represented by the general formula (IV) to the repeating structural unit represented by the general formula (V) in the resin is preferably from 1/99 to 60/40, and more preferably from 1/99 to 60/40. It is 5/95 to 50/50, more preferably 10/90 to 40/60.

The resin containing the repeating structural units represented by the general formulas (IV) and (V) may contain structural units derived from other monomers. Other monomers include hydrogenated hydroxystyrene; halogen, alkoxy or alkyl-substituted hydroxystyrene; styrene; halogen, alkoxy, acyloxy or alkyl-substituted styrene; maleic anhydride; acrylic acid derivative; methacrylic acid derivative; Examples include, but are not limited to:
The ratio between the structural units of the general formulas (IV) and (V) and the structural units of the other monomers is represented by a molar ratio [(IV) +
(V)] / [other monomer components] = 100/0 to 50 /
50, preferably 100/0 to 60/40, and more preferably 100/0 to 70/30.

Specific examples of the resin containing a repeating structural unit represented by the above formulas (IV) and (V) and other resins that can be used in the present invention include:
The following are mentioned.

[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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In the above specific examples, Me is a methyl group, E
t represents an ethyl group, nBu represents an n-butyl group, iso-Bu represents an isobutyl group, and tBu represents a t-butyl group.

When an acetal group is used as the acid-decomposable group, a polyhydroxy compound is added at the synthesis stage to adjust the alkali dissolution rate and improve heat resistance to introduce a cross-linking site connecting the polymer main chain with a polyfunctional acetal group. May be. The amount of the polyhydroxy compound to be added is 0.01 to 5 mol%, more preferably 0.05 to 4 mol%, based on the amount of hydroxyl groups of the resin. Examples of the polyhydroxy compound include those having 2 to 6 phenolic hydroxyl groups or alcoholic hydroxyl groups, preferably 2 to 4 hydroxyl groups, and more preferably 2 to 4 hydroxyl groups.
Or three. Specific examples of the polyhydroxy compound are shown below, but the present invention is not limited thereto.

[0131]

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(B) The resin having a group decomposable with an acid has a weight average molecular weight (Mw) of 2,000 to 300,000.
Is preferably within the range. If it is less than 2,000, the film is greatly reduced due to the development of the unirradiated portion, and if it exceeds 300,000, the dissolution rate of the resin itself in alkali becomes slow and the sensitivity is lowered. Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.

The component (B) of the positive resist composition of the present invention, that is, the resin having a group decomposable with an acid, is
You may mix and use more than one type. The amount of the component (B) used is 40 to 40% based on the solid content of the first composition of the present invention.
It is 99% by weight, preferably 60 to 98% by weight.

[3] (C) A compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to increase the solubility in an alkali developer ((C) component) The (C) component is an essential component of the second composition. And a component to be added to the first composition as needed. The component (C) has a group which can be decomposed by an acid, and has a molecular weight of 3,000 or less, preferably 200 to 2,000, in which the solubility in an alkali developer is increased by the action of an acid.
00, more preferably 300 to 1,500 low molecular weight compounds. The component (C) functions as a dissolution inhibitor for the alkali developer in the non-irradiated portion. In the following description, “acid-decomposable dissolution inhibiting compound” has the same meaning as component (C).

The preferred component (C), that is, the preferred acid-decomposable dissolution-inhibiting compound has at least two acid-decomposable groups in its structure, and the distance between the acid-decomposable groups is the longest. A compound that has at least 8 bonding atoms in position except for the acid-decomposable group. A more preferred acid-decomposable dissolution-inhibiting compound is (A) an acid-decomposable compound having at least two groups capable of being decomposed by an acid in its structure, and wherein the distance between the acid-decomposable groups is the farthest. At least 10 and preferably at least 11
, More preferably at least 12 compounds,
And (ii) at least three acid-decomposable groups, and the distance between the acid-decomposable groups is at least 9, and preferably at least 10, excluding the acid-decomposable groups at the farthest position. More preferably, it is a compound passing through at least 11. The upper limit of the number of the bonding atoms is preferably 50, and more preferably 30.

When the acid-decomposable dissolution-inhibiting compound has three or more, preferably four or more acid-decomposable groups, and also when it has two acid-decomposable groups, the acid-decomposable groups are mutually fixed. If the distance is not less than the distance, the dissolution inhibiting property with respect to the alkali-soluble resin is significantly improved. The distance between the acid-decomposable groups is represented by the number of via bond atoms excluding the acid-decomposable groups. For example, in the case of the following compounds (1) and (2), the distance between the acid-decomposable groups is four bonding atoms each,
In compound (3), it has 12 bonding atoms.

[0137]

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The acid-decomposable dissolution inhibiting compound may have a plurality of acid-decomposable groups on one benzene ring, but preferably one acid-decomposable group on one benzene ring. It is a compound composed of a skeleton having a group.

A group decomposable by an acid, that is, —COO-A
⁰ and a group containing a —O—B ⁰ group include —R ⁰ —COO—
A ⁰ or a group represented by —Ar—O—B ⁰ is exemplified.
Here, A ⁰ represents -C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), -Si
^{(R 01) (R 02)} (R 0 3) or -C (R ⁰⁴⁾
It represents a (R ⁰⁵ ) -OR ⁰⁶ group. B ⁰ is A ⁰ or -CO-
It represents an ^OA group. R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R
⁰⁵ is the same or different and represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ⁰⁶ represents an alkyl group or an aryl group. However, at least two of R ^{01 to} R ⁰³ are groups other than hydrogen atoms, and even if two groups of R ^{01 to} R ⁰³ and R ^{04 to} R ⁰⁶ are bonded to form a ring. Good. R ⁰ represents a divalent or higher valent aliphatic or aromatic hydrocarbon group which may have a substituent, and -Ar- represents a divalent or higher valent which may have a monocyclic or polycyclic substituent. Shows an aromatic group.

Here, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. Preferred are those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and alkenyl groups having 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Preferably, the aryl group has 6 to 1 carbon atoms such as phenyl, xylyl, toluyl, cumenyl, naphthyl and anthracenyl.
Four are preferred. Further, as a substituent, a hydroxyl group,
Halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, the above alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, s
an alkoxy group such as an ec-butoxy group and a t-butoxy group,
Methoxycarbonyl group, alkoxycarbonyl group such as ethoxycarbonyl group, benzyl group, aralkyl group such as phenethyl group, cumyl group, aralkyloxy group, formyl group, acetyl group, butyryl group, benzoyl group, cyanyl group, acyl such as valeryl group Group, acyloxy group such as butyryloxy group, the above alkenyl group, vinyloxy group,
Examples thereof include an alkenyloxy group such as a propenyloxy group, an allyloxy group and a butenyloxy group, an aryloxy group such as the above-described aryl group and phenoxy group, and an aryloxycarbonyl group such as a benzoyloxy group.

The acid-decomposable group is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a tertiary alkyl ether group, or a tertiary alkyl ester group. And tertiary alkyl carbonate groups. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, and a tetrahydropyranyl ether group.

The component (C) is preferably selected from those described in JP-A No. 1-2
89946, JP-A-1-289947, JP-A-2-
2560, JP-A-3-128959, JP-A-3-1
58855, JP-A-3-179353, JP-A-3-179
191351, JP-A-3-200251, JP-A-3-3
JP-A-200252, JP-A-3-200253, JP-A-3-200254, JP-A-3-200255, JP-A-3-259149, JP-A-3-279958, JP-A-3-279959, JP-A-4- 1650, JP-A-4-1651, JP-A-4-11260, JP-A-4
-12356, JP-A-4-12357, Japanese Patent Application No. 3-
No. 33229, Japanese Patent Application No. 3-230790, Japanese Patent Application No. 3-230
No. 320438, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-
No. 52732, No. 4-103215, No. 4-
104542, Japanese Patent Application No. 4-107885, Japanese Patent Application No. 4
No. -107889, groups shown above some or all of the phenolic OH groups of the polyhydroxy compounds described herein, such as Nos. 4-152195, -R ⁰ -COO-
Protected compounds linked by A ⁰ or B ⁰ groups are included.

More preferably, JP-A-1-289946.
JP-A-3-128959, JP-A-3-15885
5, JP-A-3-179353, JP-A-3-2002
No. 51, JP-A-3-200252, JP-A-3-200
255, JP-A-3-259149, JP-A-3-27
9958, JP-A-4-1650, JP-A-4-112
No. 60, JP-A-4-12356, JP-A-4-1235
7, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-10321
No. 5, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1078
No. 85, Japanese Patent Application Nos. 4-107889 and 4-15219
No. 5 using the polyhydroxy compound described in the specification.

In the present invention, specific examples of the preferable compound skeleton of the component (C) are shown below.

[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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R in the compounds (1) to (44) is a hydrogen atom,

[0159]

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Represents the following. However, at least two or three depending on the structure are groups other than hydrogen atoms, and each substituent R
May not be the same group.

In the case of the first composition, the content of the component (C) is as follows:
Based on the solids content of the first composition, preferably from 3 to 45
%, More preferably 5 to 30% by weight, and still more preferably 10 to 20% by weight. (C) in the case of the second composition
The contents of the components are the same as in the first composition.

[4] (E) Alkali-Soluble Resin (Component (E)) The (E) alkali-soluble resin is an essential component of the second composition of the present invention. It is a component that may be added to the first composition of the present invention. (E) The alkali-soluble resin is a resin that is insoluble in water and soluble in an alkali developer, and is used to adjust the alkali solubility of the second composition. This resin has substantially no acid-decomposable groups. As the component (E), for example, novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogenated polyhydroxystyrene, halogenated or alkyl-substituted polystyrene Hydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o /
p- and m / p-hydroxystyrene copolymers, partially O-alkylated compounds based on hydroxyl groups of polyhydroxystyrene (for example, 5 to 30 mol% of O-methylated products, O-
(1-methoxy) ethylated product, O- (1-ethoxy) ethylated product, O-2-tetrahydropyranylated product, O-
(T-butoxycarbonyl) methylated compound) or O
-Acylated (for example, 5 to 30 mol% of O-acetylated product, O- (t-butoxy) carbonylated product, etc.), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene -Hydroxystyrene copolymers, carboxyl group-containing methacrylic resins and derivatives thereof, and polyvinyl alcohol derivatives, but are not limited thereto.

Particularly preferred (E) alkali-soluble resins are novolak resins and o-polyhydroxystyrene,
Polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, partially O-alkylated or O-acylated polyhydroxystyrene, styrene-hydroxystyrene copolymer, α-methyl It is a styrene-hydroxystyrene copolymer. The novolak resin is obtained by subjecting a given monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

The weight average molecular weight of the novolak resin is 1,
It is preferably in the range of 000 to 30,000.
If it is less than 1,000, the film loss of the unirradiated portion after development is large, and if it exceeds 30,000, the development speed is reduced. Particularly preferred is the range of 2,000 to 20,000. In addition, the weight average molecular weight of the polyhydroxystyrene other than the novolak resin, its derivative, and the copolymer is 2,000 or more, preferably 5,000 to 20,000.
0, more preferably 8,000 to 100,000. Further, from the viewpoint of improving the heat resistance of the resist film, it is preferably 10,000 or more. Here, the weight average molecular weight is defined as a value in terms of polystyrene by gel permeation chromatography. In the present invention, these alkali-soluble resins may be used as a mixture of two or more kinds.

The amount of the alkali-soluble resin to be used is preferably 40 to 97% by weight, more preferably 60 to 90% by weight, based on the solid content of the second composition.

[5] (F) Nitrogen-Containing Basic Compound (Component (F)) The preferable (F) nitrogen-containing basic compound that can be blended in the positive resist composition of the present invention is more basic than phenol. Is a strong compound. Above all (A) ~
A nitrogen-containing basic compound having a structure represented by (E) is preferable. By using the nitrogen-containing basic compound, the performance change is small even with the lapse of time from irradiation to post-heating.

[0167]

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Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are the same or different and are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxy group having 1 to 6 carbon atoms. It is an alkyl group or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Also, where R ²⁵¹ and R
²⁵² may combine with each other to form a ring.

[0169]

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Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶
Is the same or different and represents an alkyl group having 1 to 6 carbon atoms). Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazol, substituted or unsubstituted Pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted amino Examples include morpholine, substituted or unsubstituted aminoalkyl morpholine, and the like, and include mono, di, trialkylamine, substituted or unsubstituted aniline, substituted or unsubstituted piperidine, mono and diethanolamine, and the like. Preferred substituents are an amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group It is.

Preferred compounds are guanidine, 1,
1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6
-Methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-
Aminoethyl) piperidine, 4-amino-2,2,6,
6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl)
Pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine ,
4,6-dihydroxypyrimidine, 2-pyrazoline, 3
-Pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diazabicyclo [5,4,0] Undec-7-ene, 2,4,5-triphenylimidazole, tri (n-butyl) amine,
Tri (n-octyl) amine, N-phenyldiethanolamine, N-hydroxyethylpiperidine, 2,6-
Diisopropylaniline, N-cyclohexyl-N'-
Examples include, but are not limited to, morpholinoethylthiourea, N-hydroxyethylmorpholine, and the like.

Of these, particularly preferred compounds are 1,5-diazabicyclo [4.3.0] non-5-
Ene, 1,8-diazabicyclo [5.4.0] undec-7ene, 2,4,5-triphenylimidazole, tri (n-butyl) amine, tri (n-octyl) amine, N-phenyldiethanolamine, N-hydroxyethylpiperidine, 2,6-diisopropylaniline,
N-cyclohexyl-N'-morpholinoethylthiourea and N-hydroxyethylmorpholine. These nitrogen-containing basic compounds can be used alone or in combination of two or more.

The amount of the nitrogen-containing basic compound to be used is generally 0.001 to 10% by weight, based on the solid content of the composition,
Preferably it is 0.01 to 5% by weight. If the amount is less than 0.001% by weight, the effect of the addition of the nitrogen-containing basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, sensitivity tends to decrease and developability of a non-irradiated portion tends to deteriorate.

[6] (G) Fluorine and / or Silicon Surfactant ((G) Component) The positive resist composition of the present invention preferably contains (G) component. The component (G) is at least one surfactant selected from a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom. When the positive resist composition of the present invention contains the above surfactant, the sensitivity, resolution, substrate adhesion, and dry etching resistance are excellent when using an exposure light source of 250 nm or less, particularly 220 nm or less, and storage over time. It is possible to obtain a resist pattern with less subsequent particles and with less development defects and scum. As these surfactants, for example, JP-A-62-36663, JP-A-61-226
No. 746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834,
The surfactants described in JP-A-9-54432 and JP-A-9-5988 can be exemplified, and the following commercially available surfactants can be used as they are. As commercially available surfactants that can be used, for example, F-top EF301, EF303, (Shin-Akita Chemical Co., Ltd.)
), Florado FC430, 431 (manufactured by Sumitomo 3M Limited),
Megafac F171, F173, F176, F189, R08 (Dai Nippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 10
3, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troysol S-
366 (manufactured by Troy Chemical Co., Ltd.) or a silicon-based surfactant.
Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant.

The amount of the surfactant is usually 0.001% by weight to 2% by weight based on the solid content in the composition of the present invention.
% By weight, preferably 0.01% to 1% by weight.
These surfactants can be used alone or in combination of two or more.

[7] Other Components Used in the Present Invention The positive resist composition of the present invention may further contain a dye, a pigment, a plasticizer, a surfactant other than those described above, a photosensitizer, And a compound having two or more phenolic OH groups for promoting solubility in a developing solution.

The compound having two or more phenolic OH groups that can be used in the present invention is preferably a phenol compound having a molecular weight of 1,000 or less. Further, it is necessary to have at least two phenolic hydroxyl groups in the molecule. If the number exceeds 10, the effect of improving the development latitude is lost. When the ratio of the phenolic hydroxyl group to the aromatic ring is less than 0.5, the film thickness dependency is large, and the development latitude tends to be narrow. If this ratio exceeds 1.4, the stability of the composition deteriorates, and it becomes difficult to obtain high resolution and good film thickness dependency, which is not preferable.

The preferred addition amount of the phenol compound is 2 to 50% by weight, more preferably 5 to 30% by weight, based on the alkali-soluble resin. 50% by weight
If the addition amount exceeds the above range, the development residue becomes worse and a new defect that the pattern is deformed at the time of development occurs, which is not preferable.

Such a phenol compound having a molecular weight of 1,000 or less can be obtained by, for example, referring to the methods described in JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and EP 219294. ,
It can be easily synthesized by those skilled in the art. Specific examples of the phenol compound are shown below, but the compounds that can be used in the present invention are not limited to these.

Resorcin, phloroglucin, 2, 3, 4
-Trihydroxybenzophenone, 2,3,4,4'-
Tetrahydroxybenzophenone, 2,3,4,3 ',
4 ', 5'-hexahydroxybenzophenone, acetone-pyrogallol condensation resin, fluoroglucoside,
4,2 ', 4'-biphenyltetrol, 4,4'-thiobis (1,3-dihydroxy) benzene, 2,2',
4,4'-tetrahydroxydiphenyl ether, 2,
2 ', 4,4'-tetrahydroxydiphenylsulfoxide, 2,2', 4,4'-tetrahydroxydiphenylsulfone, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) Cyclohexane, 4,4- (α-methylbenzylidene) bisphenol, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene,
α, α ', α "-tris (4-hydroxyphenyl)-
1-ethyl-4-isopropylbenzene, 1,2,2-
Tris (hydroxyphenyl) propane, 1,1,2-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Propane, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, 1,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,3-tris (hydroxyphenyl) butane, para [α, α , Α ', α'-tetrakis (4-hydroxyphenyl)]-xylene.

[Preparation of Positive Resist Composition and Use Thereof] The components contained in the positive resist composition of the present invention have been described above. Next, a method for preparing the positive resist composition of the present invention and a method for using the same will be described. The composition of the present invention is applied to a support by dissolving the above components in the above-mentioned solvent. As the solvent used here,
Ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methyl Pyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

Among the above, preferred solvents are 2-
Heptanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, methoxypropion And methyl ethoxypropionate, N-methylpyrrolidone and tetrahydrofuran.

At this time, it is preferable to add the above-mentioned (G) fluorine-based and / or silicon-based surfactant to the solvent. Further, a surfactant other than the component (G) can be added. As such a surfactant, specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether , Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate , Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxo Nonionic surfactants such as fatty acid esters of polyoxyethylene sorbitan such as ethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate; acrylic acid Alternatively, methacrylic acid (co) polymerized polyflow No. 75, no. 9
5 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. The amount of these surfactants is usually 2% by weight or less, preferably 1% by weight or less, based on the solid content in the composition of the present invention.

After the above composition is applied on a substrate (eg, silicon / silicon dioxide coating, SiON, TiN, SOG) such as used in the manufacture of precision integrated circuit devices by a suitable application method such as a spinner or a coater, Irradiation through a predetermined mask, baking and development can provide a good resist pattern.

When the exposure light source is DUV light, it is preferable to apply a resist film on a substrate provided with an antireflection film. Thereby, the standing wave is reduced, and the resolution is improved. Preferable examples of the antireflection film include DUV series manufactured by Brewer Science or AR series manufactured by Shipley.

Examples of the developer for the positive resist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, and n-propylamine. Primary amines such as diethylamine, di-
secondary amines such as n-butylamine, triethylamine, tertiary amines such as methyldiethylamine, dimethylethanolamine, alcoholamines such as triethanolamine, tetramethylammonium hydroxide,
An alkaline aqueous solution such as a quaternary ammonium salt such as tetraethylammonium hydroxide, or a cyclic amine such as pyrrole or pichelidine can be used. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0187]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the scope of the present invention is not limited in any way by these examples.

Synthesis Example 1 (Synthesis of Sulfonic Acid Generator as Component (A)) (1) Synthesis of Compound I-1 Bis (t-butylphenyl) iodonium iodide 20
500 ml of methanol and 8.9 g of silver oxide (I) were added to the resulting mixture, and the mixture was stirred at room temperature in a dark place for 4 hours. The reaction solution was filtered through filter paper and then through a 0.1 μm filter to remove silver compounds. 11. Add perfluoroethoxyethanesulfonic acid to the filtrate.
1 g was added, and the mixture was concentrated. The resulting oil was dissolved in 1 L of ethyl acetate, and washed twice with a 2% aqueous solution of tetramethylammonium hydroxide and twice with distilled water. The organic layer was dried and concentrated to obtain 48 g of a compound I-1. 300 MHz ¹ H-NMR (CDCl ₃ ) δ 0.6 (t, 6H), δ 1.15 (s, 12H), δ
1.55 (q, 4H), δ 7.3 (d, 4H), δ 7.8
(D, 4H) Compounds (I-2) to (I-9) were also synthesized in the same manner using the corresponding sulfonium iodide.

(2) Synthesis of Compound II-1 28.1 g of triphenylsulfonium iodide was dissolved in 500 ml of methanol, and 17.3 g of silver (I) oxide was added thereto.
g was added. This was stirred at room temperature in a dark place for 4 hours, and the reaction solution was filtered through a filter paper and then through a 0.1 μm filter to remove silver compounds. 25 g of perfluoroethoxyethanesulfonic acid was added to the filtrate, and the obtained oil was concentrated. The obtained oil was dissolved in 1 L of ethyl acetate, and this was washed twice with a 2% aqueous solution of tetramethylammonium hydroxide and twice with distilled water. did. The organic layer was dried and concentrated, and the obtained solid was washed with diisopropyl ether to obtain 48 g of a compound II-1. 300 MHz < ¹ > H-NMR [delta] 7.5-7.7 (m, 15H) Compounds (II-2) to (II-16) were also synthesized in the same manner using the corresponding sulfonium iodide. Further, the compound of the general formula (III) was also synthesized using the same method as the compound of the general formula (II).

Synthesis Example 2 [Synthesis of Resin as Component (B)] (1) <p- (1- (cyclohexylethoxy) ethoxy) styrene / p-hydroxystyrene (30/70)
Synthesis of (Resin A-25)> p-hydroxystyrene (VP-8000 manufactured by Nippon Soda)
70 g was heated and dissolved in 320 g of propylene glycol monomethyl ether acetate (PGMEA), dehydrated by distillation under reduced pressure, and then cooled to 20 ° C. To this solution was added 0.35 g of pyridinium-p-toluenesulfonate and 22.4 g of cyclohexaneethanol. To this solution, 17.5 g of t-butyl vinyl ether was slowly added, and reacted at 20 ° C. for 5 hours. 0.28 g of triethylamine and 320 ml of ethyl acetate were added to the reaction solution, which was washed three times with 150 ml of distilled water. The solvent was distilled off and concentrated. The obtained oil was dissolved in 100 ml of acetone, and this was slowly poured into 2 L of distilled water. The precipitated powder was collected by filtration and dried to obtain 54 g of the desired product.

(2) <p- (1- (cyclohexylethoxy) ethoxy) styrene / p-acetoxystyrene /
p-Hydroxystyrene (30/10/60) resin A-
Synthesis of 38> p-hydroxystyrene (VP-8000 manufactured by Nippon Soda)
70 g was heated and dissolved in 320 g of propylene glycol monometer ether acetate (PGMEA), dehydrated by distillation under reduced pressure, and then cooled to 20 ° C. To this solution, 0.35 g of viridinium-p-toluenesulfonate and 22.4 g of cyclohexaneethanol were added. To this solution, 17.5 g of t-butyl vinyl ether was slowly added, and reacted at 20 ° C. for 5 hours. 5.53 g of pyridine was added to the reaction solution, and 5.9 g of acetic anhydride was slowly added thereto. The reaction was carried out at room temperature for 1 hour, and 320 ml of ethyl acetate was added to the solution, which was washed three times with 150 ml of distilled water. The solvent was distilled off and concentrated. The obtained oil was dissolved in 100 ml of acetone, and this was slowly poured into 2 L of distilled water. The precipitated powder is collected by filtration and dried to obtain 5
8 g were obtained.

(3) The following resin was synthesized by using the same method as in the above (1) and (2). A-3; p- (1-ethoxyethoxy) styrene / p-
Hydroxystyrene (35/65) molecular weight 15,000,
Dispersion degree (Mw / Mn) 1.1 A-7; p- (1-isobutoxyethoxy) styrene / p-hydroxystyrene (30/70) molecular weight 600
0, dispersity (Mw / Mn) 1.2 A-36; p- (1-phenethyloxyethoxy) styrene / p-acetoxystyrene / p-hydroxystyrene (30/10/60) molecular weight 11,000, dispersity (M
w / Mn) 1.2 A-41; p- (1- (4-t-butylcyclohexylcarboxyethoxy) ethoxystyrene / p-acetoxystyrene / p-hydroxystyrene (30/10/6)
0) Molecular weight 12000, degree of dispersion (Mw / Mn) 1.1 A-43; p- (1- (cyclohexylethoxy) ethoxy) styrene / pt-butylstyrene / p-hydroxystyrene (30/8/62) Molecular weight 18000, degree of dispersion (Mw / Mn) 2.3 A-22; p- (1-benzyloxyethoxy) styrene / p-hydroxystyrene (25/75) molecular weight 13
000, dispersity (Mw / Mn) 1.3 A-35; p- (1-benzyloxyethoxy) styrene / p-hydroxystyrene / p-acetoxystyrene (20/70/10) molecular weight 9000, dispersity (Mw) /
Mn) 1.2

Further, the following resin as the component (A) was synthesized. (4) <A-48; Synthesis of p-hydroxystyrene / t-butyl acrylate (79/21)> 84.1 g of p-vinylphenol and 22.4 g of t-butyl acrylate were dissolved in 150 g of dioxane, and nitrogen was added for 1 hour. Airflow was introduced. 6.91 g of dimethyl 2,2′-azobisisobutyrate was added, and the mixture was heated to 75 ° C. under a nitrogen stream to carry out polymerization for 12 hours. After completion of the polymerization, the reaction solution was cooled to room temperature, 150 g of acetone was added thereto, and the mixture was diluted and dropped into a large amount of hexane to obtain a solid polymer. Acetone dilution and charging into hexane were repeated three times to remove residual monomers. The obtained polymer was dried under reduced pressure at 60 ° C. to obtain a polymer A-48. As a result of NMR analysis, the composition ratio of p-vinylphenol: t-butyl acrylate was 79:21. Mw is 12,000,
The dispersity (Mw / Mn) was 2.6.

(5) <A-16; p- (1-isobutoxyethoxy) styrene / p-hydroxystyrene / t
-Synthesis of butyl acrylate (20/59/21)> 20 g of the above polymer (A-48) and 80 g of propylene glycol monoethyl ether acetate (PGMEA)
And heated to 60 ° C., and then the pressure was gradually reduced to 2
The pressure was adjusted to 0 mmHg, and PGMEA and water in the system were azeotropically dehydrated. After azeotropic dehydration, the mixture was cooled to 20 ° C, 2.2 g of isobutyl vinyl ether was added, and 3 mg of p-toluenesulfonic acid was further added. After the addition, the reaction was carried out for 2 hours, and the acid was neutralized by adding a small amount of triethylamine. Thereafter, ethyl acetate was added to the reaction solution, and the salt was removed by washing with ion-exchanged water. Further, ethyl acetate and water were distilled off from the reaction solution under reduced pressure to obtain a target product, polymer A-16.

(6) A-51; p-hydroxystyrene / styrene / t-butyl acrylate (78/7/1
5) (molecular weight 13100, degree of dispersion (Mw / Mn)
7) was synthesized in the same manner as in the resin A-48. (7) <A-49; p-hydroxystyrene / p- (t
-Butoxycarbonyloxy) styrene (60/40)
Synthesis of poly-p-hydroxystyrene (VP-800 manufactured by Nippon Soda)
0, weight average molecular weight 11,000) was dissolved in 40 ml of pyridine, and di-t-butyl dicarbonate (1.
28 g were added. After reacting at room temperature for 3 hours, the mixture was added to a solution of 1 liter of ion-exchanged water / 20 g of concentrated hydrochloric acid. The precipitated powder was filtered, washed with water, and dried to obtain a p-hydroxystyrene / p- (t-butyloxycarbonyloxy) styrene copolymer (60/40).

Examples 1 to 30, Comparative Examples 1 to 3 According to the formulations shown in Tables 1 and 2, each component was dissolved in a solvent.
The solution was adjusted to a solid concentration of 15%, and this solution was filtered through a 0.1 μm polyethylene filter to prepare a resist solution. This resist solution was evaluated as follows.

A. Evaluation of KrF Excimer Laser Irradiation DUV42 (manufactured by Brewer Science) was applied onto a hexamethyldisilazane-treated silicon wafer and heated at 215 ° C. for 60 seconds to provide an antireflection film having a thickness of 550 Å. The resist solution was uniformly applied using a spin coater, and dried by heating on a hot plate at 120 ° C. for 90 seconds to form a 0.6 μm resist film. For this resist film, KrF
Pattern irradiation was performed using an excimer laser stepper (NA = 0.63) using a line and space mask, and immediately after irradiation, the pattern was heated on a hot plate at 110 ° C. for 90 seconds. Further, it is developed with a 2.38% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds,
After rinsing with pure water for 0 second, it was dried. From the pattern on the silicon wafer thus obtained, the performance of the resist was evaluated by the following method. Table 3 shows the results.

(Resolution) Indicates the limit resolution at the irradiation dose for reproducing a 0.18 μm line-and-space (1/1) mask pattern. (Exposure margin) The optimum dose is the dose that reproduces a 0.16 μm line-and-space (1/1) mask pattern, and the optimum dose is the dose that reproduces a line width of 0.16 μm ± 10%. The divided value was expressed as a percentage (%). The larger the number, the smaller the line width change with respect to the change in irradiation dose.

(Depth of focus) A 0.15 μm line-and-space (1/1) at a dose for reproducing a 0.15 μm line-and-space (1/1) mask pattern is used.
The depth of focus of 1) was measured. The larger the value, the wider the depth of focus.

[0200]

[Table 1]

[0201]

[Table 2]

(Description of Components in Tables 1 and 2) (A) Component PAG-A; triphenylsulfonium perfluorobutanesulfonate PAG-B; bis (t-butylphenyl) iodonium perfluorobutanesulfonate

Component (B) (the blending amount is a value as a solid content) The PHS / ST of Example 22 was a p-hydroxystyrene / styrene (molar ratio: 85:15) copolymer (weight average molecular weight; 20000, dispersity: 2.9), and is an alkali-soluble resin.

(B'-1) to (B'-3) are compounds having the following structures.

[0205]

Embedded image

(D-1) to (D-3) are compounds having the following structures.

[0207]

Embedded image

(F) Basic compound component (1); 1,5-diazabicyclo [4.3.0] -5-
Nonene (2); 2,4,5-triphenylimidazole (3); tri-n-butylamine (4); N-hydroxyethylpiperidine (5); tetrabutylammonium hydroxide

(G) Surfactant component W-1: Megafac F176 (Dainippon Ink Co., Ltd.)
(Fluorine) W-2: Megafac R08 (Dai Nippon Ink Co., Ltd.)
(Fluorine and silicon type) W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) W-4; Troysol S-366 (Troy Chemical Co., Ltd.)
(Fuso system)

Solvent PGMEA: Propylene glycol monomethyl ether acetate PGME; Propylene glycol monomethyl ether (1-methoxy-2-propanol) EL; Ethyl lactate EEP; Ethyl ethoxypropionate BL; γ-butyrolactone CH; Cyclohexanone

[0211]

[Table 3]

From the results shown in Table 3, the following is clear. By irradiating the resist films of Examples 1 to 30, which are the positive resist compositions of the present invention, with a KrF laser beam, which is a far ultraviolet ray, a pattern is formed with high resolution and with a wide exposure margin and a wide depth of focus. You. On the other hand, in the case of Comparative Examples 1 to 3 not using the component (A), the exposure margin and the depth of focus are narrow. Example 1
In the evaluation of Nos. To 30, no generation of development residue was observed. In Comparative Examples 1 to 3, a fine pattern of 0.13 μm or less was not resolved by development residue.

B. Evaluation of electron beam irradiation Some of the examples described in Tables 1 and 2 above (Examples described in Table 4) were adjusted to a solid concentration of 17% to obtain a resist solution. However, 1 g of benzoyloxyvinyl ether (vinyloxyethyl benzoate) was further added to the compositions of Examples 8, 13, and 23 and Comparative Example 3. The resist solution was uniformly applied to a hexamethyldisilazane-treated silicon substrate by a spin coater, and heated and dried on a hot plate at 120 ° C. for 60 seconds to form a 0.8 μm resist film. This resist film was irradiated with an electron beam lithography apparatus (acceleration voltage: 50 keV, beam diameter: 0.20 μm), and immediately after irradiation, heated on a hot plate at 110 ° C. for 90 seconds. The film was further developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and dried. From the pattern on the silicon wafer thus obtained, the performance of the resist was evaluated by the following method. Table 4 shows the results.

(Image Evaluation Method) The formed 0.2 μm contact hole pattern was observed with a scanning electron microscope to examine the profile.

(Sensitivity Evaluation Method) Evaluation was performed using an irradiation dose (μC / cm ² ) for reproducing a contact hole pattern of 0.20 μm. (Resolving power evaluation method) The resolving power indicates a limit resolving power at an irradiation dose for reproducing a contact hole pattern of 0.20 μm.

[0216]

[Table 4]

From the results shown in Table 4, the composition of the present invention was
Further, by the electron beam irradiation, an excellent rectangular profile pattern can be formed with high sensitivity and high resolution without an inverse tapered profile caused by scattering peculiar to the electron beam irradiation.

[0218]

The positive resist composition of the present invention has an improved resolving power and a reduced development residue due to a lithography technique using a short wavelength exposure light source capable of ultrafine processing and a positive chemically amplified resist. Process tolerances, such as exposure margins and depth of focus. In addition, excellent performance is exhibited even when an electron beam is used as the irradiation energy beam.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 309/17 C07C 309/17 381/12 381/12 C08K 5/00 C08K 5/00 C08L 101/02 C08L 101/02 C09K 3/00 C09K 3/00 K G03F 7/039 601 G03F 7/039 601 H01L 21/027 H01L 21/30 502R F-term (reference) 2H025 AA02 AA04 AB03 AB16 AC04 AC08 AD03 BE00 BE07 BE10 BG00 CB41 CB42 CC20 FA17 4H006 AA01 AB76 4J002 BC04Y BC09Y BC12W BC12X BC12Y BG04X CC03Y EV236 FD206 GP03

Claims (5)

[Claims] 1. A compound which generates (A) a sulfonic acid represented by the following general formula (X) upon irradiation with actinic rays by the action of at least one type of (B) acid, and has a solubility in an alkaline developer. A positive resist composition comprising a resin having a group that increases the value of Embedded image In the general formula _{(X), R 1 a~R 13} a is a hydrogen atom, an alkyl group, an alkyl group substituted with a halogen atom, a halogen atom, a hydroxyl group. A represents a divalent linking group having a hetero atom or a single bond. However, when A is a single bond, R
₁ a to R ₁₃ all of a is not simultaneously represent a fluorine atom, and R ₁ a to R ₁₃ all a do not simultaneously represent hydrogen atoms. m represents an integer of 0 to 12. n represents the integer of 0-12. q represents an integer of 1 to 3. 2. The composition further comprises (C) a low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less, which has a group decomposable by an acid and whose dissolution rate in an alkaline developer is increased by the action of an acid. The positive resist composition according to claim 1, wherein (A) a compound capable of decomposing the sulfonic acid-generating compound represented by the general formula (X) according to claim 1 upon irradiation with actinic rays with at least one kind of (C) acid; The dissolution rate in an alkaline developer is increased by the action of an acid;
0 or less low molecular dissolution inhibiting compound (E) A positive resist composition comprising a resin which is insoluble in water and soluble in an alkali developing solution. 4. The compound represented by the general formula (X) according to claim 1.
Sulfonic acid is CF _ThreeCF_Two-O-CF_TwoCF_TwoSO_ThreeIn H
The method according to any one of claims 1 to 3, wherein
Positive resist composition. 5. An iodonium salt or a sulfonium salt compound represented by the following general formulas (I) to (III). Embedded image In the above general formulas (I) to (III), R ₁ To R ₃₇ each independently represent a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group, a cyclic alkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, It represents a halogen atom or -S-R ₃₈ group,. Wherein R ₃₈ represents represents a linear or branched alkyl group, C 3 -C 8 cyclic alkyl groups or number 6-14 aryl group having a carbon carbon having a carbon number of 1 to 12. X
^- is an anion of sulfonic acid represented by formula of claim 1 (X).