JP2001312055A - Positive type resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type electron beam or X-ray resist composition having high resolving power and a positive type electron beam or X-ray resist composition having high sensitivity as well as high resolving power. SOLUTION: In the positive type electron beam or X-ray resist compositions each containing (A) a compound which generates an acid when irradiated with electron beams or X-rays and (B1) a low molecular dissolution inhibiting compound having a group which can be decomposed by the action of the acid, having solubility in an alkali developing solution increased by the action of the acid and having a molecular weight of >1,000 to 3,000, the dissolution inhibiting compound has a structure formed by combining two or more triphenylmethane structures in an unconjugated state in a part where the group which can be decomposed by the action of the acid is not present.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive electron beam or X-ray resist composition, and more particularly to a positive electron beam or X-ray resist composition having excellent resolving power for electron beam or X-ray exposure.

[0002]

2. Description of the Related Art In an i-line resist, a KrF excimer laser resist, an ArF excimer laser resist, and the like, since the resist absorbs at an exposure wavelength, the exposure amount is smaller at the exposed surface and at the bottom at the bottom, In the case of a positive resist, a pattern profile called a tapered shape is generally obtained.

However, in the case of an electron beam resist, the incident electrons have electric charges and interact with the nuclei and electrons of the material constituting the resist, so that scattering always occurs when the electron beam enters the resist film ( For electron scattering, see "THOMPSON, WILLSON, BOWDEN,""Introduction to
Microlithograghy "ACS Symposium series 219, p47-6
3 ". ). Therefore, in the exposed portion, the exposed area is larger at the bottom than at the surface of the resist film. In the case of a positive resist, there is a problem that a pattern profile called an inverse tapered shape is formed.
In addition, even if exposure is performed with a reduced beam diameter in order to resolve a fine pattern, there is also a problem that the scattering increases the exposure area and deteriorates the resolving power. Also, in X-ray lithography, there is a similar problem of resolution degradation.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive electron beam or X-ray resist composition having a high resolution and a high sensitivity positive electron beam or X-ray resist composition in addition to a high resolution. To provide.

[0005]

That is, according to the present invention,
It has been found that the above object of the present invention can be achieved by adding a compound which generates an acid upon irradiation with an electron beam or X-ray or a specific low-molecular dissolution inhibiting compound to a positive electron beam or X-ray resist composition. Was. That is, the present invention has the following configuration.

(1) (A) a compound capable of generating an acid upon irradiation with an electron beam or X-ray, (B1) a group capable of decomposing under the action of an acid, and its solubility in an alkali developing solution is increased by the action of an acid. Molecular weight exceeding 1000, molecular weight 3
In a positive resist composition containing a low molecular weight dissolution inhibiting compound of 2,000 or less, two or more triphenylmethane structures are non-conjugated to a portion other than a group of the low molecular weight dissolution inhibiting compound which can be decomposed by the action of an acid. A positive electron beam or X-ray resist composition having a structure linked to:

(2) The positive compound according to (1), wherein the low molecular weight dissolution inhibiting compound is at least one compound selected from the group consisting of compounds represented by the following general formula (b1). Type electron beam or X-ray resist composition.

[0008]

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In the general formula (b1), R₁₀₁~ R₁₁₈Are the same
And may be different from each other, such as a hydrogen atom, a linear alkyl group,
Shows branched alkyl group, cyclic alkyl group, and alkenyl group.
You. L represents a methylene group which may have a substituent.
Z may be the same or different and each represents a hydrogen atom, -A⁰, −
R²⁰⁰-COOA⁰, -ArOB⁰It is. However, Z
Of these, 50 mol% or more are not hydrogen atoms. A⁰Is -C
(R²⁰¹) (R²⁰²) (R²⁰³), -Si (R²⁰¹) (R²⁰²)
(R²⁰³), -C (R ²⁰⁴) (R²⁰⁵) -OR²⁰⁶Represents B
⁰Is A⁰Or -COOA⁰Represents R²⁰⁰Is a single bond,
Divalent aliphatic or aromatic carbon which may have a substituent
Represents a hydrogen group, -Ar- is a monocyclic or polycyclic substituent
Represents a divalent aromatic hydrocarbon group which may be present. R²⁰¹,
R²⁰², R²⁰³, R²⁰⁴, R²⁰⁵Are the same but different
Hydrogen atom, linear alkyl group, branched alkyl group
Kill group, cyclic alkyl group, alkenyl group or aryl
R²⁰⁶Is a linear alkyl group, a branched alkyl group
Represents a kill group or an aryl group. Where R²⁰¹~ R
²⁰³At least two of them are groups other than a hydrogen atom,
Also, R²⁰¹~ R²⁰³, And R²⁰⁴~ R²⁰⁶Two of
The groups may be linked together to form a ring.

(3) (A) a compound capable of generating an acid upon irradiation with an electron beam or X-ray, (B2) a group capable of decomposing under the action of an acid, and its solubility in an alkali developing solution is increased by the action of an acid. Molecular weight exceeding 1000, molecular weight 3
In a positive resist composition containing a low molecular weight dissolution inhibiting compound of not more than 000, the low molecular weight dissolution inhibiting compound has a structure represented by the following general formula (b2) as a partial structure:
A positive electron beam or X-ray resist composition comprising at least one non-conjugated structure, wherein the structure is non-conjugated.

[0011]

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In the general formula (b2), R₁₁₉~ R₁₂₆Are the same
And may be different from each other, such as a hydrogen atom, a linear alkyl group,
Shows branched alkyl group, cyclic alkyl group, and alkenyl group.
You. L represents a methylene group which may have a substituent.
Z may be the same or different and each represents a hydrogen atom, -A⁰, −
R²⁰⁰-COOA⁰, -ArOB⁰It is. However, Z
Of these, 50 mol% or more are not hydrogen atoms. A⁰Is -C
(R²⁰¹) (R²⁰²) (R²⁰³), -Si (R²⁰¹) (R²⁰²)
(R²⁰³), -C (R ²⁰⁴) (R²⁰⁵) -OR²⁰⁶Represents B
⁰Is A⁰Or -COOA⁰Represents R²⁰⁰Is a single bond,
Divalent aliphatic or aromatic carbon which may have a substituent
Represents a hydrogen group, -Ar- is a monocyclic or polycyclic substituent
Represents a divalent aromatic hydrocarbon group which may be present. R²⁰¹,
R²⁰², R²⁰³, R²⁰⁴, R²⁰⁵Are the same but different
Hydrogen atom, linear alkyl group, branched alkyl group
Kill group, cyclic alkyl group, alkenyl group or aryl
R²⁰⁶Is a linear alkyl group, a branched alkyl group
Represents a kill group or an aryl group. Where R²⁰¹~ R
²⁰³At least two of them are groups other than a hydrogen atom,
Also, R²⁰¹~ R²⁰³, And R²⁰⁴~ R²⁰⁶Two of
The groups may be linked together to form a ring.

(4) The low molecular weight dissolution inhibiting compound is at least one compound selected from the group consisting of compounds represented by the following general formulas (b3) and (b4). The positive electron beam or X-ray resist composition according to (3).

[0014]

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In the general formula (b3), R₁₂₇~ R₁₃₂Are the same
And may be different from each other, such as a hydrogen atom, a linear alkyl group,
Shows branched alkyl group, cyclic alkyl group, and alkenyl group.
You. L represents a methylene group which may have a substituent.
Z may be the same or different and each represents a hydrogen atom, -A⁰, −
R²⁰⁰-COOA⁰, -ArOB⁰It is. However, Z
Of these, 50 mol% or more are not hydrogen atoms. A⁰Is -C
(R²⁰¹) (R²⁰²) (R²⁰³), -Si (R²⁰¹) (R²⁰²)
(R²⁰³), -C (R ²⁰⁴) (R²⁰⁵) -OR²⁰⁶Represents B
⁰Is A⁰Or -COOA⁰Represents R²⁰⁰Is a single bond,
Divalent or higher valent aliphatic or aromatic which may have a substituent
Represents a hydrocarbon group, and -Ar- is a monocyclic or polycyclic substituent
It represents a divalent or higher valent aromatic hydrocarbon group which may have a group.
R²⁰¹, R²⁰², R²⁰³, R²⁰⁴, R²⁰⁵Are the same
And may be different from each other, such as a hydrogen atom, a linear alkyl group,
A branched alkyl group, a cyclic alkyl group, an alkenyl group or
Represents an aryl group;²⁰⁶Is a linear alkyl group,
Represents a branched alkyl group or an aryl group. Where R
²⁰¹~ R²⁰³At least two of which are groups other than hydrogen atoms
Yes, and R²⁰¹~ R²⁰³, And R²⁰⁴~ R²⁰⁶Of
Two groups may combine with each other to form a ring. Y is
Represents a hydrogen atom or a methyl group.

[0016]

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In the general formula (b4), R₁₃₃~ R₁₄₄Are the same
And may be different from each other, such as a hydrogen atom, a linear alkyl group,
Shows branched alkyl group, cyclic alkyl group, and alkenyl group.
You. L represents a methylene group which may have a substituent.
Z may be the same or different and each represents a hydrogen atom, -A⁰, −
R²⁰⁰-COOA⁰, -ArOB⁰It is. However, Z
Of these, 50 mol% or more are not hydrogen atoms. A⁰Is -C
(R²⁰¹) (R²⁰²) (R²⁰³), -Si (R²⁰¹) (R²⁰²)
(R²⁰³), -C (R ²⁰⁴) (R²⁰⁵) -OR²⁰⁶Represents B
⁰Is A⁰Or -COOA⁰Represents R²⁰⁰Is a single bond,
Divalent aliphatic or aromatic carbon which may have a substituent
Represents a hydrogen group, -Ar- is a monocyclic or polycyclic substituent
Represents a divalent aromatic hydrocarbon group which may be present. R²⁰¹,
R²⁰², R²⁰³, R²⁰⁴, R²⁰⁵Are the same but different
Hydrogen atom, linear alkyl group, branched alkyl group
Kill group, cyclic alkyl group, alkenyl group or aryl
R²⁰⁶Is a linear alkyl group, a branched alkyl group
Represents a kill group or an aryl group. Where R²⁰¹~ R
²⁰³At least two of them are groups other than a hydrogen atom,
Also, R²⁰¹~ R²⁰³, And R²⁰⁴~ R²⁰⁶Two of
The groups may be linked together to form a ring.

(5) (A) a compound capable of generating an acid upon irradiation with an electron beam or X-ray; (B3) a group capable of decomposing under the action of an acid; the solubility in an alkali developing solution is increased by the action of an acid. A low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less, wherein the low molecular weight dissolution inhibiting compound has a biphenyl structure or a triphenylene structure as a partial structure, and the benzene other than the benzene ring contained in the group decomposable by the acid; A positive electron beam or X-ray resist composition, wherein the total number of rings is 3 or more and 13 or less.

(6) The low molecular weight dissolution inhibiting compound is at least one compound selected from the group consisting of compounds represented by the following formulas (Ih-1) to (Ih-7). The positive electron beam or X-ray resist composition according to the above (5).

[0020]

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[0021]

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[0022]

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[0023] In the above formula (Ih-1) ~ (Ih -7), R 101 '~R 110', R 112 '~R 21 3' , which may be the same or different, a hydrogen atom, a linear , A branched or cyclic alkyl group or an alkenyl group. R ₁₁₁ ′ represents a hydrogen atom, a linear, branched or cyclic alkyl group, alkenyl group or phenyl group. R ₁₃₁ ′ and R ₁₃₂ ′
It may combine with each other to form a ring. Y ′ represents hydrogen or a methyl group. A plurality of Z's in the same molecule may be the same or different. Z 'is a hydrogen atom, -A ^0', -
R _{300 represents} —COOA ⁰ ′ or —Ar—OB ⁰ ′. However, in the above formulas (Ih-1) to (Ih-4), 90 mol% or more of Z ′ is not hydrogen. In addition, the above formula (Ih-
In 5) to (Ih-7), 50 mol% or more of Z ′ is not hydrogen. A ⁰ ′ is -C (R ₃₀₁ ) (R ₃₀₂ )
_{(R 303), - Si (} R 301) (R 302) (R 3 03) or -
C (R ₃₀₄ ) (R ₃₀₅ ) -OR ₃₀₆ . B ⁰ ′ is −
Represents A ⁰ ′ or —COOA ⁰ ′. R ₃₀₀ represents a single bond or a divalent aliphatic or aromatic group which may have a substituent. Ar represents a divalent aromatic group which may have a substituent. R ₃₀₁ , R ₃₀₂ , R ₃₀₃ , R ₃₀₄ , R ₃₀₅ are
They may be the same or different and represent a hydrogen atom, a linear or branched alkyl group, a cyclic alkyl group, an alkenyl group, an aralkyl group or an aryl group. R ₃₀₆ represents an alkyl group or an aryl group. Any two of R _{301 to} R ₃₀₃ or any two of R _{304 to} R ₃₀₆ may combine to form a ring.

(7) (A) a compound capable of generating an acid upon irradiation with an electron beam or X-ray, (B4) a group capable of decomposing under the action of an acid, and its solubility in an alkali developing solution is increased by the action of an acid. A positive electron beam or X-ray resist composition comprising a low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less, wherein the low molecular weight dissolution inhibiting compound has a fluorene structure as a partial structure.

(8) The low molecular weight dissolution inhibiting compound is at least one compound selected from the group consisting of compounds represented by the following formulas (Ih-8) to (Ih-10). The positive electron beam or X-ray resist composition according to the above (7).

[0026]

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In the above formulas (Ih-8) to (Ih-10), R _{310 to} R ₃₆₅ may be the same or different,
Represents a hydrogen atom, a linear, branched or cyclic alkyl group or an alkenyl group. R ₃₁₁ and R ₃₁₈ , R ₃₂₉ and R ₃₃₀ ,
R ₃₄₂ and R ₃₅₅ may form a ring by a single bond with each other.
Z ′ has the same meaning as described above, but a plurality of Z ′ in the same molecule
May be the same or different. More than 90 mol% of Z in the molecule is not hydrogen.

Preferred embodiments are described below. (9) The above-mentioned (1), comprising at least one of (c) a resin whose solubility in an alkali developing solution is increased by the action of an acid and (d) a resin insoluble in water and soluble in an alkali developing solution. The positive electron beam or X-ray resist composition according to any one of (1) to (8).

(10) The compound capable of generating an acid upon irradiation with an electron beam or X-ray is represented by any of the following general formulas (I) to (II)
(1) to (1), which are at least one compound selected from the group consisting of compounds represented by (I).
The positive electron beam or X-ray resist composition according to any one of (9).

[0030]

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In the formula, R _{1 to} R ₅₃ may be the same or different and are a hydrogen atom, an alkyl group which may be branched or cyclic, an alkoxy group which may be branched or cyclic, a hydroxy group , A halogen atom, or-
Represents SR ₅₄ . R ₅₄ represents an alkyl group or an aryl group which may be branched or cyclic. Also,
Two or more of R _{1 to} R ₁₅ , R _{16 to} R ₄₃ , and R _{44 to} R ₅₃ are bonded to form a single bond, a carbon atom, an oxygen atom, a sulfur atom,
And a ring containing one or more selected from nitrogen and nitrogen. X ^- is optionally substituted;
It represents an anion of alkanesulfonic acid, benzenesulfonic acid or anthracenesulfonic acid having 1 to 18 carbon atoms.

(11) In the above general formulas (I) to (III), X ^- is substituted with at least one fluorine atom and at least one fluorine atom, and may be a branched or cyclic alkyl group. An alkoxy group substituted with at least one fluorine atom, which may be branched or cyclic, an acyl group substituted with at least one fluorine atom, an acyloxy group substituted with at least one fluorine atom, At least one sulfonyl group substituted with at least one fluorine atom, a sulfonyloxy group substituted with at least one fluorine atom, a sulfonylamino group substituted with at least one fluorine atom,
Aryl groups substituted with at least one fluorine atom, at least one
Benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least one selected from the group consisting of an aralkyl group substituted with at least one fluorine atom and an alkoxycarbonyl group substituted with at least one fluorine atom The positive electron beam or X-ray resist composition according to the above (10), which is an anion of

(12) The above (1) to (e), which contain (e) a compound having a cationically polymerizable function.
The positive electron beam or X-ray resist composition according to any of (11).

(13) The compound having a cationic polymerizable function is at least one compound selected from a vinyl compound, a cycloalkane compound, a vinyl compound, a cyclic ether compound, a lactone compound and an aldehyde compound. The positive electron beam or X-ray resist composition according to the above (12).

(14) The positive electron beam or X-ray resist composition according to the above (12), wherein the compound having cationic polymerizability is a compound represented by the general formula (A).

[0036]

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R _a , R _b , R _c , which may be the same or different, represent a hydrogen atom, an alkyl group or an aryl group which may have a substituent, and two of them are bonded to each other; A saturated or olefinically unsaturated ring may be formed.
R _d represents an alkyl group or a substituted alkyl group.

(15) The positive electron beam or X-ray resist composition according to any one of the above (1) to (14), which further comprises (f) a fluorine-based and / or silicon-based surfactant. object. (16) The positive electron beam or X-ray resist composition according to any one of the above (1) to (15), further comprising an organic basic compound.

(17) Solvents of the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monomethyl ether, methyl lactate, ethyl lactate, linear ketones having 6 to 9 carbon atoms, and γ-butyrolactone The positive type electron beam or X-ray resist composition according to any one of the above (1) to (16), comprising at least one of the above.

[0040]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The positive electron beam or X-ray resist composition of the present invention will be described below.

[I] (A) Compound that generates an acid upon irradiation with an electron beam or X-ray (hereinafter also referred to as “component (A)”) As the component (A), an acid is generated upon irradiation with an electron beam or X-ray. Any compound can be used as long as it generates, but the compounds represented by formulas (I) to (III) are preferable.

[I-1] Compounds represented by the general formulas (I) to (III) In the general formulas (I) to (III), a linear group represented by R _{1 to} R ₅₄
As the branched alkyl group, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-
Examples thereof include those having 1 to 4 carbon atoms such as -butyl group and t-butyl group. Examples of the cyclic alkyl group include those having 3 to 8 carbon atoms which may have a substituent, such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group. Examples of the linear or branched alkoxy group represented by R _{1 to} R ₅₃ include a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a t-butoxy group. Such a C1-C4 thing is mentioned. Examples of the cyclic alkoxy group include a cyclopentyloxy group and a cyclohexyloxy group. Examples of the halogen atom for R _{1 to} R ₅₃ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The aryl group of R _54, for example, a phenyl group, a tolyl group, methoxyphenyl group, and a good number of 6 to 14 carbon which may have a substituent such as naphthyl.

As these substituents, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (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.

Further, R _{1 to} R ₁₅ , R _{16 to} R ₄₃ , R _{44 to} R
Of _53, two or more of formed by combining a single bond, carbon, oxygen, one selected sulfur, and nitrogen or 2
Examples of the ring containing more than one kind include a furan ring, a dihydrofuran ring, a pyran ring, a trihydropyran ring, a thiophene ring, a pyrrole ring, and the like.

Further, at least two of R _{16 to} R ₂₀
One, at least two of R ₂₁ to R _25, at least two of R ₂₆ to R _29, at least two of R ₃₀ to R _33, at least two of R ₃₄ to R _38, R _{39 to} R ₄₃
Preferably, at least two of them are hydrogen atoms.

[0046] In the general formula (I) ~ (III), X - represents an anion which may be substituted, alkanesulfonic acids having a carbon number of 1 18, benzenesulfonic acid or anthracene sulfonic acid. In the present invention, X ⁻ is preferably an anion of benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid having at least one selected from the following groups. Thereby, the rectangularity of the profile shape becomes excellent. At least one fluorine atom, a linear, branched or cyclic alkyl group substituted with at least one fluorine atom; a linear, branched or cyclic alkoxy group substituted with at least one fluorine atom. Acyl group substituted with a fluorine atom acyloxy group substituted with at least one fluorine atom sulfonyl group substituted with at least one fluorine atom sulfonyloxy group substituted with at least one fluorine atom at least one fluorine Sulfonylamino group substituted with an atom Aryl group substituted with at least one fluorine atom Aralkyl group substituted with at least one fluorine atom and alkoxycarbonyl group substituted with at least one fluorine atom

The linear, branched or cyclic alkyl group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specifically, trifluoromethyl group, pentafluoroethyl group, 2,
Examples thereof include a 2,2-trifluoroethyl group, a heptafluoropropyl group, a heptafluoroisopropyl group, a perfluorobutyl group, a perfluorooctyl group, a perfluorododecyl group and a perfluorocyclohexyl group. Among them, a perfluoroalkyl group having 1 to 4 carbon atoms, all of which is substituted by fluorine, is preferable.

The linear, branched or cyclic alkoxy group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specifically, a trifluoromethoxy group, a pentafluoroethoxy group,
Examples include a heptafluoroisopropyloxy group, a perfluorobutoxy group, a perfluorooctyloxy group, a perfluorododecyloxy group, a perfluorocyclohexyloxy group, and the like. Among them, a perfluoroalkoxy group having 1 to 4 carbon atoms, all of which is substituted by fluorine, is preferable.

The acyl group has 2 to 12 carbon atoms.
Wherein those substituted with 1 to 23 fluorine atoms are preferred. Specific examples include a trifluoroacetyl group, a fluoroacetyl group, a pentafluoropropionyl group, and a pentafluorobenzoyl group.

The acyloxy group has 2 to 2 carbon atoms.
12 which is substituted with 1 to 23 fluorine atoms is preferred. Specific examples include a trifluoroacetoxy group, a fluoroacetoxy group, a pentafluoropropionyloxy group, and a pentafluorobenzoyloxy group.

The sulfonyl group has 1 to 1 carbon atoms.
12 which is substituted with 1 to 25 fluorine atoms is preferred. Specific examples include a trifluoromethanesulfonyl group, a pentafluoroethanesulfonyl group, a perfluorobutanesulfonyl group, a perfluorooctanesulfonyl group, a pentafluorobenzenesulfonyl group, and a 4-trifluoromethylbenzenesulfonyl group.

The sulfonyloxy group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specific examples include a trifluoromethanesulfonyloxy group, a perfluorobutanesulfonyloxy group, and a 4-trifluoromethylbenzenesulfonyloxy group.

The sulfonylamino group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specific examples include a trifluoromethanesulfonylamino group, a perfluorobutanesulfonylamino group, a perfluorooctanesulfonylamino group, and a pentafluorobenzenesulfonylamino group.

The aryl group has 6 to 1 carbon atoms.
4, which is substituted with 1 to 9 fluorine atoms is preferable. Specifically, a pentafluorophenyl group, 4
-Trifluoromethylphenyl, heptafluoronaphthyl, nonafluoroanthranyl, 4-fluorophenyl, 2,4-difluorophenyl, and the like.

The aralkyl group has 7 to 7 carbon atoms.
It is preferably 10 and substituted by 1 to 15 fluorine atoms. Specific examples include a pentafluorophenylmethyl group, a pentafluorophenylethyl group, a perfluorobenzyl group, a perfluorophenethyl group, and the like.

The alkoxycarbonyl group preferably has 2 to 13 carbon atoms and is substituted by 1 to 25 fluorine atoms. Specific examples include a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a pentafluorophenoxycarbonyl group, a perfluorobutoxycarbonyl group, and a perfluorooctyloxycarbonyl group.

The most preferred X ⁻ is a fluorine-substituted benzenesulfonate anion, and among them, a pentafluorobenzenesulfonate anion is particularly preferred.

The benzene sulfonic acid, naphthalene sulfonic acid or anthracene sulfonic acid having a fluorine-containing substituent may further include a linear, branched or cyclic alkoxy group, an acyl group, an acyloxy group, a sulfonyl group,
It may be substituted with a sulfonyloxy group, a sulfonylamino group, an aryl group, an aralkyl group, an alkoxycarbonyl group (the number of carbon atoms is the same as described above), a halogen (excluding fluorine), a hydroxyl group, a nitro group and the like.

Specific examples of the compound represented by formula (I) are shown below.

[0060]

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[0061]

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Specific examples of the compound represented by formula (II) are shown below.

[0063]

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Specific examples of the compound represented by formula (III) are shown below.

[0065]

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The compounds represented by formulas (I) to (III) may be used alone or in combination of two or more.

The compounds of the general formulas (I) and (II) can be prepared by reacting an aryl Grignard reagent such as aryl magnesium bromide with a substituted or unsubstituted phenylsulfoxide to give the resulting triarylsulfonium halide with the corresponding sulfone. A salt exchange with an acid, a condensation or salt exchange between a substituted or unsubstituted phenylsulfoxide and a corresponding aromatic compound using an acid catalyst such as methanesulfonic acid / diphosphorus pentoxide or aluminum chloride, or diaryliodonium The salt and the diaryl sulfide can be synthesized by a method of condensation and salt exchange using a catalyst such as copper acetate. The compound of the formula (III) can be synthesized by reacting an aromatic compound with periodate. The sulfonic acid or sulfonic acid salt used for the salt exchange is obtained by, for example, a method of hydrolyzing a commercially available sulfonic acid chloride, a method of reacting an aromatic compound with chlorosulfonic acid, or a method of reacting an aromatic compound with sulfamic acid. Can be obtained by

Hereinafter, a method for synthesizing specific compounds of the general formulas (I) to (III) will be described below. (Synthesis of Pentafluorobenzenesulfonic Acid Tetramethylammonium Salt) 25 g of pentafluorobenzenesulfonyl chloride was dissolved in 100 ml of methanol under ice cooling.
To this was slowly added 100 g of a 25% aqueous solution of tetramethylammonium hydroxide. After stirring at room temperature for 3 hours, a solution of pentafluorobenzenesulfonic acid tetramethylammonium salt was obtained. This solution was used for salt exchange with sulfonium salt and iodonium salt.

(Synthesis of triphenylsulfonium pentafluorobenzenesulfonate: Synthesis of specific example (I-1)) Diphenylsulfoxide 509 was converted to benzene 800 m
1 and 200 g of aluminum chloride was added thereto and refluxed for 24 hours. The reaction solution was slowly poured into 2 L of water, and 400 ml of concentrated hydrochloric acid was added thereto, followed by heating at 70 ° C. for 10 minutes. This aqueous solution was washed with 500 ml of ethyl acetate,
After filtration, 200 g of ammonium iodide was added to 400 m of water.
The solution dissolved in 1 was added. The precipitated powder was collected by filtration, washed with water, washed with ethyl acetate and dried to obtain 70 g of triphenylsulfonium iodide. 30.5 g of triphenylsulfonium iodide was added to 1000 ml of methanol.
And 19.1 g of silver oxide was added to the solution, followed by stirring at room temperature for 4 hours. The solution was filtered, and an excess amount of the solution of tetramethylammonium pentafluorobenzenesulfonate synthesized above was added thereto. The reaction solution was concentrated, and this was dissolved in 500 ml of dichloromethane.
% Tetramethylammonium hydroxide aqueous solution and water. After drying the organic phase over anhydrous sodium sulfate,
Concentration provided triphenylsulfonium pentafluorobenzenesulfonate.

(Synthesis of triarylsulfonium pentafluorobenzenesulfonate: Specific examples (I-9) and (II)
Synthesis of a mixture with -1) 50 g of triarylsulfonium chloride (a 50% aqueous solution of triphenylsulfonium chloride, manufactured by Fluka) is dissolved in 500 ml of water, and an excess amount of a solution of tetramethylammonium pentafluorobenzenesulfonate is added thereto. And an oily substance precipitated. The supernatant was removed by decantation, and the obtained oily substance was washed with water and dried to obtain triarylsulfonium pentafluorobenzensulfonate (specific examples (I-9) and (II-1)).
) As a main component.

(Synthesis of di (4-t-amylphenyl) iodonium pentafluorobensensulfonate: Synthesis of Specific Example (III-1)) 60 g of t-amylbenzene, 39.5 g of potassium iodate, 81 g of acetic anhydride, 170 ml of dichloromethane And 66.8 concentrated sulfuric acid under ice-cooling.
g was slowly added dropwise. After stirring for 2 hours under ice cooling, the mixture was stirred at room temperature for 10 hours. To the reaction mixture was added 500 ml of water under ice cooling, and the mixture was extracted with dichloromethane. The organic phase was washed with sodium bicarbonate and water, and concentrated to obtain di (4-t-amylphenyl) iodonium sulfate. This sulfate was added to a solution of an excess amount of tetramethylammonium pentafluorobenzenesulfonate. To this solution was added 500 ml of water, and the mixture was extracted with dichloromethane. The organic phase was washed with a 5% aqueous solution of tetramethylammonium hydroxide and water, and then concentrated to obtain di (4-t-amylphenyl) iodonium pentafluorobenzenesulfonate. Was done. Other compounds can be synthesized using the same method.

[I-2] Other Acid Generators that can be Used as Component (A) In the present invention, the component (A) decomposes by irradiation with an electron beam or X-ray to Can be used. In the present invention, as the component (A), a compound represented by the following general formulas (I) to (III) is used in combination with a compound capable of generating an acid by being decomposed by irradiation of the following radiation. May be. The amount of the photoacid generator that can be used in combination with the compounds represented by the above general formulas (I) to (III) in the present invention is usually in a molar ratio (component (A) / other acid generator). 100/0
20/80, preferably 100/0 to 40/60, and more preferably 100/0 to 50/50.

The total content of the component (A) is based on the solid content of the positive electrode or X-ray resist composition of the present invention.
Usually, it is 0.1 to 20% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 7% by weight.

Examples of such a radiation acid generator include an initiator for photocationic polymerization, an initiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, and a radiation initiator used for microresist. Known compounds that generate an acid upon irradiation and mixtures thereof can be appropriately selected and used.

For example, SISchlesinger, Photogr.Sci.E
ng., 18,387 (1974), TSBal etal, Polymer, 21,423 (198
0) etc., U.S. Pat.No.4,069,055
No. 4,069,056, Re 27,992, Japanese Patent Application No. 3-140,140
Salt, DCNecker etal, Macrom
olecules, 17, 2468 (1984), CSwen et al, Teh, Proc. Con
f.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Patent No.
Nos. 4,069,055 and 4,069,056, and phosphonium salts described in JVCrivello et al., Macromorecules, 10 (6), 1307 (19
77), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 10
No. 4,143, U.S. Pat.Nos. 339,049, 410,201, JP-A-2-150,848, iodonium salts described in JP-A-2-296,514, etc., JVCrivello et al., Polymer J. 17, 73 (1985),
JVCrivelloetal.J.Org.Chem., 43, 3055 (1978), WRWa
tt etal, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (19
84), JVCrivello etal, Polymer Bull., 14,279 (198
5), JVCrivello etal, Macromorecules, 14 (5), 1141 (19
81), JVCrivello etal, J. PolymerSci., Polymer Che
m.Ed., 17,2877 (1979), European Patent Nos. 370,693, 3,90
No. 2,114, No. 233,567, No. 297,443, No. 297,442, U.S. Pat.Nos. 4,933,377, 161,811, No. 410,201, No. 3
No. 39,049, No. 4,760,013, No. 4,734,444, No. 2,833,82
No. 7, Dokoku Patent Nos. 2,904,626, 3,604,580, 3,60
No. 4,581, etc., sulfonium salt, JVCrivello eta
l, Macromorecules, 10 (6), 1307 (1977), JVCrivello et
al, J. PolymerSci., Polymer Chem. Ed., 17,1047 (1979)
Selenonium salts, CSwen et al, Teh, Proc.Co
Onium salts such as arsonium salts described in nf.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.
No., JP-B-46-4605, JP-A-48-36281, JP-A-55-3
No. 2070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401
No., JP-A-63-70243, organic halogen compounds described in JP-A-63-298339, K. Meier et al., J. Rad.Curing, 13
(4), 26 (1986), TPGill et al., Inorg.Chem., 19, 3007 (1
980), D. Astruc, Acc. Chem. Res., 19 (12), 377 (1896), and organometallic / organic halides described in JP-A-2-14145, S. Hayase et al., J. Polymer Sci. ., 25,753 (1987), ER
eichmanis etal, J.Pholymer Sci., Polymer Chem.Ed., 2
3,1 (1985), QQ Zhuetal, J. Photochem., 36, 85, 39, 317 (19
87), B. Amit etal, Tetrahedron Lett., (24) 2205 (1973),
DHR Barton et al., J. Chem Soc., 3571 (1965), PMCol
lins et al., J. Chem.SoC., Perkin I, 1695 (1975), M. Rudins
tein etal, Tetrahedron Lett., (17), 1445 (1975), JWW
alker etal J. Am. Chem. Soc., 110, 7170 (1988), SCBusma
n etal, J. Imaging Technol., 11 (4), 191 (1985), HMHoul
ihan etal, Macormolecules, 21, 2001 (1988), PMCollins
etal, J. Chem. Soc., Chem. Commun., 532 (1972), S. Hayase
etal, Macromolecules, 18, 1799 (1985), E. Reichmanis eta
l, J.Electrochem.Soc., Solid State Sci.Technol., 130
(6), FM Houlihan et al, Macromolcules, 21, 2001 (198
8), European Patent Nos. 0290,750, 046,083, 156,535
No. 271,851, No. 0,388,343, U.S. Pat.No. 3,901,7
No. 10, 4,181,531, JP-A-60-198538, JP-A-53-1
Acid generator having an o-nitrobenzyl-type protecting group described in No. 33022, etc., M. TUNOOKA et al., Polymer Preprints Japa
n, 35 (8), G.Berner et al., J.Rad.Curing, 13 (4), WJMijs
etal, Coating Technol., 55 (697), 45 (1983), Akzo, H.Adac
hi etal, Polymer Preprints, Japan, 37 (3), European Patent No.
0199,672, 84515, 199,672, 044,115,
No. 0101,122, U.S. Pat.Nos. 618,564, 4,371,605,
No. 4,431,774, JP-A-64-18143, JP-A-2-245756
No., compounds which decompose to generate sulfonic acid represented by iminosulfonate described in Japanese Patent Application No. 3-140109,
Disulfone compounds described in JP-A-61-166544 can be exemplified.

Further, a compound in which a group or a compound which generates an acid upon irradiation with such a radiation is introduced into a main chain or a side chain of a polymer, for example, MEWoodhouse et al., JA
m. Chem. Soc., 104, 5586 (1982), SPPappas et al., J. Ima
ging Sci., 30 (5), 218 (1986), S. Kondo et al., Makromol. C
hem., Rapid Commun., 9, 625 (1988), Y. Yamadaetal, Makro
mol. Chem., 152, 153, 163 (1972), JVCrivello et al., J.
PolymerSci., Polymer Chem.Ed., 17, 3845 (1979), U.S. Pat.No. 3,849,137, Dokoku Patent 3914407, JP-A-63-266
No. 53, JP-A-55-164824, JP-A-62-69263, JP-A-6-69263
3-146038, JP-A-63-163452, JP-A-62-153853
And JP-A-63-146029 can be used.

Further, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
The compounds capable of generating an acid described in DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, and EP 126,712 can also be used.

Among the above-mentioned compounds which decompose upon irradiation with 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).

[0079]

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In the formula, R ¹²⁰¹ represents a substituted or unsubstituted aryl group or alkenyl group, and R ¹²⁰² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C
(Y) Show ₃ . Y represents a chlorine atom or a bromine atom.
Specific examples include the following compounds, but the present invention is not limited thereto.

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[0082]

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

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Here, 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 ¹²⁰³ , R ¹²⁰⁴ and R ¹²⁰⁵ 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 those having 1 carbon atom for the aryl group.
C1 to C8 alkoxy, C1 to C8 alkyl, nitro, carboxyl, hydroxy, and halogen atoms, and C1 to C8 alkoxy, carboxyl, and alkoxycarbonyl for alkyl. It is.

[0088] 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 ¹²⁰³ , R ¹²⁰⁴ and R ¹²⁰⁵ and Ar ¹ and Ar ² may be bonded via a single bond or a substituent.

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

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[0092]

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[0100]

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[0101]

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The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JWKnapczyk
etal, J. Am. Chem. Soc., 91, 145 (1969), ALMaycok eta
l, J. Org. Chem., 35, 2532, (1970), E. Goethas et al., Bul
l.Soc.Chem.Belg., 73,546, (1964), HM Leicester, JA
me.Chem.Soc., 51,3587 (1929), JVCrivello etal, J.Po
Chem. Ed., 18,2677 (1980), U.S. Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331.

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

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In the formula, Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ¹²⁰⁶ May be replaced
Represents an unsubstituted alkyl group or aryl group. A is also a substitution
Or unsubstituted alkylene, alkenylene, aryl
Represents a len group. Specific examples include the compounds shown below.
However, the present invention is not limited to these.

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[II] (B) Low molecular acid decomposable dissolution inhibiting compound ("(B) component") The first low molecular acid decomposable dissolution inhibiting compound ((B1), (B2)) used in the present invention. ) Will be described. In the present invention, the compound (B1) has a group that can be decomposed by the action of an acid, and the solubility in an alkali developer exceeds a molecular weight of 1,000, which is increased by the action of an acid.
It is a low molecular weight dissolution inhibiting compound having a molecular weight of 000 or less, and a dissolution inhibiting compound in which two or more triphenylmethane structures are non-conjugatedly linked as a partial structure. The compound (B2) is a low-molecular-weight dissolution inhibiting compound having a molecular weight that can be decomposed by the action of an acid and has a molecular weight of not more than 1000 and a molecular weight of 3,000 or less whose solubility in an alkali developing solution is increased by the action of an acid. The structure is represented by the general formula (b)
It is a dissolution inhibiting compound containing three or more structures represented by 2), and the structures are non-conjugatedly linked.

As the compound (B1), compounds represented by the aforementioned general formula (b)
It is preferably at least one selected from the group consisting of the compounds represented by 1). As the compound (B2), the compounds represented by the aforementioned general formulas (b3) and (b)
It is preferably at least one selected from the group consisting of the compounds represented by 4).

Further, the acid-decomposable dissolution-inhibiting compound (B1) or (B2) may have a plurality of acid-decomposable groups on one benzene ring, but is preferably one benzene ring. It is a compound composed of a skeleton having one acid-decomposable group thereon. Furthermore, the molecular weight of the acid-decomposable dissolution-inhibiting compound (B1) or (B2) of the present invention is 3,000 or less, preferably 1,000 to 2,750, more preferably 1,000 to 2,500. is there.

In the general formulas (b1) to (b4), R
Of ¹⁰¹ to R ¹⁴⁴ linear, as the branched alkyl group, methyl group, ethyl group, propyl group, n- butyl group, sec-
Preferred are those having 1 to 4 carbon atoms such as a butyl group and a t-butyl group. As the cyclic alkyl group, a cyclopropyl group,
Those having 3 to 10 carbon atoms such as a cyclobutyl group, a cyclohexyl group and an adamantyl group are preferred. R ^{101 to} R ¹⁴⁴
As the alkenyl group, those having 2 to 4 carbon atoms such as a vinyl group, a propenyl group, an allyl group and a butenyl group are preferable.

The linking group L in the general formulas (b1) to (b4) represents a methylene group which may have a substituent,
As a substituent, a methyl group is preferable. Y represents a hydrogen atom or a methyl group.

Further, the acid-decomposable groups Z in the general formulas (b1) to (b4) may be the same or different, and the hydrogen atom and the acid-decomposable group include -R ²⁰⁰ -COOA ⁰ or -R ^200.
Ar-OB ⁰ is preferably mentioned. Where A ^{0
Is, -C (R 201) (R} 202) (R 203), - Si
^{(R 201) (R 202)} (R 203) or -C (R ²⁰⁴⁾
Shows the (R ²⁰⁵⁾ -O-R ²⁰⁶ groups. B ⁰ is A ⁰ or —CO
Shows a -O-A ⁰ group.

R ²⁰⁰ represents a single bond or a divalent aliphatic or aromatic hydrocarbon group which may have a substituent;
-Represents a divalent aromatic hydrocarbon group which may have a monocyclic or polycyclic substituent. R ²⁰¹ , R ²⁰² , R ²⁰³ , R ²⁰⁴ ,
R ²⁰⁵ may each be the same or different, represent a hydrogen atom, a linear alkyl group, branched alkyl, cyclic alkyl group, an alkenyl group or an aryl group, R ²⁰⁶
Represents a linear alkyl group, a branched alkyl group or an aryl group. However, at least two of R ^{201 to} R ²⁰³ are groups other than a hydrogen atom, and R ^{201 to} R ²⁰³ ,
And two groups of R ^{204 to} R ²⁰⁶ may be bonded to each other to form a ring.

A linear alkyl group for R ^{201 to} R ²⁰⁶ ,
The branched alkyl group, cyclic alkyl group or alkenyl group is the same as those described above for R ^{101 to} R ¹⁴⁴ . The aryl group represented by R ^{201 to} R ²⁰⁶ is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a xylyl group, a toluyl group, a cumenyl group, a naphthyl group, and an anthracenyl group.

Examples of the divalent aliphatic or aromatic hydrocarbon group for R ²⁰⁰ include —CH ₂ —, —CH ₂ CH ₂ —, and —C
_{H 2 CH 2 CH 2 -,} - CH (CH 3) CH 2 -, - CH 2 C
H (CH ₃₎ -, p- phenylene, m- phenylene, o
-Phenylene, 1,8-naphthylene, 2,6-naphthylene, 9,10-anthrene.

Examples of the divalent aromatic hydrocarbon group of Ar include:
It represents the same as those of the R ^200. R ^{201 to} R ²⁰³ ,
And the ring formed by bonding two groups out of R ^{204 to} R ²⁰⁶ to each other includes a cyclopentane ring, a cyclohexane ring and the like, or a tetrahydrofuran ring and a tetrahydropyran ring.

Examples of the substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, and the above-mentioned alkyl groups, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group. Alkoxy groups such as groups, n-butoxy groups, isobutoxy groups, sec-butoxy groups, t-butoxy groups, alkoxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups, aralkyl groups such as benzyl groups, phenethyl groups and cumyl groups, Aralkyloxy group, formyl group, acetyl group, butyryl group, benzoyl group, cyanyl group, acyl group such as valeryl group, acyloxy group such as butyryloxy group, the above alkenyl group, vinyloxy group, propenyloxy group, allyloxy group, butenyloxy group Alkenyloxy groups such as Serial aryl group, an aryloxy group such as phenoxy group, and an aryloxycarbonyl group such as benzoyloxy group.

-A ⁰ , R ²⁰⁰ -COOA ⁰ or -Ar-O
The group represented by B ⁰ 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, 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.

In the general formulas (b1) to (b4), Z represents a hydrogen atom, -A ⁰ , -R ²⁰⁰ -COOA ⁰ or -Ar-O
Represents B ^0, and at least 50 mol%, preferably 60 mol% or more in the same molecule is represented by —A ⁰ , —R ²⁰⁰ —COOA
⁰ or an -Ar-OB ^0. Multiple Zs in the same molecule are
They may be the same or different.

In the present invention, general formulas (b1) to (b)
Specific examples of the compound represented by 4) are shown below.

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Z in the above exemplified compounds is a hydrogen atom or
Represents the structure shown below.

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Next, the second low molecular weight acid-decomposable dissolution inhibiting compound ((B3), (B4)) used in the present invention will be described. In the present invention, the compound (B3) has a group decomposable with an acid (also referred to as an acid-decomposable group), and the solubility in an alkali developing solution is increased by the action of an acid. It is a low molecular dissolution inhibiting compound having a biphenyl structure or a triphenylene structure as a partial structure, and having a total number of 3 to 13 benzene rings other than the benzene ring contained in the acid-decomposable group. Further, the compound of (B4) is
Having a group that can be decomposed by an acid (also referred to as an acid-decomposable group),
It is a low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less, whose solubility in an alkali developing solution is increased by the action of an acid, and a low molecular weight dissolution inhibiting compound having a fluorene structure as a partial structure.

The compound (B3) preferably contains 1 to 3 biphenyl structures or triphenylene structures per molecule, more preferably 1 or 2 biphenyl structures or triphenylene structures. When two or more biphenyl structures are contained, they can be connected to each other by a single bond, an alkylene group or an arylene group. The total number of the benzene rings is preferably 3 to 6. In the compound (B4), one or two fluorene structures are preferably contained in one molecule, more preferably one. When two or more fluorene structures are contained, they can be connected to each other by a single bond, an alkylene group or an arylene group. In addition, two fluorene structures can be linked in a spiro ring at the 9-position.

In the compound of (B3) or (B4),
The number of acid-decomposable groups in one molecule is usually 1 to 10,
Preferably it is 2 to 6. In addition, (B3) or (B
The dissolution inhibiting compound 4) may have a plurality of acid-decomposable groups on one benzene ring, but is composed of a skeleton having one acid-decomposable group on one benzene ring. Preferably, it is a compound. Furthermore, (B3) or (B4)
Has a molecular weight of 3,000 or less, preferably 300 to 3,000, and more preferably 500 to 2,500.

The acid-decomposable group is described in detail below.
_{^{A 0 ', -R 300 -COOA 0}} ' may be preferably exemplified or -Ar-OB ⁰ '. In the present invention, the compound (B3) is preferably a compound represented by the above general formulas (Ih-1) to (Ih-1).
h-7), and the compound (B4) is preferably a compound represented by the above general formulas (Ih-8) to (Ih-).
The compound represented by 10) is mentioned.

In the formulas (Ih-1) to (Ih-10), the groups decomposable by an acid (Z ′ other than a hydrogen atom) include —A ⁰ ′, —R ₃₀₀ —COOA ⁰ ′ and —Ar— O
And a group represented by B ⁰ '. Here, A ⁰ ′ is −C
(R ₃₀₁ ) (R ₃₀₂ ) (R ₃₀₃ ), -Si (R ₃₀₁ ) (R _30
2) (representing R ₃₀₃₎ or _{-C (R 304) (R 305} ) -OR 306. B ⁰ 'is, -A ^0' represents a or -COOA ⁰ '. R ₃₀₀
Represents a single bond or a divalent aliphatic or aromatic group which may have a substituent. Ar represents a divalent aromatic group which may have a substituent. R ₃₀₁ , R ₃₀₂ , R ₃₀₃ ,
R ₃₀₄ and R ₃₀₅ may be the same or different and represent a hydrogen atom, a linear or branched alkyl group, a cyclic alkyl group, an alkenyl group, an aralkyl group or an aryl group. R
₃₀₆ represents an alkyl group or an aryl group. R _{301 to} R
Any two of ₃₀₃ or any two of R _{304 to} R ₃₀₆ may combine to form a ring.

Here, the linear and branched alkyl groups include a methyl group, an ethyl group, a propyl group, an n-butyl group and a
Those having 1 to 4 carbon atoms, such as c-butyl group and t-butyl group, are preferred. As the cyclic alkyl group, those having 3 to 10 carbon atoms, such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, are preferred. The alkenyl group is preferably a group having 2 to 4 carbon atoms such as a vinyl group, a propenyl group, an allyl group and a butenyl group.

The aralkyl group is preferably a benzyl group, an α-phenethyl group or a β-phenethyl group.
Fourteen are preferred. Examples of the divalent aliphatic or aromatic group _{R 300, -CH 2 -, -} CH 2 CH 2 -, -
_{CH 2 CH 2 CH 2 -,} - CH (CH 3) CH 2 -, - CH 2 C
H (CH ₃₎ -, p- phenylene, m- phenylene, o-
Examples include phenylene, 1,8-naphthylene, 2,6-naphthylene, and 9,10-anthrene.

Examples of the divalent aromatic group of Ar include the above R
Represents a similar one to ₃₀₀ . The ring formed by bonding any two of R _{301 to} R ₃₀₃ or any two of R _{304 to} R ₃₀₆ is a cyclopentane ring, a cyclohexane ring, or the like, or a tetrahydrofuran ring, a tetrahydropyran ring, or the like. Is mentioned.

Further substituents on these groups include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above-mentioned alkyl group, a methoxy group, an ethoxy group, and a hydroxyethoxy group.・ Propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, alkoxy group such as t-butoxy group, alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, benzyl group, phenethyl group, cumyl Aralkyl groups such as aralkyloxy group, acetyl group, acetyl group, butyryl group, benzoyl group, cyanyl group, acyl group such as valeryl group, acyloxy group such as butyryloxy group, the above alkenyl group, vinyloxy group and propenyloxy group・ Allyloxy group, butenyloxy group, etc. Keniruokishi group, said aryl group, an aryloxy group such as phenoxy group, and an aryloxycarbonyl group such as benzoyloxy group.

The group represented by -COOA ⁰ ', -R ₃₀₀ -COOA ⁰ ' or -Ar-OB ⁰ 'is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, Examples include an enol ester group, a tertiary alkyl ether group, a tertiary alkyl ester group, and a tertiary alkyl carbonate group. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, and a tetrahydropyranyl ether group.

In the formulas (Ih-1) to (Ih-10), as the linear, branched or cyclic alkyl group for R ₁₀₁ ′ to R ₂₁₃ ′ and R _{310 to} R ₃₅₅ , a methyl group, an ethyl group, Propyl group, n-butyl group, sec-butyl group,
1 to 10 carbon atoms such as t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group
Are preferred, and the alkenyl group is a vinyl group,
2 to 2 carbon atoms such as a propenyl group, an allyl group and a butenyl group
Four are preferred. Examples of the ring formed by combining R ₁₃₁ ′ and R ₁₃₂ ′ with each other include a 5- to 6-membered ring, and specific examples include cyclopentane and cyclohexane.

In the formulas (Ih-1) to (Ih-7),
A plurality of Z in the same molecule 'may be the same or different, Z' is a hydrogen _{^{atom, -A 0 ', -R 300 -COOA}} 0' represents a or -Ar-OB ⁰ ', Formula (Ih -1) to (Ih-
In 4), 90 mol% or more, preferably 95 mol% or more of Z 'in the same molecule is represented by any one of the formulas (Ih-5) to (Ih-7)
In the same Z in a molecule 'of 50 mol% or more, preferably 60 mol% or more, -A ^0' represents a, -R ₃₀₀ -COOA ⁰ 'or -Ar-OB ^0'.

In formulas (Ih-8) to (Ih-10), a plurality of Z's in the same molecule may be the same or different, and Z 'is a hydrogen atom, -A ⁰ ', -R _300- COOA ⁰ '
Or -Ar-OB ⁰ ′, and represents 90 ′ of Z ′ in the same molecule.
Mol% or more, preferably 95 mol% or more is -A ⁰ ',-
R _{300 represents} —COOA ⁰ ′ or —Ar—OB ⁰ ′.

In the present invention, the compounds represented by formulas (Ih-1) to (Ih-1)
Specific examples of the compound represented by (Ih-10) are shown below.

[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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Z ′ in the above exemplified compounds is a hydrogen atom, or

[0174]

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Represents the following. Each substituent Z ′ may not be the same group. However, (Ih-a) to (Ih-i) and (Ih-a)
In (s) to (Ih-2b), 90 mol% or more of Z 'is not hydrogen, and in (Ih-j) to (Ih-r) and (Ih-2c), 50 mol% or more of Z' is Not hydrogen.

In the present invention, the following dissolution inhibiting compounds can be used in addition to the above dissolution inhibiting compounds. In this case, the amount of the dissolution inhibiting compound used in combination is preferably 50% by weight or less, more preferably 35% by weight or less, based on the total amount of the dissolution inhibiting compound.

[0177]

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[0178]

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[0179]

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[0180]

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[0181]

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[0182]

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[0183]

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[0184]

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[0185]

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[0186]

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[0187]

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[0188]

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[0189]

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In the present invention, (C) a resin having a group that can be decomposed by an acid and having an increased solubility in an alkali developing solution by the action of an acid (hereinafter, also referred to as “component (C)”); D) It is preferable to contain at least one of a resin that is insoluble in water and soluble in an alkali developer (hereinafter, also referred to as “(D) component” or “(D) alkali-soluble resin”).

[III] (C) A resin having a group decomposable by an acid and having increased solubility in an alkali developing solution by the action of an acid Component used in the positive electron beam or X-ray resist composition of the present invention (C) is a resin having an acid-decomposable group in the main chain or side chain of the resin, or 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. Preferred groups that can be decomposed with an acid are -COOA ⁰ , -COOA ⁰ ',
—O—B ⁰ and —O—B ⁰ ′ groups, and further containing these groups include —R ⁰ —COOA ⁰ , —R ₃₀₀ —COOA ⁰ ′,
-Ar-O-B radical represented by ⁰ or -Ar-O-B ⁰ 'and the like. Here, A ⁰ is -C (R ⁰¹ ) (R ⁰² ) (R
^{03), - Si (R 01} ) (R 02) (R 0 3) or -C
It represents a (R ⁰⁴ ) (R ⁰⁵ ) -OR ⁰⁶ group. B ⁰ indicates the A ⁰ or -CO-O-A ⁰ group ^{(R 0, R 01 ~R 06} , and A
r is as defined 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.

Next, when the group decomposable with these acids is bonded as a side chain, the base resin may be -OH or -COOH, preferably -R ⁰ -COOH, -R ₃₀₀
It is an alkali-soluble resin having a -COOH or -Ar-OH group. 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) (at 23 ° C.) and measured at 170 ° C.
A / sec or more is preferable. Particularly preferably 330A
/ Sec or more (A is angstroms). From such a viewpoint, a particularly preferred alkali-soluble resin is
o-, m-, p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen- or alkyl-substituted poly (hydroxystyrene), part of poly (hydroxystyrene), O-alkyl And styrene-hydroxystyrene copolymers, α-methylstyrene-hydroxystyrene copolymers and hydrogenated novolak resins.

The component (C) used in the present invention is described in European Patent No. 254853, JP-A-2-25850 and 3-2.
No. 23860, 4-251259, etc., an alkali-soluble resin is reacted with a precursor of an acid-decomposable group, or an alkali-soluble resin monomer to which an acid-decomposable group is bonded is used. It can be obtained by copolymerization with various monomers.

Specific examples of the component (C) used in the present invention are shown below, but it should not be construed that the invention is limited thereto.

[0197]

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[0198]

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[0199]

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[0200]

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[0201]

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[0202]

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[0203]

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The content of acid-decomposable groups is determined by the number of acid-decomposable groups in the resin (B) and the number of alkali-soluble groups not protected by acid-decomposable groups (S). B /
It is represented by (B + S). The content is preferably 0.01 to
0.7, more preferably 0.05 to 0.50, even more preferably 0.05 to 0.40. B / (B + S)>
A value of 0.7 is not preferred because it causes film shrinkage after PEB, poor adhesion to the substrate, and scum. On the other hand, B / (B + S) <
A value of 0.01 is not preferable because standing waves may remarkably remain on the pattern side wall.

The weight average molecular weight (Mw) of the component (C) is
It is preferably in the range of 2,000 to 200,000. If the molecular weight is less than 2,000, the film loss is large due to the development of the unexposed portion. If the molecular weight exceeds 200,000, the dissolution rate of the alkali-soluble resin itself in alkali becomes slow and the sensitivity is lowered. More preferably, 5,000 to 100,0
00, more preferably from 8,000 to 50,
000. In addition, molecular weight distribution (Mw / Mn)
Is preferably 1.0 to 4.0, more preferably 1.0 to 4.0.
-2.0, particularly preferably 1.0-1.6, and the smaller the degree of dispersion, the better the heat resistance and image forming properties (pattern profile, defocus latitude, etc.).
Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography. The component (C) may be used in combination of two or more.

The amount of the component (C) used in the composition is preferably from 40 to 99% by weight based on the solid content of the whole composition.
More preferably, it is 50 to 90% by weight.

[IV] (D) A resin that is insoluble in water and soluble in an alkali developer (hereinafter referred to as “(D) component” or “(D)
In the positive type electron beam or X-ray resist composition of the present invention, as the component (D),
A resin that is insoluble in water and soluble in an aqueous alkaline solution can be used. When the component (D) is used, it is not always necessary to incorporate a resin having a group that is decomposed by the action of the acid (C) and increases the solubility in an alkaline developer. Of course, this does not exclude the combination with the component (C).

The alkali-soluble resin (D) used in the present invention includes, for example, novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogen Polyhydroxystyrene,
Halogen or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m / p-hydroxystyrene copolymer, part of O- to hydroxyl group of polyhydroxystyrene
Alkyl compounds (for example, 5 to 30 mol% of O-methyl compound, O- (1-methoxy) ethyl compound, O- (1-ethoxy) ethyl compound, O-2-tetrahydropyranyl compound, O- (t- Butoxycarbonyl) methylated product) or O-acylated product (for example, 5 to 30 mol% o-
Acetylated product, O- (t-butoxy) carbonylated product, etc.), styrene-maleic anhydride copolymer, styrene-
Examples thereof include, but are not limited to, hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxyl group-containing methacrylic resin and its derivative, and polyvinyl alcohol derivative.

Particularly preferred (D) alkali-soluble resins are novolak resins and o-polyhydroxystyrene, m-
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.

Examples of the predetermined monomer include phenol and m
Cresols such as -cresol, p-cresol and o-cresol, xylenols such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol and 2,3-xylenol, m-ethylphenol, p- Alkylphenols such as ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol, 2,3,5-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, Alkoxyphenols such as -methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol and p-butoxyphenol, 2-methyl-4-isopropyl Fenault Bis-alkylphenols etc., m
Hydroxychloro compounds such as -chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol can be used alone or as a mixture of two or more, but are not limited thereto. It is not something to be done.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-
Phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o -Methylbenzaldehyde, m-methylbenzaldehyde,
p-Methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural, chloroacetaldehyde, and their acetal compounds, such as chloroacetaldehyde diethyl acetal, among which formaldehyde is used Is preferred. These aldehydes are used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used.

The weight average molecular weight of the novolak resin thus obtained is preferably in the range of 1,000 to 30,000. If it is less than 1,000, the film loss of the unexposed portion after development is large, and if it exceeds 30,000, the developing speed is reduced. Particularly preferred are 2,000-20,
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.
~ 200000, more preferably 5000-10000
0. Here, the weight average molecular weight is defined as a value in terms of polystyrene by gel permeation chromatography. These (D) alkali-soluble resins in the present invention may be used in combination of two or more.

In the present invention, the cationic polymerization means
It refers to addition polymerization in which the growing chain is a positive ion such as a carbonium ion or an oxonium ion. In the present invention, such a monomer capable of cationic polymerization is referred to as a compound having a cationically polymerizable function. Taking a vinyl compound as an example, the cationic polymerizability of a vinyl monomer can be discussed by the Qe value used in radical polymerization.
That is, it is known that when the e-value is smaller than about -0.3, cationic polymerization is exhibited.

[V] (E) Cationic polymerizable compound As the cationic polymerizable compound used in the present invention, any compound having a cationic polymerizable function can be used. Examples include compounds, cycloalkane compounds, cyclic ether compounds, lactone compounds, aldehyde compounds and the like. Examples of the vinyl compound include vinyl ethers described below, styrene, α-methylstyrene, m-methoxystyrene, p-
Methoxystyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-nitrostyrene, m
Styrenes such as -nitrostyrene, p-bromostyrene, 3,4-dichlorostyrene, 2,5-dichlorostyrene, p-dimethylaminostyrene, 2-isopropenylfuran, 2-vinylbenzofuran and 2-vinyldibenzofuran; Vinylfurans such as vinylfurans, 2-isopropenylthiophene and 2-vinylphenoxatin, N-vinylcarbazoles, vinylnaphthalene, vinylanthracene, acenaphthylene and the like can be used.

Examples of cycloalkane compounds include phenylcyclopropane, spiro [2,4] heptane, spiro [2,5] octane, spiro [3,4] octane,
Methyl spiro [2,5] octane, spiro [2,7] decane and the like can be used. As the cyclic ether compound, dioxane such as 4-phenyl-1,3-dioxane, oxetane such as 3,3-bischloromethyloxetane, and compounds such as trioxane and 1,3-dioxepane can be used. Further, glycidyl ethers such as allyl glycidyl ether and phenyl glycidyl ether, glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, bisphenol A type epoxy resins and tetrabromobisphenol A type epoxy resins commercially available under the trade name of Epicoat, Compounds such as bisphenol F type epoxy resin, phenol novolak type epoxy resin, and cresol novolak type epoxy resin can be used.

Examples of the lactone compound include propiolactone, butyrolactone, valerolactone, caprolactone, β-methyl-β-propiolactone, α, α-dimethyl-β-propiolactone, α-methyl-β-propiolactone. And the like.

Examples of the aldehyde compound include aliphatic saturated aldehyde compounds such as valeraldehyde, hexanal, heptanal, octanal, nonanal, decanal, cyclohexanecarbaldehyde, and phenylacetaldehyde;
Aliphatic unsaturated aldehyde compounds such as -methyl-2-butenal, 2-butynal and safranal; aromatic aldehyde compounds such as benzaldehyde, tolualdehyde and cinnamaldehyde; tribromoacetaldehyde;
Halogen-substituted aldehyde compounds such as 2,3-trichlorobutyraldehyde and chlorobenzaldehyde, glyceraldehyde, aldol, salicylaldehyde, m-hydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, piperonal and the like Hydroxy and alkoxy substituted aldehyde compounds, amino and nitro substituted aldehyde compounds such as aminobenzaldehyde, nitrobenzaldehyde, succinaldehyde, glutaraldehyde,
Dialdehyde compounds such as phthalaldehyde and terephthalaldehyde, ketoaldehyde compounds such as phenylglyoxal and benzoylacetaldehyde, and derivatives thereof can be used.

The cationically polymerizable compound is preferably a vinyl compound, more preferably a vinyl ether compound, particularly preferably a compound represented by the general formula [A], in that the effects of the present invention become remarkable. In the general formula (A), when R _a , R _b and R _c are an aryl group, it generally has 4 to 20 carbon atoms, and has an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group. Group, alkyl mercapto group, aminoacyl group,
It may be substituted by a carboalkoxy group, a nitro group, a sulfonyl group, a cyano group or a halogen atom. Here, as the aryl group having 4 to 20 carbon atoms, for example,
Examples include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

When R _a , R _b and R _c represent an alkyl group, they represent a saturated or unsaturated linear, branched or alicyclic alkyl group having 1 to 20 carbon atoms, and include a halogen atom, a cyano group,
It may be substituted by an ester group, an oxy group, an alkoxy group, an aryloxy group or an aryl group. Here, as a saturated or unsaturated linear or branched or alicyclic alkyl group having 1 to 20 carbon atoms, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group,
t-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, isohexyl group, octyl group, isooctyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, vinyl group,
Propenyl, butenyl, 2-butenyl, 3-butenyl, isobutenyl, pentenyl, 2-pentenyl, hexenyl, heptenyl, octenyl, cyclopropyl, cyclobutyl, cyclopentyl,
Examples include a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclopentenyl group, a cyclohexenyl group, and the like.

Further, as a saturated or olefinically unsaturated ring formed by bonding any two of R _a , R _b and R _c , specifically, cycloalkane or cycloalkene is usually 3 to 8, Preferably it represents 5 or 6 ring members.

In the present invention, in the general formula (A),
Preferred is an enol ether group in which one of R _a , R _b and R _c is a methyl group or an ethyl group and the remainder is a hydrogen atom, and more preferred is when all of R _a , R _b and R _c are hydrogen. It is a certain general formula [A-1] below.

Formula [A-1] CH ₂ ＝ CH—O—
R (R: alkyl, substituted alkyl) Here, the alkyl group is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms. A substituted alkyl group is
It is a linear, branched or cyclic substituted alkyl group having 1 to 30 carbon atoms.

In the above, the linear, branched or cyclic alkyl group having 1 to 30 carbon atoms includes ethyl, linear, branched or cyclic propyl, butyl, pentyl, hexyl, Heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group,
Examples include a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, and the like. In the above,
Preferred as a further substituent of the alkyl group is a hydroxy group, an alkyl group, an alkoxy group, an amino group, a nitro group, a halogen atom, a cyano group, an acyl group, an acyloxy group, a sulfonyl group, a sulfonyloxy group, a sulfonylamino group, Aryl group, aralkyl group, imide group, hydroxymethyl group, -OR ₁₀₀₁ , -C (= O) -R ₁₀₀₂ , -OC (= O) -R ₁₀₀₃ , -C (= O) -O- Substituents such as R ₁₀₀₄ , -SR ₁₀₀₅ , -C (= S) -R ₁₀₀₆ , -OC (= S) -R ₁₀₀₇ , -C (= S) -OR ₁₀₀₈ , and the like. . Here, R _{1001 to} R ₁₀₀₈ are
Each independently, a linear, branched or cyclic alkyl group,
Alkoxy group, an amino group, a nitro group, a halogen atom, a cyano group, an acyl group, a sulfonyl group, a sulfonyloxy group, a sulfonylamino group, an imido group, - (CH ₂ CH ₂ -
O) _n -R ₁₀₀₉ (where n represents an integer of 1 to 20;
₁₀₀₉ represents a hydrogen atom or an alkyl group, an _optionally substituted aryl group or aralkyl group (here,
Examples of the substituent include a linear, branched or cyclic alkyl group, an alkoxy group, an amino group, a nitro group, a halogen atom, a cyano group, an acyl group, an aryl group, and an aralkyl group.

Preferred examples of the compound represented by formula (A) include the following, but are not limited thereto.

[0225]

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[0226]

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[0227]

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As a method for synthesizing the compound represented by the above general formula [A-1], for example, Stephen. C. Lapin, Polymers P.
aint Color Journal, 179 (4237), 321 (1988), i.e., by reacting alcohols or phenols with acetylene, or by reacting alcohols or phenols with halogenated alkyl vinyl ether. be able to. It can also be synthesized by reacting a carboxylic acid compound with a halogenated alkyl vinyl ether.

In the resist composition of the present invention, the amount of the cationic polymerizable compound (E) (preferably the compound represented by the above general formula (A)) is determined based on the total weight (solid content) of the composition. It is preferably 0.5 to 50% by weight, more preferably 3 to 30% by weight.

Here, examples of the constitution of the composition of the present invention are shown below. However, the content of the present invention is not limited to these. 1) A positive electron beam or X-ray resist composition containing the above component (A), the above component (B) and the above component (C). 2) Component (A), Component (B), Component (D)
A positive electron beam or X-ray resist composition comprising: 3) The component (A), the component (B), and the component (C)
And a resist composition for a positive electron beam or X-ray, comprising the above component (D). In addition to the above components, (E) a cationically polymerizable compound, and / or
Alternatively, (F) a surfactant can be added. In each of the above configuration examples, component (C) of 1) and component (D) of 2)
The amount of the component [(C) + (D)] used in the composition 3) is preferably 40 to 99% by weight, more preferably 50 to 90% by weight, based on the solid content of the whole composition. is there.

The amount of the component (B) used in the composition is 3 to 4 with respect to the solid content of the whole composition in any of the above constitution examples.
Preferably 5% by weight, more preferably 5 to 30% by weight,
More preferably, it is 10 to 20% by weight.

Others according to the present invention include (F) fluorine-based and / or
Alternatively, it is preferable to use a silicon-based surfactant.
Examples of the fluorine-based and / or silicon-based surfactant include a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom.
For example, F-top EF301, EF303 (manufactured by Shin-Akita Chemical Co., Ltd.), Florado FC430, 431 (manufactured by Sumitomo 3M Limited), MegaFac F171, F17
3, F176, F189, F08 (Dainippon Ink Co., Ltd.)
Manufactured), Surflon S-382, SC-101, 102,
103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.),
A fluorine-based surfactant such as Troysol S-366 (manufactured by Troy Chemical Co., Ltd.) or a silicon-based surfactant can be used. In addition, polysiloxane polymer KP-3
41 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant. The amount of the surfactant (F) is usually 0.001 to 0.5% by weight, preferably 0.1 to 0.5% by weight, based on the solid content of the whole composition in the composition of the present invention.
002 to 0.3% by weight.

A surfactant other than a fluorine-based and / or silicon-based surfactant can be used in combination. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether and the like Sorbitan such as polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopal Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as tate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; acrylic acid or methacrylic acid (Co) polymerized polyflow no. 75, no. 9
5 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. The amount of these other surfactants is usually 2% by weight or less, preferably 1% by weight or less, based on the solid content of the whole composition in the composition of the present invention. These surfactants may be added alone or in combination of two or more.

The organic basic compound that can be used in the present invention is a compound that is more basic than phenol. Among them, a nitrogen-containing basic compound is preferable. Preferred chemical environments include the structures of the following formulas (A) to (E).

[0235]

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Here, R ¹²⁵⁰ , R ¹²⁵¹ and R ¹²⁵² are
The same or different, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms ^Yes , where R ¹²⁵¹ and R ¹²⁵²
May combine with each other to form a ring.

[0237]

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Wherein R ¹²⁵³ , R ¹²⁵⁴ , R ¹²⁵⁵ and R
¹²⁵⁶ is the same or different and represents an alkyl group having 1 to 6 carbon atoms.

Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferred is a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. Or a compound having an alkylamino group. 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 aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are an amino group,
An aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group, a hydroxyl group, and a cyano group.

As particularly preferred compounds, guanidine and
1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylamino Pyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethyl Pyridine, 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, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, 2,4,
Examples thereof include 5-triphenylimidal and the like. Of these, 1,8-diazabicyclo [5.4.0] undec-7-ene and 1,5-diazabicyclo [4.3.0] are preferable.
Examples include, but are not limited to, nona-5-ene, 2,4,5-triphenylimidal, and the like.

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 usually 0.001 to 10% by weight, based on the solid content of the entire composition in the composition of the present invention.
Preferably it is 0.01 to 5% by weight. If it is less than 0.001% by weight, the effect of the addition cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed portion tends to deteriorate.

[VI] Other Components Used in the Present Invention The positive electron beam or X-ray resist composition of the present invention may further contain, if necessary, a dye, a pigment, a plasticizer, a photosensitizer, and a developing agent. A compound or the like having two or more phenolic OH groups that promote solubility in a liquid can be contained.

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 this phenol compound is 2 to 50% by weight, more preferably 5 to 30% by weight, based on the alkali-soluble resin (D). 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 prepared by those skilled in the art by referring to the methods described in, for example, JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and EP 219294. It can be easily synthesized at 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.

The composition of the present invention is dissolved in a solvent capable of dissolving each of the above components, and applied on a support. 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, propylene glycol monomethyl ether propionate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate,
Ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran, linear ketones having 6 to 9 carbon atoms, γ-butyrolactone, etc. Preferably, these solvents can be used alone or as a mixture. In the present invention, examples of the coating solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monomethyl ether, methyl lactate, ethyl lactate, a linear ketone having 6 to 9 carbon atoms, γ-butyrolactone, and the like. Preferably, propylene glycol monomethyl ether acetate is particularly preferred, so that in-plane uniformity is excellent. Examples of the linear ketone having 6 to 9 carbon atoms include 2-heptanone and 2-octanone.

Pursuing further advances in semiconductors, in addition to essential high-resolution performance, sensitivity, applicability, minimum required amount of application, adhesion to substrates, heat resistance, storage stability of the composition Therefore, high performance compositions are required from various viewpoints.
Recently, there has been a tendency to create devices using large diameter wafers in order to increase the absolute amount of chips that can be obtained. In particular, in the case of resists for electron beams and X-rays, exposure is performed under high vacuum in an electron beam irradiation apparatus. Will increase. However, if the coating is applied to a large diameter, there is a concern that the coating properties, particularly the in-plane film thickness uniformity, may be reduced. Therefore, it is required to improve the film thickness in-plane uniformity for a large diameter wafer. As a method for confirming the uniformity, the film thickness is measured at many points in the wafer, the standard deviation of each measured value is obtained, and the uniformity can be confirmed by a value three times the standard deviation.
It can be said that the smaller this value is, the higher the in-plane uniformity is. As the value, a value three times the standard deviation is preferably 100 or less.
The following is more preferred.

The resist composition of the present invention can be filtered after being dissolved in a solvent. The filter used for that purpose is selected from those used in the resist field, and specifically, the material of the filter is polyethylene,
Those containing nylon or polysulfone are used. More specifically, micro guard manufactured by Millipore,
Microguard Plus, Microguard Minichem-
D, Microgard Minichem-D PR, Millipore Obturizer DEV / DEV-C, Millipore Obturizer 16/14, Ultipore N66 manufactured by Pall Corporation, Posidyne, Nylon Falcon, and the like. Also,
The pore diameter of the filter can be the one confirmed by the following method. In other words, PSL standard particles (polystyrene latex beads, particle size 0.100μ
m) is dispersed and continuously flowed at a constant flow rate to the primary side of the filter by a tube pump, and the challenge concentration is measured by a particle counter. Those that can capture 90% or more can be used as a filter having a pore diameter of 0.1 μm.

The positive electron beam or X-ray resist composition of the present invention is spinner-coated on a substrate (eg, a silicon / silicon dioxide coating) as used in the manufacture of precision integrated circuit devices.
After coating by an appropriate coating method such as a coater or the like, exposure is performed through a predetermined mask, baking and development are performed, whereby a good resist pattern can be obtained.

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

[0252]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the contents of the present invention are not limited thereto. [Synthesis Example 1: Synthesis of poly (p-hydroxystyrene / styrene) copolymer] 35.25 of a p-tert-butoxystyrene monomer dehydrated and purified by distillation according to a conventional method.
g (0.2 mol) and 5.21 g of styrene monomer
(0.05 mol) was dissolved in 100 ml of tetrahydrofuran. Under a nitrogen stream and stirring, at 80 ° C., 0.033 g of azobisisobutyronitrile (AIBN) was added three times every 2.5 hours, and finally, stirring was continued for another 5 hours to carry out a polymerization reaction. . The reaction solution was hexane 1200
Then, white resin was precipitated. After drying the obtained resin, it was dissolved in 150 ml of tetrahydrofuran.
4N hydrochloric acid was added thereto, and the mixture was hydrolyzed by heating under reflux for 6 hours, and then reprecipitated in 5 L of ultrapure water. The resin was separated by filtration, washed with water and dried. Further, it was dissolved in 200 ml of tetrahydrofuran, and dropped and reprecipitated in 5 L of ultrapure water with vigorous stirring. This reprecipitation operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene / styrene) copolymer.

[Synthesis Example 2: Synthesis of Resin Example (c-21)]
32.4 g (0.2 mol) of p-acetoxystyrene and 7.01 g (0.07 mol) of t-butyl methacrylate were dissolved in 120 ml of butyl acetate, and the mixture was dissolved under a nitrogen stream and stirring.
Azobisisobutyronitrile (AIBN) at 80 ° C
0.033 g was added three times every 2.5 hours, and finally, stirring was continued for another 5 hours to carry out a polymerization reaction.
The reaction solution was poured into 1200 ml of hexane to precipitate a white resin. After drying the obtained resin, methanol 200
Dissolved in ml. 7.7 g of sodium hydroxide
An aqueous solution of (0.19 mol) / water (50 ml) was added, and the mixture was heated at reflux for 1 hour to hydrolyze. Thereafter, 200 ml of water was added for dilution, and neutralized with hydrochloric acid to precipitate a white resin. This resin was separated by filtration, washed with water and dried.
Further, it was dissolved in 200 ml of tetrahydrofuran, and dropped and reprecipitated in 5 L of ultrapure water with vigorous stirring. This reprecipitation operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene / t-butyl methacrylate) copolymer.

[Synthesis 3: Synthesis of Resin Example (c-3)] Poly (p-hydroxystyrene) (VP-800 manufactured by Nippon Soda Co., Ltd.)
0) 10 g was dissolved in 50 ml of pyridine, and 3.63 g of di-t-butyl dicarbonate was added dropwise thereto with stirring at room temperature. After stirring at room temperature for 3 hours, the mixture was added dropwise to a solution of 1 L of ion-exchanged water / 20 g of concentrated hydrochloric acid. The precipitated powder was filtered, washed with water, and dried to obtain Resin Example (c-3).

[Synthesis 4: Synthesis of Resin Example (c-33)] p
-83.1 g (0.5 mol) of cyclohexylphenol
Was dissolved in 300 ml of toluene, then 150 g of 2-chloroethyl vinyl ether, 25 g of sodium hydroxide,
5 g of tetrabutylammonium bromide and 60 g of triethylamine were added and reacted at 120 ° C. for 5 hours. The reaction solution was washed with water, excess chloroethyl vinyl ether and toluene were distilled off, and the obtained oil was purified by distillation under reduced pressure.
4-Cyclohexylphenoxyethyl vinyl ether was obtained. 20 g of poly (p-hydroxystyrene) (VP-8000 manufactured by Nippon Soda Co., Ltd.) and 6.5 g of 4-cyclohexylphenoxyethyl vinyl ether in 80 ml of THF.
, And 0.01 g of p-toluenesulfonic acid was added thereto and reacted at room temperature for 18 hours. The reaction solution was distilled water 5
L was dripped with vigorous stirring, and the precipitated powder was filtered,
After drying, a resin example (c-33) was obtained.

Resin Examples (c-4), (c-28), (c-
30) was also synthesized by the same method using the corresponding trunk polymer and vinyl ether.

(Synthesis Example 1 of Dissolution Inhibitor Compound: Synthesis of Compound Example Ih-10) The following compound (Ih-10-ra)
(w: Honshu Chemical Industry Co., Ltd.) (20 g) was dissolved in a mixed solvent of N, N-dimethylformamide / ethyl acetate, and t-butyl bromoacetate having an equimolar hydroxyl group was added. While stirring, an aqueous solution of choline (50% by weight) was added dropwise in an equimolar amount to the hydroxyl group, and the mixture was stirred at room temperature for 4 hours. Equimolar amount of acetic acid was added to choline and stirred, water was added and extracted with ethyl acetate. Drying yielded 19 g of solid (Ih-n).

[0258]

Embedded image

The other dissolution inhibiting compounds were synthesized in the same manner.

[0260]

(Synthesis Example 2 of Dissolution Inhibitor Compound: Compound Example Ih-n Synthesis) 20 g of the following compound (Ih-n-raw: manufactured by Honshu Chemical Industry Co., Ltd.) was added to N, N-dimethylformamide /
It was dissolved in a mixed solvent of ethyl acetate, and an equimolar t-butyl bromoacetate having a hydroxyl group was added. While stirring, an aqueous solution of choline (50% by weight) was added dropwise in an equimolar amount to the hydroxyl group, and the mixture was stirred at room temperature for 4 hours. Add an equimolar amount of acetic acid to choline and stir,
Water was added and extracted with ethyl acetate. Dry to a solid (Ih
-N) 18 g were obtained. Other dissolution inhibiting compounds were similarly synthesized.

[0262]

Embedded image

[Synthesis Example of Compound Represented by Formula (A)] (Synthesis Example-1) Synthesis of A-22 (benzoyloxyethyl vinyl ether) 244 g (2 mol) of benzoic acid
Was dissolved in 3000 ml of toluene, then 320 g of 2-chloroethyl vinyl ether was added, and 88 g of sodium hydroxide and 25 g of tetrabutylammonium bromide were further added.
g and 100 g of triethylamine were added, and the mixture was heated and stirred at 120 ° C. for 5 hours. The reaction solution was washed with water, and excess 2-chloroethyl vinyl ether and toluene were removed by distillation under reduced pressure. From the obtained oil, 300 g of benzoyloxyethyl vinyl ether as a target substance was distilled off under reduced pressure.
Obtained. (Synthesis Examples 2 to 8) Synthesis of A-23 to A-29 The A-23 to A- in the same manner as in the synthesis of A-22.
29 was synthesized.

[1] Examples 1-1 to 1-34, Comparative Example 1
-101 to 1-104 (1) Application of resist The components shown in Tables 1 and 2 below were dissolved in 8.2 g of propylene glycol monomethyl ether acetate, and the solution was filtered through a 0.1 μm Teflon (registered trademark) filter. Thus, a resist solution was prepared. Each sample solution was applied on a silicon wafer using a spin coater, and 12
The resist film was dried on a vacuum suction type hot plate at 0 ° C. for 90 seconds to obtain a resist film having a thickness of 0.3 μm.

(2) Preparation of resist pattern An electron beam lithography system (pressing voltage 50 Ke
Irradiation was performed using V). 110 ° C each after irradiation
Heating for 60 seconds with a vacuum adsorption type hot plate,
It was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. The cross-sectional shape of the obtained contact hole pattern was observed with a scanning electron microscope.

(3) Evaluation of sensitivity and resolving power The limiting resolving power (minimum diameter of the hole) in the contact hole pattern was defined as the resolving power, and the minimum irradiation dose capable of resolving the limiting resolving power was defined as the sensitivity.

[0267]

[Table 1]

[0268]

[Table 2]

The acid generators PAG-1 and PAG-2 are as follows.

[0270]

Embedded image

The composition, physical properties and the like of the binder resin used are as follows. (C-3): p-humanoxystyrene / pt-butoxycarboxystyrene copolymer (molar ratio: 80/2)
0), weight average molecular weight 13000, molecular weight distribution (Mw /
Mn) 1.4 (c-4): p-hydroxystyrene / p- (1-ethoxyethoxy) styrene copolymer (molar ratio: 70/3)
0), weight average molecular weight 12000, molecular weight distribution (Mw /
Mn) 1.3 (c-21): p-hydroxystyrene / t-butyl methacrylate copolymer (molar ratio: 70/30), weight average molecular weight 16,000, molecular weight distribution (Mw / Mn) 2.0 (c- 22): p-hydroxystyrene / p- (1-t
-Butoxyethoxy) styrene copolymer (molar ratio: 85)
/ 15), weight average molecular weight 12000, molecular weight distribution (M
w / Mn) 1.1 (c-28): p-hydroxystyrene / p- (1-phenethyloxyethoxy) styrene copolymer (molar ratio:
85/15), weight average molecular weight 12,000, molecular weight distribution (Mw / Mn) 1.2 (c-30): p-hydroxystyrene / p- (1-phenoxyethoxyethoxy) styrene copolymer (molar ratio: 85/15) 15), weight average molecular weight 13000, molecular weight distribution (Mw / Mn) 1.2 (PHS): poly-p-hydroxystyrene (manufactured by Nippon Soda Co., Ltd., trade name VP-15000) (PHS / St: Synthesis Example 1) P-hydroxystyrene / styrene (molar ratio: 80/20), weight average molecular weight 26000, molecular weight distribution (Mw / Mn)
1.9

[0272]

[Table 3]

[0273]

[Table 4]

From the results shown in Tables 3 and 4, it can be seen that the positive electron beam resist composition of the present invention has a high resolution and gives a rectangular pattern profile.

Examples 1-1, 1-10, and 1- of Tables 1-2
28, 1-29 and 1-30, which are cationically polymerizable compounds A-8, A-10, A-12 and A-1
5, A-18, A-22, A-23, A-24, A-2
The compositions in which 5, p-methoxystyrene, spirooctane, caprolactone, and terephthalaldehyde were replaced by 10% by weight of the solid content showed improved resolving power and profile shape, respectively.

Further, Examples 1-1 and 1-1 in Tables 1 and 2 were used.
0, 1-28, 1-29 and 1-30, having the same structure as surfactants, Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), Megafac F176 (manufactured by Dainippon Ink Co., Ltd.), Megafac R08 (manufactured by Dainippon Ink Co., Ltd.) and polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
The compositions to which 0 to 300 ppm were added showed an improvement in resolution and profile shape, respectively.

Further, Examples 1-1 and 1-1 shown in Tables 1 and 2 were used.
With the same configuration as that of 0, 1-28, 1-29 and 1-30, the organic base compound was converted to 1,8-diazabicyclo [5.4.0].
Undec-7-ene, 1,5-diazabicyclo [4.
3.0] Nona-5-ene, N-cyclohexyl-N'-morpholinoethylthiourea, and the composition changed to 4-dimethylaminopyridine showed the same performance.

Further, in the same structure as in Tables 1 and 2, the solvent was
Propylene glycol monomethyl ether acetate /
Propylene glycol monomethyl ether = 80/20
The composition changed to shows the same performance.

Further, the components shown in Tables 1 and 2 were dissolved in the above solvent, and the composition solutions of Examples 1-1 to 1-34 were filtered through a 0.1 μm polyethylene filter to obtain a resist solution. Was prepared. The in-plane uniformity of each of these resist solutions was evaluated as described below.

(In-plane uniformity) Each resist solution was 8 in.
h. A resist coating film for measuring in-plane uniformity was obtained by coating on a silicon wafer and performing the same processing as the coating of a resist layer as described above. This is a Dainippon Screen Lambd
At aA, the coating film thickness was measured at 36 points evenly so as to form a cross along the wafer diameter direction. The standard deviation of each measured value is taken.
The above was evaluated as x. As a result, those using propylene glycol monomethyl ether acetate (PGMEA) as a resist coating solvent (Examples 1 to 3)
In 4), the in-plane uniformity was ○. In addition, the composition in which the solvent was changed to propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 80/20 with the same configuration as that of Example 1-1 to Example 1-34 also showed similar in-plane uniformity. Was.

(4) Patterning by X-ray Exposure at 1: 1 Using each resist composition of Example 1-1 and Comparative Examples 1-101 and 102, a film thickness of 0.40 μm was obtained in the same manner as in (1) above. Was obtained. Next, patterning was performed in the same manner as in the above (2) except that an equal-magnification X-ray exposure apparatus (gap value: 20 nm) was used, and the resist performance (sensitivity, resolution) was evaluated in the same manner as in the above (3). . Table 5 shows the evaluation results.

Table 5 Resist Composition Sensitivity (mJ / cm ² ) Resolution (μm) Example 1-1 80 0.07 Comparative Example 1-101 90 0.10 Comparative Example 1-102 90 0.10

As is clear from Table 5, it can be seen that the resist composition of the present invention shows extremely excellent performance even in X-ray exposure. The positive electron beam or X-ray resist composition of the present invention has a high resolution.

[2] Examples 2-1 to 2-44, Comparative Example 2
-101 to 2-106 (1) Coating of resist The components shown in Tables 6 and 7 below were dissolved in 8.2 g of propylene glycol monomethyl ether acetate, and this was filtered through a 0.1 μm Teflon filter to obtain a resist solution. Prepared. Each sample solution was applied on a silicon wafer using a spin coater and dried on a vacuum adsorption type hot plate at 120 ° C. for 90 seconds to form a film having a thickness of 0.3 μm.
A μm resist film was obtained.

(2) Preparation of resist pattern An electron beam lithography system (pressing voltage 50 Ke
Irradiation was performed using V). 110 ° C each after irradiation
Heating for 60 seconds with a vacuum adsorption type hot plate,
It was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. The cross-sectional shape of the obtained contact hole pattern was observed with a scanning electron microscope.

(3) Evaluation of sensitivity and resolving power The limiting resolving power (minimum diameter of the hole) in the contact hole pattern was defined as the resolving power, and the minimum irradiation dose capable of resolving the limiting resolving power was defined as the sensitivity.

[0287]

[Table 5]

[0288]

[Table 6]

The acid generators PAG-1 and PAG-2 are as follows.

[0290]

Embedded image

The composition, physical properties and the like of the binder resin used are as follows. (C-3): p-humanoxystyrene / pt-butoxycarboxystyrene copolymer (molar ratio: 80/2)
0), weight average molecular weight 13000, molecular weight distribution (Mw /
Mn) 1.4 (c-4): p-hydroxystyrene / p- (1-ethoxyethoxy) styrene copolymer (molar ratio: 70/3)
0), weight average molecular weight 12000, molecular weight distribution (Mw /
Mn) 1.3 (c-21): p-hydroxystyrene / t-butyl methacrylate copolymer (molar ratio: 70/30), weight average molecular weight 16,000, molecular weight distribution (Mw / Mn) 2.0 (c- 22): p-hydroxystyrene / p- (1-t
-Butoxyethoxy) styrene copolymer (molar ratio: 85)
/ 15), weight average molecular weight 12000, molecular weight distribution (M
w / Mn) 1.1 (c-28): p-hydroxystyrene / p- (1-phenethyloxyethoxy) styrene copolymer (molar ratio:
85/15), weight average molecular weight 12,000, molecular weight distribution (Mw / Mn) 1.2 (c-30): p-hydroxystyrene / p- (1-phenoxyethoxyethoxy) styrene copolymer (molar ratio: 85/15) 15), weight average molecular weight 13000, molecular weight distribution (Mw / Mn) 1.2 (PHS): poly-p-hydroxystyrene (manufactured by Nippon Soda Co., Ltd., trade name VP-8000) (PHS / St: Synthesis Example 1) P-hydroxystyrene / styrene (molar ratio: 80/20), weight average molecular weight 26000, molecular weight distribution (Mw / Mn)
1.9

[0292]

[Table 7]

[0293]

[Table 8]

From the results of Tables 8 and 9, it can be seen that the positive electron beam resist composition of the present invention has high sensitivity.

With the same structure as in Examples 2-1 to 2-4 of Tables 6 and 7, the cationically polymerizable compounds were A-8, A-10, and A-8.
-12, A-15, A-18, A-22, A-23, A
-25, p-methoxystyrene, spirooctane, caprolactone, and a composition changed to terephthalaldehyde also showed similar performance.

Further, a surfactant similar to that of Examples 2-2 to 2-4 in Tables 6 to 7 was used except that a surfactant was used for Megafac F176.
(Dai Nippon Ink Co., Ltd.), Megafac R08 (Dai Nippon Ink Co., Ltd.), polysiloxane polymer KP-3
41 (manufactured by Shin-Etsu Chemical Co., Ltd.) also exhibited similar performance.

Further, with the same constitution as in Examples 2-1 to 2-4 in Tables 6 and 7, the organic base compound was changed to 1,8-diazabicyclo [5.4.0] undec-7-ene, Compositions changed to 5-diazabicyclo [4.3.0] non-5-ene, N-cyclohexyl-N'-morpholinoethylthiourea, and 4-dimethylaminopyridine also showed similar performance.

Further, with the same structure as in Tables 6 and 7, the solvent was
Propylene glycol monomethyl ether acetate /
Propylene glycol monomethyl ether = 80/20
The composition changed to shows the same performance.

Further, the components shown in Tables 6 and 7 were dissolved in the above solvent, and the composition solutions of Examples 2-1 to 2-44 were filtered through a 0.1 μm polyethylene filter to obtain a resist solution. Was prepared. The in-plane uniformity of each of these resist solutions was evaluated as described below.

(In-plane uniformity) Each resist solution was 8 in.
h. A resist coating film for measuring in-plane uniformity was obtained by coating on a silicon wafer and performing the same processing as the coating of a resist layer as described above. This is a Dainippon Screen Lambd
At aA, the coating film thickness was measured at 36 points evenly so as to form a cross along the wafer diameter direction. The standard deviation of each measured value is taken.
The above was evaluated as x. As a result, Example 2-
In Examples 1-2-44, the in-plane uniformity was ○. Therefore, it is understood that it is preferable to use a silicon-based / fluorine-based surfactant in the present invention. Further, compositions having the same configuration as in Example 2-2 to Example 2-44 and changing the solvent to propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 80/20 also show similar in-plane uniformity. Was.

(6) Patterning by X-ray Exposure at 1: 1 Using each resist composition of Example 2-20 and Comparative Examples 2-102 and 2-104, a film thickness of 0 was obtained in the same manner as in (1) above. A .40 μm resist film was obtained. Next, patterning was performed in the same manner as in the above (2) except that an equal-size X-ray exposure apparatus (gap value: 20 nm) was used, and the resist performance (sensitivity) was evaluated in the same manner as in the above (3). Table 10 shows the evaluation results.

Table 10 Resist Composition Sensitivity (mJ / cm ² ) Example 2-20 60 Comparative Example 2-102 90 Comparative Example 2-104 90

As is clear from Table 10, the resist composition of the present invention shows extremely excellent performance even in X-ray exposure. The positive electron beam or X-ray resist composition of the present invention has high sensitivity to electron beam or X-ray exposure.

[0304]

According to the present invention, it is possible to provide a positive electron beam or X-ray resist composition having a high resolution and a high sensitivity positive electron beam or X-ray resist composition in addition to a high resolution. it can.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/00 C08L 101/00 H01L 21/027 H01L 21/30 502R

Claims (8)

[Claims] (A1) a compound which generates an acid upon irradiation with an electron beam or X-ray; (B1) a molecular weight which has a group which can be decomposed by the action of an acid and whose solubility in an alkali developing solution is increased by the action of an acid. In a positive resist composition containing a low molecular weight dissolution inhibiting compound having a molecular weight of not more than 1000 and not more than 3000, two or more triphenylmethanes are added to a portion other than the group of the low molecular weight dissolution inhibiting compound which can be decomposed by the action of an acid. A positive electron beam or X-ray resist composition, wherein the composition has a non-conjugated structure. 2. The low molecular weight dissolution inhibiting compound is represented by the following general formula:
A small number selected from the group consisting of the compounds represented by (b1)
2. The compound according to claim 1, which is at least one kind of compound.
A positive electron beam or X-ray resist composition as described in the above. Embedded imageIn the general formula (b1), R₁₀₁~ R₁₁₈Are the same but different
Hydrogen atom, linear alkyl group, branched alkyl
Group, cyclic alkyl group, or alkenyl group. L is a substitution
Represents a methylene group which may have a group. Z is the same
May be different, a hydrogen atom, -A⁰, -R²⁰⁰-COOA
⁰, -ArOB⁰It is. However, 50 mol% or less of Z
Above is not a hydrogen atom. A⁰Is -C (R²⁰¹) (R²⁰²) (R
²⁰³), -Si (R²⁰¹) (R²⁰²) (R²⁰³), -C (R ²⁰⁴) (R
²⁰⁵) -OR²⁰⁶Represents B⁰Is A⁰Or -COOA⁰To
Represent. R²⁰⁰Is a single bond, a divalent group which may have a substituent.
Represents an aliphatic or aromatic hydrocarbon group, and -Ar-
Divalent aromatic carbon optionally having a cyclic or polycyclic substituent
Represents a hydride group. R²⁰¹, R²⁰², R²⁰³, R²⁰⁴, R²⁰⁵
May be the same or different, and each represents a hydrogen atom,
Alkyl group, branched alkyl group, cyclic alkyl group,
A alkenyl group or an aryl group;²⁰⁶Is a linear
Alkyl group, branched alkyl group or aryl group
Represent. Where R²⁰¹~ R²⁰³At least two are water
A group other than an elemental atom;²⁰¹~ R²⁰³, And R
²⁰⁴~ R²⁰⁶Two of the groups combine to form a ring
May be. 3. The method according to claim 1, wherein (A) irradiation with an electron beam or X-ray
(B2) a compound capable of decomposing under the action of an acid,
Molecular weight whose solubility in the developer is increased by the action of acid
Inhibition of low molecular weight dissolution exceeding 1,000 and molecular weight of 3000 or less
Wherein the low-molecular-weight dissolution inhibiting compound has the following general formula as a partial structure:
It contains three or more structures represented by (b2),
A positive-type electron beam,
Or an X-ray resist composition. Embedded imageIn the general formula (b2), R₁₁₉~ R₁₂₆Are the same but different
Hydrogen atom, linear alkyl group, branched alkyl
Group, cyclic alkyl group, or alkenyl group. L is a substitution
Represents a methylene group which may have a group. Z is the same
May be different, a hydrogen atom, -A⁰, -R²⁰⁰-COOA
⁰, -ArOB⁰It is. However, 50 mol% or less of Z
Above is not a hydrogen atom. A⁰Is -C (R²⁰¹) (R²⁰²) (R
²⁰³), -Si (R²⁰¹) (R²⁰²) (R²⁰³), -C (R ²⁰⁴) (R
²⁰⁵) -OR²⁰⁶Represents B⁰Is A⁰Or -COOA⁰To
Represent. R²⁰⁰Is a single bond, a divalent group which may have a substituent.
Represents an aliphatic or aromatic hydrocarbon group, and -Ar-
Divalent aromatic carbon optionally having a cyclic or polycyclic substituent
Represents a hydride group. R²⁰¹, R²⁰², R²⁰³, R²⁰⁴, R²⁰⁵
May be the same or different, and each represents a hydrogen atom,
Alkyl group, branched alkyl group, cyclic alkyl group,
A alkenyl group or an aryl group;²⁰⁶Is a linear
Alkyl group, branched alkyl group or aryl group
Represent. Where R²⁰¹~ R²⁰³At least two are water
A group other than an elemental atom;²⁰¹~ R²⁰³, And R
²⁰⁴~ R²⁰⁶Two of the groups combine to form a ring
May be. 4. The low molecular weight dissolution inhibiting compound is represented by the following general formula:
(B3) and a compound represented by the general formula (b4)
At least one compound selected from the group
4. The positive electron beam or X-ray laser according to claim 3, wherein
Dist composition. Embedded imageIn the general formula (b3), R₁₂₇~ R₁₃₂Are the same but different
Hydrogen atom, linear alkyl group, branched alkyl
Group, cyclic alkyl group, or alkenyl group. L is a substitution
Represents a methylene group which may have a group. Z is the same
May be different, a hydrogen atom, -A⁰, -R²⁰⁰-COOA
⁰, -ArOB⁰It is. However, 50 mol% or less of Z
Above is not a hydrogen atom. A⁰Is -C (R²⁰¹) (R²⁰²) (R
²⁰³), -Si (R²⁰¹) (R²⁰²) (R²⁰³), -C (R ²⁰⁴) (R
²⁰⁵) -OR²⁰⁶Represents B⁰Is A⁰Or -COOA⁰To
Represent. R²⁰⁰Is a single bond, divalent or more which may have a substituent
Represents the above aliphatic or aromatic hydrocarbon group, -Ar-
Is a divalent or higher valent which may have a monocyclic or polycyclic substituent
Represents an aromatic hydrocarbon group. R²⁰¹, R²⁰², R²⁰³,
R²⁰⁴, R²⁰⁵May be the same or different,
Atom, linear alkyl group, branched alkyl group, cyclic
Represents an alkyl group, an alkenyl group or an aryl group;
²⁰⁶Is a linear alkyl group, a branched alkyl group or
Represents an aryl group. Where R²⁰¹~ R²⁰³Less of
And two are groups other than a hydrogen atom.²⁰¹~ R
²⁰³, And R²⁰⁴~ R²⁰⁶Two groups are bonded to each other
To form a ring. Y is a hydrogen atom or methyl
Represents a group. Embedded imageIn the general formula (b4), R₁₃₃~ R₁₄₄Are the same but different
Hydrogen atom, linear alkyl group, branched alkyl
Group, cyclic alkyl group, or alkenyl group. L is a substitution
Represents a methylene group which may have a group. Z is the same
May be different, a hydrogen atom, -A⁰, -R²⁰⁰-COOA
⁰, -ArOB⁰It is. However, 50 mol% or less of Z
Above is not a hydrogen atom. A⁰Is -C (R²⁰¹) (R²⁰²) (R
²⁰³), -Si (R²⁰¹) (R²⁰²) (R²⁰³), -C (R ²⁰⁴) (R
²⁰⁵) -OR²⁰⁶Represents B⁰Is A⁰Or -COOA⁰To
Represent. R²⁰⁰Is a single bond, a divalent group which may have a substituent.
Represents an aliphatic or aromatic hydrocarbon group, and -Ar-
Divalent aromatic carbon optionally having a cyclic or polycyclic substituent
Represents a hydride group. R²⁰¹, R²⁰², R²⁰³, R²⁰⁴, R²⁰⁵
May be the same or different, and each represents a hydrogen atom,
Alkyl group, branched alkyl group, cyclic alkyl group,
A alkenyl group or an aryl group;²⁰⁶Is a linear
Alkyl group, branched alkyl group or aryl group
Represent. Where R²⁰¹~ R²⁰³At least two are water
A group other than an elemental atom;²⁰¹~ R²⁰³, And R
²⁰⁴~ R²⁰⁶Two of the groups combine to form a ring
May be. 5. (A) a compound which generates an acid upon irradiation with an electron beam or X-ray; (B3) a molecular weight which has a group which can be decomposed by the action of an acid and whose solubility in an alkali developing solution is increased by the action of an acid. A low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less, wherein the low molecular weight dissolution inhibiting compound has a biphenyl structure or a triphenylene structure as a partial structure, and a benzene ring other than a benzene ring contained in the group decomposable by the acid. A positive electron beam or X-ray resist composition, wherein the total number is 3 or more and 13 or less. 6. The low molecular weight dissolution inhibiting compound is at least one compound selected from the group consisting of compounds represented by the following formulas (Ih-1) to (Ih-7). The positive electron beam or X-ray resist composition according to claim 5, wherein Embedded image Embedded image Embedded image In the above formulas (Ih-1) to (Ih-7), R ₁₀₁ ′
_{R 110 ', R 112' ~R} 21 3 ' , which may be the same or different, represent a hydrogen atom, a linear, branched or cyclic alkyl group, or an alkenyl group. R ₁₁₁ ′ represents a hydrogen atom, a linear, branched or cyclic alkyl group, alkenyl group or phenyl group. R ₁₃₁ ′ and R ₁₃₂ ′ may combine with each other to form a ring. Y ′ represents hydrogen or a methyl group. A plurality of Z's in the same molecule may be the same or different. Z ′ is a hydrogen atom, —A ⁰ ′, —R ₃₀₀ —CO
Represents OA ⁰ 'or -Ar-OB ⁰ '. However, the above formula (I
In h-1) to (Ih-4), 90 mol% or more of Z ′ is not hydrogen. Further, the above formulas (Ih-5) to (Ih-
In 7), 50 mol% or more of Z ′ is not hydrogen.
A ⁰ ′ represents —C (R ₃₀₁ ) (R ₃₀₂ ) (R ₃₀₃ ), —Si
_{(R 301) (R 302)} (R 3 03) , or -C (R ₃₀₄₎ (R
₃₀₅ ) -OR ₃₀₆ . B ⁰ ′ is -A ⁰ ′ or -COOA
Represents ⁰ '. R ₃₀₀ represents a single bond or a divalent aliphatic or aromatic group which may have a substituent. Ar represents a divalent aromatic group which may have a substituent.
R ₃₀₁ , R ₃₀₂ , R ₃₀₃ , R ₃₀₄ , and R ₃₀₅ may be the same or different and include a hydrogen atom, a linear or branched alkyl group,
Represents a cyclic alkyl group, alkenyl group, aralkyl group or aryl group. R ₃₀₆ represents an alkyl group or an aryl group. Any two of R _{301 to} R ₃₀₃ or R ₃₀₄
To ₃₀₆ may combine with each other to form a ring. 7. (A) a compound capable of generating an acid upon irradiation with an electron beam or X-ray, (B4) a molecular weight having a group decomposable by the action of an acid, and having a solubility in an alkali developing solution increased by the action of an acid. A positive electron beam or X-ray resist composition comprising 3000 or less low molecular weight dissolution inhibiting compound, wherein the low molecular weight dissolution inhibiting compound has a fluorene structure as a partial structure. 8. The low-molecular-weight dissolution-inhibiting compound is at least one compound selected from the group consisting of compounds represented by the following formulas (Ih-8) to (Ih-10). The positive electron beam or X-ray resist composition according to claim 7. Embedded image In the above formulas (Ih-8) to (Ih-10), R ₃₁₀
~ R ₃₆₅ may be the same or different, and represent a hydrogen atom,
Represents a linear, branched or cyclic alkyl group or alkenyl group. R ₃₁₁ and R ₃₁₈ , R ₃₂₉ and R ₃₃₀ , R ₃₄₂ and R
₃₅₅ may form a ring by a single bond with each other. Z ′ has the same meaning as described above, but a plurality of Z ′s in the same molecule may be the same or different. More than 90 mol% of Z 'in the molecule is not hydrogen.