JP2002341539A - Positive resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive resist composition excellent in resolution and exposure margin, which can be suitably used for microphotofabrication using far-UV rays, particularly ArF excimer laser light. SOLUTION: The positive resist composition contains (A) a specified resin which has aliphatic cyclic hydrocarbon groups and increases the dissolving rate with respect to an alkali developer by the effect of an acid and (B) a specified compound which produces an acid by irradiation with active rays or radiation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive resist composition used in an ultra microlithography process such as the production of an ultra LSI or a high-capacity microchip, and other photofabrication processes.

[0002]

2. Description of the Related Art In recent years, the degree of integration of integrated circuits has been increasing more and more, and in the manufacture of semiconductor substrates such as ultra LSIs, processing of ultra fine patterns having a line width of less than half a micron is required. It has become. In order to meet the need, the wavelength used in an exposure apparatus used for photolithography is becoming shorter and shorter, and now it is considered to use excimer laser light (XeCl, KrF, ArF, etc.) having a short wavelength among far ultraviolet rays. Up to now.
A chemically amplified resist is used for forming a lithography pattern in this wavelength region.

Generally, chemically amplified resists can be broadly classified into three types: so-called two-component, 2.5-component and three-component resists. The two-component system combines a compound that generates an acid by photolysis (hereinafter referred to as a photoacid generator) and a binder resin. The binder resin is a resin having in its molecule a group (also referred to as an acid-decomposable group) that is decomposed by the action of an acid to increase the solubility of the resin in an alkaline developer. The 2.5-component system further contains a low molecular compound having an acid-decomposable group in addition to such a two-component system. The three-component system contains a photoacid generator, an alkali-soluble resin, and the above low-molecular compound.

[0004] The above-mentioned chemically amplified resist is suitable for a photoresist for irradiating ultraviolet rays or far-ultraviolet rays. As a photoresist composition for an ArF light source, a resin having an alicyclic hydrocarbon site introduced therein for the purpose of imparting dry etching resistance has been proposed. However, such a phenomenon that the development with an aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH), which has been widely used as a resist developing solution in the past, becomes difficult, and the resist is peeled off from the substrate during the development. Can be seen. In response to such a resist hydrophobization, measures such as mixing an organic solvent such as isopropyl alcohol in a developing solution have been studied. Although some results have been obtained, concerns about the swelling of the resist film and the process become complicated. This is not necessarily a solution. In the approach of improving the resist, many measures have been taken to compensate various hydrophobic alicyclic hydrocarbon sites by introducing a hydrophilic group.

JP-A-10-10739 discloses an energy-sensitive resist containing a polymer obtained by polymerizing a monomer having an alicyclic structure such as a norbornene ring in the main chain, maleic anhydride, and a monomer having a carboxyl group. Materials are disclosed. JP-A-10-111569 discloses a radiation-sensitive resin composition containing a resin having an alicyclic skeleton in the main chain and a radiation-sensitive acid generator.

JP-A-10-130340 discloses a chemically amplified resist containing a terpolymer having a specific repeating structural unit having a norbornene structure in its main chain. JP-A-11-305444 discloses a resin containing a repeating structural unit having an adamantane structure in a side chain and a resin containing maleic anhydride as a repeating structural unit. EP1048983A1 includes a repeating unit composed of norbornene having a specific acid-decomposable group, a repeating unit composed of an anhydride, and a fat for improving storage stability, transparency, dry etching property, sensitivity, resolution, pattern shape and the like. A composition comprising a resin having a repeating unit having a cyclic group is disclosed.
JP-T-11-501909 proposes a compound having an imide or methide acid which is a strong acid as an anion from the viewpoint of improving the solubility of an initiator, a curing agent, or a salt used as a catalyst in an organic solvent and a catalytic activity. are doing. Research Disclosure 437031 proposes the possibility of applying a compound generating imide or methide acid by photolysis to a resist composition.

[0007] However, the conventional positive resist composition has not been able to obtain satisfactory results in the evaluation of the resolving power and the exposure margin in microphotofabrication using far ultraviolet light, particularly ArF excimer laser light. .

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a micro-photofabrication using far-ultraviolet light, particularly ArF excimer laser light, which is excellent in resolution and exposure margin. To provide a positive resist composition.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies on the constituent materials of a positive-type chemically amplified resist composition, and as a result, by using a specific acid-decomposable resin and a specific photoacid generator, The inventors have found that the object of the present invention is achieved, and have reached the present invention. That is, the above object is achieved by the following constitutions.

(1) (A) a resin having an aliphatic cyclic hydrocarbon group and increasing the dissolution rate in an alkali developing solution by the action of an acid; and (B) a compound capable of generating an acid by irradiation with actinic rays or radiation. Wherein the resin of (A) comprises a repeating structural unit represented by the following general formula (I), a repeating structural unit represented by the following general formula (II), and a general formula (III) A positive resist composition comprising a resin having a repeating structural unit represented by the formula: wherein the compound (B) is a compound represented by the following formula (Ia) or (IIb).

[0011]

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In the formula (I), R ₁₁ ′ and R ₁₂ ′ each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group. Z ′ is two bonded carbon atoms (C—C)
And an atomic group for forming an alicyclic structure which may have a substituent.

[0013]

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In the general formula (II): Z ₂ represents —O— or —
N (R ₄₁ )-. Here, R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OSO ₂ —R
Represents ₄₂ . R ₄₂ represents an alkyl group, a haloalkyl group, a cycloalkyl group, or a camphor residue.

[0015]

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In the general formula (III), R ₉₁ is a hydrogen atom,
Represents a lower alkyl group, a halogen atom or -CN. X ₅
Is, -O -, - S -, - NR 93 -, or -NR ₉₃ SO ₂
Represents-. R ₉₃ represents a hydrogen atom, a chain or a cyclic alkyl group. B represents a single bond or a linking group. R ₉₂ represents a hydrogen atom, a chain or cyclic alkyl group, an alkoxy group, a hydroxyl group, a carboxy group, a cyano group, —COOR ₉₄ , or a group represented by any of the following formulas (IV) to (X) . R ₉₄ represents a hydrogen atom or a chain or cyclic alkyl group.

[0017]

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[0018] _{^{-N + (R 95) (R}} 96) (R 97) · X - (VIII) -R 98 -A 50 -R 99 (IX) -SO 3 R 100 (X)

In the formula (IV), Ra₁, Rb₁, R
c₁, Rd₁, And Re₁Is independently a hydrogen atom or
Represents an alkyl group having 1 to 4 carbon atoms. m and n are each independently
Represents an integer of 0 to 3, and m + n is 2 or more and 6 or less.
In the formulas (V-1) to (V-4), R_1b~ R_5bIs each
Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or
Represents an alkenyl group. R_1b~ R_5bTwo of the
To form a ring. In the formula (VII), R_1d~
R_8dEach independently represents a hydrogen atom or an alkyl group.
R_d0Represents a hydrogen atom, a chain or cyclic alkyl group,
Represents an alkyl group or an aralkyl group. m is an integer of 1 to 10
Represent. In the formula (VIII), R₉₅~ R₉₇Are each independently water
Atom, chain or cyclic alkyl group, alkenyl group,
Represents a reel group or an aralkyl group. Where R₉₅~ R ₉₇
May combine with each other to form a non-aromatic ring or an aromatic ring.
X^-Is R-SO_Three ^-Represents R is an aliphatic hydrocarbon group or
Represents an aromatic hydrocarbon group. In the formula (IX), R₉₈Is simple
Alkylene group, arylene group, or a combination thereof.
Represents a divalent group. A₅₀Is one of the functional groups shown below
Indicates the difference.

[0020]

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R ₉₉ represents a hydrogen atom or an alkyl group. In the formula (X), R ₁₀₀ is a chain or cyclic alkyl group,
Represents an aryl group or an aralkyl group.

[0022]

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(In the above formula, R _{1 to} R ₅ each independently represent an aliphatic hydrocarbon group or an aromatic hydrocarbon group which may have a substituent, provided that R _{1 to} R ₃ represent And R ₄ and R ₅ may combine with each other to form a ring, and X ⁻ represents any of the following anions: Represents.)

[0024]

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(In the above formula, R _{6 to} R ₁₀ are each independently
Represents an aliphatic hydrocarbon group which may have a substituent. However, R ₆ and R ₇ may be bonded to each other to form a ring, or two of R _{8 to} R ₁₀ may be bonded to each other to form a ring. )

(2) Z ′ in the general formula (I)
Represents an atomic group for forming a bridged alicyclic structure which contains two bonded carbon atoms (CC) and may have a substituent, (1) The positive resist composition according to the above. (3) The positive resist composition according to (1), wherein the general formula (I) is the following general formula (II-A) or general formula (II-B).

[0027]

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In the formulas (II-A) and (II-B): R ₁₃ ′ to R _13
16 ′ each independently represents a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR ₅ , a group decomposed by the action of an acid, —C (＝ O) —XA′—R ₁₇ ′, or substituted Represents an alkyl group or a cyclic hydrocarbon group which may have a group. Here, R ₅ represents an alkyl group, a cyclic hydrocarbon group or the following —Y group which may have a substituent. X
It represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-. A ′ represents a single bond or a divalent linking group. Also, at least two of R ₁₃ ′ to R ₁₆ ′ may combine to form a ring. n represents 0 or 1.
R ₁₇ ′ represents —COOH, —COOR ₅ , —CN, a hydroxyl group,
An alkoxy group which may have a substituent, -CO-NH
—R ₆ , —CO—NH—SO ₂ —R ₆ or the following —Y group. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. A —Y group;

[0029]

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(In the —Y group, R ₂₁ ′ to R ₃₀ ′ each independently represent a hydrogen atom or an alkyl group which may have a substituent. A and b represent 1 or 2.)

(4) The composition further comprises a fluorine-based and / or silicon-based surfactant.
The positive resist composition according to any one of (3). (5) The positive resist composition according to any one of (1) to (4), further comprising an organic basic compound.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, components used in the present invention will be described in detail. [1] (A) A resin whose dissolution rate in an alkali developer is increased by the action of an acid (also referred to as “acid-decomposable resin”).

The acid-decomposable resin (A) of the present invention is represented by the above general formula (I), which has an aliphatic cyclic hydrocarbon group and increases the dissolution rate in an alkali developer by the action of an acid. A resin having a repeating structural unit represented by the general formula (II) and a repeating structural unit represented by the general formula (III) is used.

In the above general formula (I), R ₁₁ ′ and R ₁₂ ′
Is independently a hydrogen atom, a cyano group, a halogen atom,
Or an alkyl group which may have a substituent. Z '
Represents an atomic group for forming an alicyclic structure which has two bonded carbon atoms (CC) and may have a substituent.

Examples of the halogen atom in R ₁₁ ′ and R ₁₂ ′ include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom. The above R ₁₁ ′, R ₁₂ ′, R ₂₁ ′ to R
The alkyl group at ₃₀ ′ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and still more preferably Methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group,
They are a sec-butyl group and a t-butyl group. Also,
The alkyl group in R ₁₁ ′, R ₁₂ ′ and R ₂₁ ′ to R ₃₀ ′ may have a substituent.

Further substituents in the above alkyl group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, an iodine atom,
Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the acyl group include a formyl group and an acetyl group. Is an acetoxy group.

The atomic group for forming the alicyclic structure of Z 'is an atomic group for forming a repeating unit of an alicyclic hydrocarbon which may have a substituent on the resin. An atomic group for forming a bridged alicyclic structure forming a repeating unit of the alicyclic hydrocarbon of the formula is preferred. Examples of the alicyclic hydrocarbon skeleton to be formed include those represented by the following structures.

[0038]

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[0039]

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Preferred skeletons of bridged alicyclic hydrocarbons include (5), (6), (7),
(9), (10), (13), (14), (15),
(23), (28), (36), (37), (42),
(47).

The alicyclic hydrocarbon skeleton may have a substituent. Examples of such a substituent include R ₁₃ ′ to R ₁₆ ′ in the general formula (II-A) or (II-B). Among the repeating units having a bridged alicyclic hydrocarbon, a repeating unit represented by the above general formula (II-A) or (II-B) is more preferable.

Formula (II-A) or (II-B)
In the formula, R ₁₃ ′ to R ₁₆ ′ each independently represent a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR ₅ , a group decomposed by the action of an acid, —C (＝ O) —XA ′. -R
₁₇ ′ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. R ₅ represents an alkyl group, a cyclic hydrocarbon group or the above-mentioned —Y group which may have a substituent. X is an oxygen atom, a sulfur atom, -NH-, -NH
Represents SO ₂ — or —NHSO ₂ NH—. A ′ represents a single bond or a divalent linking group. Also, at least two of R ₁₃ ′ to R ₁₆ ′ may combine to form a ring. n is 0
Or represents 1. R ₁₇ ′ represents —COOH, —COOR ₅ ,
—CN, a hydroxyl group, an optionally substituted alkoxy group, —CO—NH—R ₆ , —CO—NH—SO ₂ —R ₆
Or, represents the following -Y group. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. The-
In the Y group, R ₂₁ ′ to R ₃₀ ′ each independently represent a hydrogen atom or an alkyl group which may have a substituent;
b represents 1 or 2.

Examples of the halogen atom in R ₁₃ ′ to R ₁₆ ′ include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom.

The alkyl group for R ₅ , R ₆ and R ₁₃ ′ to R ₁₆ ′ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms.
Six linear or branched alkyl groups, more preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group.

Examples of the cyclic hydrocarbon group for R ₅ , R ₆ and R ₁₃ ′ to R ₁₆ ′ include a cyclic alkyl group and a bridged hydrocarbon group, such as a cyclopropyl group, a cyclopentyl group,
Cyclohexyl group, adamantyl group, 2-methyl-2-
Examples thereof include an adamantyl group, a norbornyl group, a boronyl group, an isobornyl group, a tricyclodecanyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, and a tetracyclododecanyl group. The ring formed by bonding at least two of R ₁₃ ′ to R ₁₆ ′ is cyclopentene,
Rings having 5 to 12 carbon atoms such as cyclohexene, cycloheptane, cyclooctane and the like can be mentioned.

Examples of the alkoxy group for R ₁₇ ′ include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

Further substituents in the above alkyl group, cyclic hydrocarbon group and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group, an alkyl group and a cyclic hydrocarbon group. Can be mentioned. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the acyl group include a formyl group and an acetyl group. Examples thereof include an acetoxy group. Also,
Examples of the alkyl group and the cyclic hydrocarbon group include those described above.

The divalent linking group represented by A ′ is selected from the group consisting of an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group and a urea group. The selected one or a combination of two or more groups may be mentioned. Examples of the alkylene group and substituted alkylene group in A ′ include groups represented by the following formula. -[C (R _a ) (R _b )] _r-wherein R _a and R _b represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group,
Both may be the same or different. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. As the substituent of the substituted alkyl group,
Examples include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r represents an integer of 1 to 10.

The above general formula (II-A) or general formula (II
The various substituents of R ₁₃ ′ to R ₁₆ ′ in -B) are an atomic group for forming an alicyclic structure or an atomic group for forming a bridged alicyclic structure in the general formula (I). Z also serves as a substituent.

The above general formula (II-A) or general formula (II
Specific examples of the repeating unit represented by -B) include the following [II
-1] to [II-175], but the present invention is not limited to these specific examples.

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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In the general formula (II), Z ₂ represents-
Represents O- or -N ( _R41 )-. Here, R ₄₁ is a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OS
Represents O ₂ -R ₄₂ . R ₄₂ represents an alkyl group, a haloalkyl group, a cycloalkyl group, or a camphor residue.

The alkyl group for R ₄₁ and R ₄₂ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. And more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, or an n-
A butyl group, an isobutyl group, a sec-butyl group and a t-butyl group. Examples of the haloalkyl group for R ₄₁ and R ₄₂ include a trifluoromethyl group, a nanofluorobutyl group, a pentadecafluorooctyl group, and a trichloromethyl group. Examples of the cycloalkyl group for R ₄₂ include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

The alkyl group and haloalkyl group as R ₄₁ and R ₄₂ , the cycloalkyl group or camphor residue as R ₄₂ may have a substituent. Examples of such a substituent include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom), and an alkoxy group (preferably having 1 to 1 carbon atoms).
4, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like, an acyl group (preferably having 2 to 5 carbon atoms, for example, a formyl group, an acetyl group and the like), and an acyloxy group (preferably having 2 to 5 carbon atoms, for example, An acetoxy group) and an aryl group (preferably having 6 to 14 carbon atoms, for example, a phenyl group).

Specific examples of the repeating unit represented by the above general formula (II) include the following [I'-1] to [I'-7], but the present invention is limited to these specific examples. Not something.

[0074]

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[0075]

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Next, the repeating unit represented by formula (III) will be described. In the formula (III), R ₉₁ is
Represents a hydrogen atom, a lower alkyl group, a halogen atom, or a cyano group. As the lower alkyl group for R ₉₁ ,
5 are preferable, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group. This lower alkyl group may further have a substituent. Examples of such a substituent include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (eg, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom) and an alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy group). Group, ethoxy group,
A propoxy group, a butoxy group and the like), an acyl group (preferably having 2 to 5 carbon atoms, such as a formyl group and an acetyl group),
An acyloxy group (preferably having 2 to 5 carbon atoms, for example, an acetoxy group), an aryl group (preferably having 6 to 14 carbon atoms,
For example, a phenyl group) and the like.

[0077] X ₅ is, -O -, - S -, - NR 93 -, or -NR ₉₃ SO ₂ - it represents a. R ₉₃ represents a hydrogen atom, a chain or a cyclic alkyl group. The chain alkyl group as R ₉₃ is a lower alkyl group, preferably one having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Examples of the cyclic alkyl group include those having 3 to 12 carbon atoms. These may further have a substituent, as a substituent,
For example, a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom), an alkoxy group (preferably having 1 to 4 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, A butoxy group), an acyl group (preferably having 2 to 5 carbon atoms, for example,
Examples thereof include a formyl group and an acetyl group, an acyloxy group (preferably having 2 to 5 carbon atoms, for example, an acetoxy group), and an aryl group (preferably having 6 to 14 carbon atoms, for example, a phenyl group).

B represents a single bond or a linking group. Examples of the linking group for B include a single or a combination of two or more groups selected from the group consisting of an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, and an ester group. As the cycloalkylene group for B, those having 3 to 10 carbon atoms are preferable, and examples thereof include a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group. Examples of the alkylene group for B include groups represented by the following formula. -[C ( _RX ) ( _RY )] _Z -Rx and Ry each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, or a linear or cyclic alkyl group or an alkoxy group which may have a substituent. , An alkenyl group, an aryl group, or an aralkyl group. However, Rx and Ry may combine with each other to form a cyclic alkyl ring. Examples of the linear alkyl group of Rx or Ry include a linear or branched alkyl group, which may have a substituent. Linear,
As the branched alkyl group, a linear or branched alkyl group having 1 to 12 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable. Methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s
ec-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. Examples of the cyclic alkyl group include those having 3 to 30 carbon atoms, and may include a hetero atom such as an oxygen atom or a nitrogen atom. Specifically, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group,
Norbornyl group, boronyl group, tricyclodecanyl group,
Examples thereof include a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, a tetracyclododecanyl group, a steroid residue, a tetrahydropyranyl group, and a morpholino group. The alkoxy group generally has 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. Examples thereof include a methoxy group, an ethoxy group, a propoxy group and a butoxy group. And the like. Examples of the alkenyl group include an alkenyl group having 2 to 6 carbon atoms,
It may have a substituent. Specifically, vinyl group, propenyl group, allyl group, butenyl group, pentenyl group, hexenyl group, cyclopentenyl group, cyclohexenyl group,
Examples include a 3-oxocyclohexenyl group, a 3-oxocyclopentenyl group, and a 3-oxoindenyl group. Among these, the cyclic alkenyl group may contain an oxygen atom. Examples of the aryl group include those having 6 to 10 carbon atoms, which may have a substituent. Specific examples include a phenyl group, a tolyl group, and a naphthyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a mesitylmethyl group. Examples of the substituent which the above-mentioned chain or cyclic alkyl group, alkoxy group, alkenyl group, aryl group or aralkyl group may have include, for example, carboxyl group, cyano group, hydroxyl group, halogen atom (chlorine atom, bromine atom , A fluorine atom, an iodine atom, etc.), an alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy group, ethoxy group, propoxy group, butoxy group), an acetylamide group, an alkoxycarbonyl group, an acyl group (preferably having 2 carbon atoms) To 10, for example, formyl group, acetyl group, propionyl group), acyloxy group (preferably having 2 to 2 carbon atoms)
10, for example, an acetoxy group) and an aryl group (preferably having 6 to 14 carbon atoms, for example, a phenyl group). R
As for the aryl group or aralkyl group as x or Ry, as a substituent, an alkyl group (preferably having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group) , A cyclopentyl group, etc.). The alkyl group as a substituent may further have a substituent such as a hydroxyl group, a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group). . Z is an integer of 1 to 10, preferably 1 to 4.

R ₉₂ is a hydrogen atom, a chain or cyclic alkyl group, an alkoxy group, a hydroxyl group, a carboxy group, a cyano group,
—COOR ₉₄ or a group represented by any of the above formulas (IV) to (X). _Examples of the chain alkyl group as R ₉₂ and R ₉₄ generally include those having 1 to 30 carbon atoms, preferably 6 to 20 carbon atoms. For example, a methyl group,
Ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group,
Nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and the like can be mentioned. R ₉₂ and R
The cyclic alkyl group as ₉₄ generally has 3 carbon atoms.
To 40, preferably 6 to 20. For example, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, tricyclodecanyl group, dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl Group, steroid residue, tetrahydropyranyl group, morpholino group and the like.

The chain alkyl groups as R ₉₂ and R ₉₄ may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (eg, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom),
An alkoxy group (preferably having 1 to 4 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.), an alkoxycarbonyl group, an acyl group (preferably having 2 carbon atoms)
To 5, for example, a formyl group, an acetyl group, etc.), an acyloxy group (preferably, having 2 to 5 carbon atoms, for example, an acetoxy group), an aryl group (preferably having 6 to 14 carbon atoms, for example, a phenyl group), and an acetylamide group. Can be mentioned. Here, examples of the alkoxy group in the alkoxycarbonyl group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. The cyclic alkyl group as R ₉₂ and R ₉₄ is
As a substituent, a carboxyl group, a cyano group, a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, an iodine atom),
An alkoxy group (preferably having 1 to 4 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.), an alkoxycarbonyl group, an acyl group (preferably having 2 carbon atoms)
To 5, for example, a formyl group, an acetyl group, etc.), an acyloxy group (preferably, having 2 to 5 carbon atoms, for example, an acetoxy group), an aryl group (preferably having 6 to 14 carbon atoms, for example, a phenyl group), and an acetylamide group. It may be.
Here, examples of the alkoxy group in the alkoxycarbonyl group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

The repeating unit represented by the above formula (III) wherein R ₉₂ is a cyclic alkyl group is preferably a repeating unit represented by the following formula (IIIa) or (IIIb).

[0082]

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The general formulas (IIIa) and (IIIa)
In b), R ₀ represents a hydrogen atom, a lower alkyl group, a halogen atom, or a cyano group. R ₆₁ and R ₆₂ represent a lower alkyl group. R _{63 to} R ₆₈ each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom.
R ₆₃ and R ₆₄ or R ₆₅ and R ₆₆ may together form a carbonyl group. R ₆₃ and R ₆₅ may be linked to form an alkylene chain. k and l are integers of 2 to 5.

The above general formulas (IIIa) and (IIIb)
In the repeating unit represented by, acid-decomposability is exhibited by the presence of a tertiary carbon atom to which _R61 is bonded. R ₀ is preferably a hydrogen atom. The lower alkyl group represented by R ₀ and R _{61 to} R ₆₈ has 1 to 6 carbon atoms, and preferably has 1 to 4 carbon atoms. Specific examples include, for example, a methyl group, an ethyl group, a linear or branched propyl group, and a linear or branched butyl group. The lower alkoxy group represented by R _{63 to} R ₆₈ has 1 to 6 carbon atoms, preferably 1 carbon atom.
~ 4. Specific examples include, for example, a methoxy group, an ethoxy group, a linear or branched propoxy group, and a linear or branched butoxy group. The lower alkyl groups as R ₀ and R _{61 to} R ₆₈ and the lower alkoxy groups as R _{63 to} R ₆₈ may have a substituent. As the substituent,
Examples thereof include a halogen atom such as a chlorine atom and a bromine atom, and an alkoxy group (preferably having 1 to 3 carbon atoms) such as a methoxy group and an ethoxy group.

R ₆₃ and R ₆₄ or R ₆₅ and R ₆₆ may together form a carbonyl group. k and l are preferably 2 to 4, more preferably 2 or 3. The alkylene chain which may be formed by linking R ₆₃ and R ₆₅ preferably has 3 or less carbon atoms, such as a methylene chain, an ethylene chain and a propylene chain.

The alkoxy group represented by R ₉₂ generally has 1 to 30, preferably 3 to 20, more preferably 4 to 15 carbon atoms. Examples thereof include methoxy, ethoxy, propoxy and butoxy. And the like. The alkoxy group for R ₉₂ may further have a substituent, and examples of the substituent are the same as those described as the substituent for the chain or cyclic alkyl group as R ₉₂ .

Hereinafter, R ₉₂ is an alkyl group, an alkoxy group,
A repeating unit represented by the general formula (III), which is a hydrogen atom,
And specific examples of the repeating unit represented by the general formula (IIIa) and the general formula (IIIb), but are not limited thereto.

[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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*) Units differing in the number of groups in parentheses are a mixture of units, indicating that the group has an average of 1.4 groups in parentheses.

Specific examples of the repeating unit represented by the general formula (III), the repeating unit represented by the general formula (IIIa) and the monomer corresponding to the repeating unit represented by the general formula (IIIb) are shown below. However, the present invention is not limited to these.

[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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Further, a repeating structural unit in which R ₉₂ in the formula (III) has a structure represented by the following general formula (IV) will be described.

[0103]

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Ra ₁ , Rb ₁ , Rc ₁ , Rd ₁ , and Re ₁ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m and n each independently represent an integer of 0 to 3, and m + n
Is 2 or more and 6 or less. Ra _{1 to} Re ₁ having 1 to 4 carbon atoms
Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and s.
Examples thereof include an ec-butyl group and a t-butyl group. These alkyl groups may be substituted with a substituent such as an alkoxy group (preferably having 1 to 4 carbon atoms).

Hereinafter, specific examples of the repeating structural unit having the structure of the general formula (IV) will be shown, but it should not be construed that the invention is limited thereto.

[0106]

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[0107]

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[0108]

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In the specific examples of the repeating unit having the structure of the general formula (IV), (IV-17) to (IV-36) are preferable from the viewpoint that the exposure margin becomes better. Further, as the structure of the general formula (IV), a structure having an acrylate structure is preferable from the viewpoint that edge roughness is improved.

Further, the following general formulas (V-1) to (V-
The repeating unit structure having a group represented by any of 4) will be described.

[0111]

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In the general formulas (V-1) to (V-4),
R _{1b to} R _5b each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group. Two of R _{1b to} R _5b may combine to form a ring.

In the general formulas (V-1) to (V-4),
Examples of the alkyl group for R _{1b to} R _5b include a linear or branched alkyl group. As the straight-chain or branched alkyl group, a straight-chain or branched alkyl group having 1 to 12 carbon atoms is preferable, more preferably 1 to 1 carbon atom.
0 linear or branched alkyl groups, more preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, A hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. R _{1b to} R
The cycloalkyl group in _5b is preferably a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. As the alkenyl group for R _{1b to} R _5b ,
For example, those having 2 to 6 carbon atoms such as a vinyl group, a propenyl group, a butenyl group, and a hexenyl group are preferable. Also, R _1b
Examples of the ring formed by combining two of R to _R5b include a 3- to 8-membered ring such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring.

[0114] The alkyl group as R _1b to R _5b, cycloalkyl group, of the alkenyl group, and R _1b to R _5b 2
The rings formed by the bonding may each have a substituent. Preferred substituents include a hydroxyl group, a carboxy group, a nitro group, a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), and a carbon number of 1 to 4.
And an alkoxycarbonyl group having 2 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, and the like. Note that R _{1b to} R _5b in the general formulas (V-1) to (V-4) may be connected to any of the carbon atoms constituting the cyclic skeleton.

Preferred as the repeating unit having a group represented by any of formulas (V-1) to (V-4) is a repeating unit represented by the following formula (AI).

[0116]

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In the general formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. R
The alkyl group of _b0 may have a substituent, and a preferable substituent is an alkyl group represented by R _1b in formulas (V-1) to (V-4). Examples of the substituent include those described above. R _b0
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R _b0 is preferably a hydrogen atom. B ₂ represents a group represented by any of formulas (V-1) to (V-4). A ′ is represented by the formula (II
It is the same as the definition of B in I). In A ′, examples of the combined divalent group include those represented by the following formula.

[0118]

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In the above formula, Rab and Rbb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, and they may be the same or different. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r
1 represents an integer of 1 to 10, preferably an integer of 1 to 4.
m represents an integer of 1 to 3, preferably 1 or 2.

The specific examples of the repeating units represented by formula (AI) are shown below, but the invention is not limited thereto.

[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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Next, a repeating structural unit having a structure represented by the following formula (VI) will be described.

[0129]

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The bridged alicyclic ring containing Z may have a substituent. Examples of the substituent include a carboxyl group, a hydroxyl group, a halogen atom, an alkyl group (preferably having 1 to 4 carbon atoms) and an alkoxy group (preferably having 1 to 4 carbon atoms).
4), an alkoxycarbonyl group (preferably having 2 to 2 carbon atoms)
5), an acyl group (eg, a formyl group, a benzoyl group), an acyloxy group (eg, a propylcarbonyloxy group, a benzoyloxy group), and an alkylsulfonylsulfamoyl group (—CONHSO ₂ CH _{3 and the} like). In addition, the alkyl group as a substituent further includes a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms).
And so on.

In the general formula (III), B represents the general formula (V
It may be bonded at any position of the carbon atom constituting the bridged alicyclic structure containing Z in I).

Specific examples of the repeating unit having the structure represented by formula (VI) are shown below, but it should not be construed that the invention is limited thereto.

[0133]

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[0134]

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Further, a repeating structural unit in which R ₉₂ in the formula (III) has a structure represented by the following general formula (VII) will be described.

[0136]

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In the general formula (VII), R _{1d to} R _8d are
Each independently represents a hydrogen atom or a chain alkyl group. R
_d0 represents a hydrogen atom, a chain or cyclic alkyl group, an aryl group or an aralkyl group. m represents an integer of 1 to 10.

R _{1d to} R _8d and R _d0 in the general formula (VII)
Examples of the chain alkyl group include a linear, branched or cyclic alkyl group, which may have a substituent. The linear or branched alkyl group has 1 to 1 carbon atoms.
Twelve linear or branched alkyl groups are preferred,
More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms, and still more preferably, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and t -Butyl, pentyl, hexyl, heptyl, octyl, nonyl,
Decyl group. _Examples of the cyclic alkyl group for R _d0 include those having 3 to 30 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, and a tricyclodecanyl group. Group, dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group, steroid residue and the like.

The aryl group represented by R _d0 has 6 to 2 carbon atoms.
Zero thing is mentioned, and it may have a substituent. Specific examples include a phenyl group, a tolyl group, and a naphthyl group. _Examples of the aralkyl group for R _d0 include those having 7 to 20 carbon atoms, which may have a substituent. Examples thereof include a benzyl group, a phenethyl group, and a cumyl group. In the present invention, R _{1d to} R _8d are preferably a hydrogen atom or a methyl group. R _d0 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m is preferably 1 to 6.

The above-mentioned chain or cyclic alkyl group, aryl group, aralkyl group, alkylene group, cyclic alkylene group,
Further substituents in the arylene group include a carboxyl group, a cyano group, a hydroxyl group, a halogen atom (eg, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc.), an alkyl group, a substituted alkyl group, an alkoxy group (preferably having 1-4, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group), an alkoxycarbonyl group, an acyl group, an acyloxy group (for example, an acetoxy group), and an acetylamide group. Here, examples of the alkyl group include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group. As the substituent of the substituted alkyl group, a hydroxyl group, a halogen atom,
An alkoxy group (preferably having 1 to 4 carbon atoms) can be mentioned.

Specific examples of the repeating unit having the structure represented by the general formula (VII) are shown below, but it should not be construed that the invention is limited thereto.

[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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Next, a repeating structural unit in which R ₉₂ in the formula (III) has a structure represented by the following general formula (VIII) will be described. −N ⁺ (R ₉₅ ) (R ₉₆ ) (R ₉₇ ) · X ⁻ (VIII)

In the formula (VIII), R _{95 to} R ₉₇ each independently represent a hydrogen atom, a chain or cyclic alkyl group, an alkenyl group, an aryl group, or an aralkyl group. However,
R ₉₅ to R _97, taken together non-aromatic ring, may form an aromatic ring. Examples of the chain alkyl group include a linear or branched alkyl group, which may have a substituent. A linear or branched alkyl group having 1 to 12 carbon atoms is preferable, a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable, and a methyl group, an ethyl group, and a propyl group are more preferable. , Isopropyl group, n-
Butyl, isobutyl, sec-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl.

The cyclic alkyl group may have 3 to 3 carbon atoms.
Zero atoms are mentioned, and they may contain a hetero atom such as an oxygen atom or a nitrogen atom. Specifically, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, tricyclodecanyl group, dicyclopentenyl group, nobornane epoxy group,
Menthyl, isomenthyl, neomenthyl, tetracyclododecanyl, steroid residues, tetrahydropyranyl, morpholino and the like can be mentioned.

Examples of the alkenyl group include alkenyl groups having 2 to 6 carbon atoms, which may have a substituent.
Specifically, vinyl, propenyl, allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, 3-oxocyclohexenyl, 3-oxocyclopentenyl, 3-oxoindenyl and the like are exemplified. No. Among these, the cyclic alkenyl group may contain an oxygen atom. Examples of the aryl group include those having 6 to 10 carbon atoms, which may have a substituent. Specific examples include a phenyl group, a tolyl group, and a naphthyl group.

Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and a mesitylmethyl group.

[0153] chain or cyclic alkyl group as R ₉₅ to R _97, an alkenyl group, an aryl group, or an aralkyl group, and R ₉₅ to R ₉₇ are bonded may form a non-aromatic ring, the aromatic ring is Yes Examples of the optionally substituted substituent include a carboxyl group, a cyano group, a hydroxyl group, a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc.) and an alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy Group, ethoxy group, propoxy group, butoxy group), acetylamide group, alkoxycarbonyl group, acyl group (preferably having 2 to 10 carbon atoms, for example, formyl group, acetyl group, propionyl group), acyloxy group (preferably having carbon number Two
10, for example, an acetoxy group) and an aryl group (preferably having 6 to 14 carbon atoms, for example, a phenyl group). R
_{95 to} R ₉₇ as an aryl group or an aralkyl group and R ₉₅
To R ₉₇ are combined to form non-aromatic ring may be, for the aromatic ring, as a substituent, an alkyl group (preferably having from 1 to 5 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl Group, cyclopropyl group, cyclobutyl group, cyclopentyl group, etc.). The alkyl group as a substituent may further have a substituent such as a hydroxyl group, a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group). .

X ^- has a specific structure R-SO ₃ as described above.
^- with a. The aliphatic hydrocarbon group for R is preferably a linear or branched alkyl group having 1 to 20 carbon atoms or a cyclic alkyl group, and may have a substituent. Also,
The aromatic hydrocarbon group for R is preferably an aromatic group having 6 to 14 carbon atoms, and may have a substituent.

Examples of the alkyl group represented by R include a methyl group, an ethyl group, a propyl group and an n-
Butyl group, n-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, decyl group, dodecyl group and the like, and as the cyclic alkyl group, a cyclopentyl group which may have a substituent , Cyclohexyl, cyclooctyl, cyclododecyl, adamantyl, norbornyl, camphor, tricyclodecanyl, menthyl and the like. Examples of the aromatic group include a phenyl group and a naphthyl group which may have a substituent.

Examples of the substituent which the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have include, for example, a halogen atom, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group,
Examples include a camphor group, specifically, methyl group, t-butyl group, methoxy group, ethoxy group, t-butoxy group, fluorine atom, chlorine atom, bromine atom, cyano group, hydroxyl group, methoxycarbonyl group, ethoxy group Examples include a carbonyl group, a t-butoxycarbonyl group, and a t-amyloxycarbonyl group. Further, an aryl group (preferably having 6 to 14 carbon atoms) can be mentioned as a substituent for an aliphatic hydrocarbon group, and an alkyl group (1 to 15 carbon atoms) can be given as a substituent for an aromatic hydrocarbon group.

Hereinafter, specific examples of the repeating unit having the structure represented by formula (VIII) will be shown. However, the content of the present invention is not limited to these.

[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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Further, a repeating structural unit in which R ₉₂ in the formula (III) has a structure represented by the following formula (IX) or (X) will be described. -R ₉₈ -A ₅₀ -R ₉₉ (IX) -SO ₃ R ₁₀₀ (X)

In the formula (IX), R ₉₈ represents a single bond, an alkylene group, an arylene group, or a combination thereof.
Represents a valence group. The arylene group has 6 to 10 carbon atoms.
And may have a substituent. Specific examples include a phenylene group, a tolylene group and a naphthylene group.

Examples of the alkylene group include the groups shown below. -[C (Rf) (Rg)] r- wherein Rf and Rg each represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group or an alkoxy group, and both may be the same or different; The group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, and more preferably represents a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group and an isopropyl group. . Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. r represents an integer of 1 to 10. In the above, examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

A ₅₀ represents any of the following functional groups.

[0167]

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R ₉₉ represents a hydrogen atom or an alkyl group.
The chain alkyl group for R ₉₉ may be linear or branched, and may have a substituent. As the linear or branched alkyl group, those having 1 to 12 carbon atoms are preferable, and those having 1 to 10 carbon atoms are more preferable.
Specifically, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl Are preferred.

R ₁₀₀ in the general formula (X) represents a chain or cyclic alkyl group, an aryl group or an aralkyl group;
It may have a substituent. The chain alkyl group for R ₁₀₀ may be linear or branched, and may have a substituent. The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably has 1 to 10 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, Preferred examples include an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of the cyclic alkyl group represented by R ₁₀₀ include those having 3 to 30 carbon atoms, and specifically, cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, boronyl, and tricyclodecanyl groups. , Dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group, steroid residue and the like. The ring structure may have a heteroatom and a double bond. Such examples include tetrahydropyran and pentene rings.

The aryl group represented by R ₁₀₀ has 6 to 6 carbon atoms.
20 and may have a substituent. Specific examples include a phenyl group, a tolyl group, and a naphthyl group. The aralkyl group represented by R ₁₀₀ has 7 to 20 carbon atoms.
And may have a substituent. Specific examples include a benzyl group, a phenethyl group, and a cumyl group.

Examples of the substituent which the chain alkyl group for R _99, the chain or cyclic alkyl group for R ₁₀₀ , the alkoxy group, the aryl group or the aralkyl group may have include
Carboxyl group, cyano group, hydroxyl group, halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom, etc.), alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy group,
Ethoxy group, propoxy group, butoxy group), acetylamide group, alkoxycarbonyl group, acyl group (preferably having 2 to 10 carbon atoms, for example, formyl group, acetyl group,
A propionyl group), an acyloxy group (preferably having 2 to 10 carbon atoms, for example, an acetoxy group), and an aryl group (preferably having 6 to 14 carbon atoms, for example, a phenyl group). As for the aryl group or aralkyl group as R _100, as a substituent, an alkyl group (preferably having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group, A cyclopentyl group). The alkyl group as a substituent may further have a substituent such as a hydroxyl group, a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group). . The ring structure may form a condensed ring.

[0172] Hereinafter, -NH-SO ₂ - formula containing
Specific examples (2) to (5) of the monomer corresponding to the repeating unit represented by (III), and specific examples (6) of the monomer corresponding to the repeating structural unit having the structure represented by formula (IX) To (15), but are not limited thereto.

[0173]

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[0174]

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[0175]

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Hereinafter, specific examples of the monomer corresponding to the repeating structural unit having the structure represented by formula (X) will be shown, but it should not be construed that the invention is limited thereto.

[0177]

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[0178]

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[0179]

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The acid-decomposable resin used in the present invention may further contain a repeating unit represented by the following formula (XI).

[0181]

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With respect to the general formula (XI), R ₉₁ c, X ₅ c,
R ₉₃ c and B c are the same as R ₉₁ , X ₅ , R ₉₃ and B in the formula (III), respectively. R _92c represents a group represented by the following general formula (XI ′).

[0183]

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In the general formula (XI ′), R ₂ c to R ₄ c
Each independently represents a hydrogen atom or a hydroxyl group. Where R
At least one of ₂ c to R ₄ c represents a hydroxyl group.

The structure represented by formula (XI) is preferably a dihydroxy form or a monohydroxy form, more preferably a dihydroxy form.

Specific examples of the repeating unit having the structure represented by formula (XI) are shown below, but it should not be construed that the invention is limited thereto.

[0187]

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[0188]

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In the resin according to the present invention, the structure of the acid-decomposable group is represented, for example, by —C (＝ O) —X ₁ —R ₀ . In the formula, R ₀ represents a tertiary alkyl group such as t-butyl group, t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxy 1-alkoxyethyl group such as ethyl group, alkoxymethyl group such as 1-methoxymethyl group, 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3- An oxocyclohexyl ester group, a 2-methyl-2-adamantyl group, a mevalonic lactone residue and the like can be mentioned. X ₁ is an oxygen atom, a sulfur atom, -NH-, -NHS
O ₂ — or —NHSO ₂ NH— is represented. In the resin according to the present invention, an acid-decomposable group represented by the following general formula (a) is more preferable, and an acid-decomposable group represented by the general formula (b) is particularly preferable.

[0190]

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In the above structure, R _{1a to} R _3a each independently represent
Represents an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and an adamantyl. Examples of such a monomer having an acid-decomposable group include the above-described 5, 6, 7, 8, 9, 10, and 10 as monomers corresponding to the repeating structural unit represented by the general formula (III).
27, 28, 29 and the like. Further, as a repeating structural unit having such an acid-decomposable group,
For example, the above-mentioned II-6 to II-8 listed as the repeating structural units represented by the general formulas (II-A) and (II-B),
II-11, II-12, II-16 to II-19, II-21,
II-23 to II-26, II-29, II-30, II-41,
II-46, II-50 to II-52, II-58, II-61,
II-81, II-113, II-167, II-169 to II-
171 and the like.

In the resin according to the present invention, the acid-decomposable group is a repeating structural unit having a partial structure containing an alicyclic hydrocarbon represented by the aforementioned general formula (I);
Embedded image and at least one of the repeating units of the copolymer component described below.

The acid-decomposable resin as the component (A) has, in addition to the above-mentioned repeating structural units, dry etching resistance, suitability for a standard developing solution, substrate adhesion, a resist profile, and general necessary properties of a resist. Various repeating structural units can be contained for the purpose of adjusting resolution, heat resistance, sensitivity and the like.

Examples of such a repeating structural unit include repeating structural units corresponding to the following monomers, but are not limited thereto. Thereby, the performance required for the acid-decomposable resin, in particular, (1) solubility in a coating solvent, (2) film forming property (glass transition point), (3) alkali developability, (4) film sliding (affinity) Aqueous and alkali-soluble groups can be selected), (5) Adhesion of the unexposed portion to the substrate, (6) Dry etching resistance, etc. can be finely adjusted. As such monomers, for example, acrylates, methacrylates,
Examples include compounds having one addition-polymerizable unsaturated bond selected from acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like.

Specific examples include the following monomers. Acrylic esters (preferably alkyl acrylates having 1 to 10 carbon atoms in the alkyl group): methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acryl Acid-t-octyl, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate,
Trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate,
Methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate and the like.

Methacrylates (preferably alkyl methacrylates having an alkyl group of 1 to 10 carbon atoms): methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate,
Cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, penta Erythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate and the like.

Acrylamides: acrylamide, N-
Alkyl acrylamide (the alkyl group has 1 carbon atom
And 10 such as methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl, cyclohexyl, and hydroxyethyl. ), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group,
Cyclohexyl group, etc.), N-hydroxyethyl-
N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like.

Methacrylamides: methacrylamide,
N-alkyl methacrylamide (an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group,
Butyl group, ethylhexyl group, hydroxyethyl group, cyclohexyl group, etc.), N, N-dialkylmethacrylamide (alkyl group includes ethyl group, propyl group, butyl group, etc.), N-hydroxyethyl-N-
Methyl methacrylamide and the like.

Allyl compounds: allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol etc.

Vinyl ethers: alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether,
-Methyl-2,2-dimethylpropyl vinyl ether,
2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether,
Dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether and the like.

Vinyl esters: vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl chloride acetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl Acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like.

Dialkyl itaconates: dimethyl itaconate, diethyl itaconate, dibutyl itaconate and the like. Dialkyl esters or monoalkyl esters of fumaric acid; dibutyl fumarate and the like.

Others crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilenitrile and the like.

In addition, as long as it is an addition-polymerizable unsaturated compound copolymerizable with the monomer corresponding to the above-mentioned various repeating structural units, it may be copolymerized.

In the acid-decomposable resin, the molar ratio of each repeating structural unit depends on the dry etching resistance of the resist, the suitability for a standard developing solution, the substrate adhesion, the resist profile, and the resolution, which is a general required performance of the resist, heat resistance. It is set as appropriate to adjust the properties, sensitivity, and the like.

In the acid-decomposable resin, the content of the repeating unit represented by the general formula (I) is 10 to 10 in all the repeating structural units.
It is preferably 60 mol%, more preferably 15 to 55 mol%, and still more preferably 20 to 50 mol%. In the acid-decomposable resin, the content of the repeating unit represented by the general formula (II) is preferably from 10 to 70 mol%, more preferably from 15 to 60 mol%, even more preferably from 20 to 50 mol%, based on all repeating structural units. Mol%. In the acid-decomposable resin, a compound of the general formula (I
The content of the repeating unit represented by II) is preferably from 2 to 80 mol%, more preferably from 4 to 70 mol%, and still more preferably from 6 to 60 mol%, based on all the repeating structural units. The content of the repeating unit having an acid-decomposable group, including the case where the repeating unit of the formula (I) or (III) has an acid-decomposable group, is preferably from 15 to 90 mol% of all the repeating structural units, and more preferably. Is from 15 to 85 mol%, more preferably from 20 to 80 mol%.

The acid-decomposable resin used in the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, monomer species are charged into a reaction vessel at once or in the middle of a reaction, and if necessary, a reaction solvent such as tetrahydrofuran, 1,4-dioxane, ethers such as diisopropyl ether and methyl ethyl ketone, Ketones such as methyl isobutyl ketone, ester solvents such as ethyl acetate, and further dissolved in a solvent that dissolves the composition of the present invention such as propylene glycol monomethyl ether acetate described below to make uniform, and then nitrogen, argon, etc. The polymerization is initiated by heating under an inert gas atmosphere, if necessary, using a commercially available radical initiator (such as an azo initiator or peroxide).
If desired, an initiator is added or added in portions, and after completion of the reaction, the mixture is poured into a solvent to recover a desired polymer by a method such as powder or solid recovery. Reaction concentration is 20% by weight
Or more, preferably 30% by weight or more, more preferably 40% by weight or more. Reaction temperature is 10 ° C. to 150
° C, preferably from 30 ° C to 120 ° C, more preferably from 50 to 100 ° C.

The weight average molecular weight of the resin according to the present invention is G
It is preferably 1,000 to 200,000 in terms of polystyrene by the PC method. When the weight average molecular weight is less than 1,000, heat resistance and dry etching resistance are deteriorated, so that it is not preferable. When the weight average molecular weight exceeds 200,000, developability is deteriorated and viscosity becomes extremely high, so that film forming property is deteriorated. And so on, which produces very unfavorable results. When the composition of the present invention is for ArF exposure,
It is preferable that the resin does not have an aromatic ring from the viewpoint of transparency to light.

In the positive photoresist composition for deep ultraviolet exposure according to the present invention, the amount of all the resins according to the present invention in the total composition is from 40 to 99.
It is preferably 99% by weight, more preferably 50 to 99.9.
7% by weight.

[2] (B) Compound that Generates an Acid upon Irradiation with Actinic Rays or Radiation (Photoacid Generator) The photoacid generator used in the present invention is represented by the general formula (Ia) or the general formula (I)
It is a compound represented by Ib). In the general formulas (Ia) and (IIb), R _{1 to} R ₅ each independently represent an aliphatic hydrocarbon group or an aromatic hydrocarbon group which may have a substituent. However, two of R _{1 to} R ₃ may be bonded to each other to form a ring, and R ₄ and R ₅ may be bonded to each other to form a ring. X ^- represents any one of the anion. In the above-mentioned anions, R _{6 to} R
Each ₁₀ independently represents an aliphatic hydrocarbon group. Where R
₆ and R ₇ may be bonded to each other to form a ring, and two of R _{8 to} R ₁₀ may be bonded to each other to form a ring.

The aliphatic hydrocarbon group for R _{1 to} R ₅ includes, for example, a saturated aliphatic hydrocarbon group having 1 to 15 carbon atoms, an unsaturated aliphatic hydrocarbon group, Alicyclic aliphatic hydrocarbon groups can be mentioned. As the saturated aliphatic hydrocarbon group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, se
c-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc. Examples of the hydrocarbon group include a vinyl group, a propenyl group, an allyl group, an isopropenyl group, and a butenyl group.Examples of the alicyclic aliphatic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, Examples thereof include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

The above saturated aliphatic hydrocarbon group, unsaturated aliphatic hydrocarbon group and alicyclic aliphatic hydrocarbon group may have a substituent, for example, a carboxyl group, a cyano group,
Alkyl group (preferably having 1 to 12 carbon atoms), substituted alkyl group (preferably having 1 to 12 carbon atoms), halogen atom, hydroxyl group, alkoxy group (preferably having 1 to 12 carbon atoms), acetylamide group, alkoxycarbonyl group ( Preferably 1 to 12 carbon atoms, an acyl group (preferably 1 to 1 carbon atoms)
2), a phenylthio group, a nitro group, an acyloxy group (preferably having 1 to 12 carbon atoms) and the like. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the acyloxy group include an acetoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

Examples of the aromatic hydrocarbon group represented by R _{1 to} R ₅ include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and a 9-fluorenyl group. As R _{1 to} R ₅ , a phenyl group is particularly preferred.

The aromatic hydrocarbon group may have a substituent, for example, a carboxyl group, a cyano group, an alkyl group (preferably having 1 to 12 carbon atoms), a substituted alkyl group (preferably having 1 carbon atom). To 12), a halogen atom, a hydroxyl group, an alkoxy group (preferably having 1 to 12 carbon atoms), an acetylamide group, an alkoxycarbonyl group (preferably having 1 to 12 carbon atoms), and an acyl group (preferably having 1 to 1 carbon atoms).
2), a phenylthio group, a nitro group, an acyloxy group (preferably having 1 to 12 carbon atoms) and the like. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the acyloxy group include an acetoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

As the aliphatic hydrocarbon group for R _{6 to} R ₁₀ ,
Examples thereof include a saturated aliphatic hydrocarbon group having 1 to 15 carbon atoms, an unsaturated aliphatic hydrocarbon group, and an alicyclic aliphatic hydrocarbon group which may have a substituent. Examples of the saturated aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group,
sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc. Examples of the hydrocarbon group include a vinyl group, a propenyl group, an allyl group,
Isopropenyl group, butenyl group and the like,
Examples of the alicyclic aliphatic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group. As R _{6 to} R ₁₀ , a saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms is particularly preferable.

The saturated aliphatic hydrocarbon group, unsaturated aliphatic hydrocarbon group and alicyclic aliphatic hydrocarbon group may have a further substituent, for example, a carboxyl group, a cyano group, an alkyl group Groups (preferably having 1 to 5 carbon atoms), substituted alkyl groups (preferably having 1 to 5 carbon atoms), halogen atoms,
Hydroxyl group, alkoxy group (preferably 1 to 5 carbon atoms), acetylamide group, alkoxycarbonyl group (preferably 1 to 5 carbon atoms), acyl group (preferably 1 to 5 carbon atoms)
5), nitro group, acyloxy group (preferably having 1 carbon atom)
To 5). Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group. As the substituent of the substituted alkyl group, a hydroxyl group, a halogen atom,
Examples include an alkoxy group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the acyloxy group include an acetoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.
Examples of the substituent which the saturated aliphatic hydrocarbon group, unsaturated aliphatic hydrocarbon group and alicyclic aliphatic hydrocarbon group represented by R _{6 to} R ₁₀ may have include a fluorine atom, a chlorine atom and a nitro group. , A cyano group, an alkoxycarbonyl group, an acyloxy group, an acyl group and the like are more preferable, and a fluorine atom is particularly preferable.

The ring formed by combining two members out of R _{1 to} R ₃ includes, for example, a C 3-6 carbon atom containing one sulfur atom.
Can be mentioned. Examples of the ring formed by combining R ₄ and R ₅ include a ring having 3 to 6 carbon atoms containing one iodine atom. The ring formed by the bonding of R ₆ and R ₇ is, for example, one nitrogen atom and 2
And a ring having 3 to 6 carbon atoms containing sulfur atoms. The ring formed by combining two members out of R _{8 to} R ₁₀ is, for example, a C 3-6 carbon atom containing two sulfur atoms.
Can be mentioned.

The compound represented by formula (Ia) may have a structure in which two cations are bonded via a sulfur atom.

The amount of the compound represented by formula (Ia) or (IIb) is usually in the range of 0.001 to 30% by weight based on the solid content in the composition, and is preferably Is from 0.3 to 20% by weight, more preferably from 0.5 to 20% by weight.
Used in the range of 10% by weight. If the amount is less than 0.001% by weight, the effect of the present invention may not be sufficient,
If the content is more than 30% by weight, the profile tends to deteriorate and the resolution performance tends to decrease. Formula (Ia) or Formula (II)
The compound represented by b) can be synthesized, for example, by salt exchange between a salt having a corresponding anion and a salt having a corresponding cation (for example, a sulfonium bromide salt).

Hereinafter, the compounds represented by the general formulas (Ia) and (II)
Specific examples of the compound represented by b) will be given, but the present invention is not limited thereto.

[0221]

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[0222]

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[0223]

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[0224]

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[0225]

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[0226]

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[0227]

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In the present invention, another photoacid generator may be used in combination with the compound represented by the formula (Ia) or (IIb). The addition amount of the photoacid generator which may be used in combination is usually 2000% by weight or less, preferably 1500% by weight or less, particularly preferably 1500% by weight, based on the total amount of the compound represented by the general formula (Ia) or (IIb). Is 1000% by weight or less. Photoacid generators that may be used in combination in the present invention include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, and microresists. Known light (400-20
0 nm ultraviolet light, far ultraviolet light, particularly preferably g-line, h
Ray, i-ray, KrF excimer laser beam), ArF excimer laser beam, electron beam, X-ray, molecular beam or ion beam, a compound capable of generating an acid, and a mixture thereof can be appropriately selected and used.

Other photoacid generators which may be used in combination in the present invention include, for example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts and the like, and organic halides. Compounds, organometallic / organic halides, photoacid generators having o-nitrobenzyl-type protecting groups,
Examples thereof include compounds that generate sulfonic acid upon photolysis, such as iminosulfonate, and the like, disulfone compounds, diazoketosulfones, diazodisulfone compounds, and the like. Further, a compound in which a group or a compound capable of generating an acid by such light is introduced into a main chain or a side chain of a polymer can be used.

Furthermore, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
Compounds that generate an acid by light 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 compounds capable of decomposing upon irradiation with actinic rays or radiation to generate an acid, those particularly effectively used in combination 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).

[0232]

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

[0234]

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

[0236]

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Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. R ²⁰³ , R ²⁰⁴ ,
R ²⁰⁵ each independently represents a substituted or unsubstituted alkyl group or aryl group.

Z ^- represents a counter anion, for example, B
F ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ²⁻ , Cl
_{^{O 4 -, CF 3 SO 3}} - perfluoroalkane sulfonate anion such as, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group Dyes and the like can be mentioned, but are not limited thereto.

Further, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ 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.

[0241]

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[0242]

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[0243]

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[0244]

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[0245]

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[0246]

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[0247]

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[0248]

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[0249]

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In the above, Ph represents a phenyl group.
The onium salts represented by the general formulas (PAG3) and (PAG4) are known and can be synthesized, for example, by the methods described in 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).

[0252]

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In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group.

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

[0255]

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[0256]

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[0257]

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[0258]

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[0259]

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

[0261]

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Here, R represents a linear, branched or cyclic alkyl group, or an optionally substituted aryl group. Specific examples include the following compounds, but are not limited thereto.

[0263]

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[0264]

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[3] Other Additives The positive resist composition of the present invention may further contain, if necessary, an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer, a surfactant,
A photosensitizer, an organic basic compound, a compound that promotes solubility in a developer, and the like can be contained.

The positive resist composition of the present invention preferably contains a fluorine-based and / or silicon-based surfactant. The positive resist composition of the present invention preferably contains one or more of a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom. . When the positive resist composition of the present invention contains the above-mentioned acid-decomposable resin and the above-mentioned surfactant, it is particularly effective when the line width of the pattern is smaller, and the development defects are further improved. As these surfactants, for example, JP-A-62-36663, JP-A-61-2
No. 26746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834
No., JP-A-9-54432, JP-A-9-5988, U.S. Pat.
No. 20, 5360692, 5529881, 5296330, 543
No. 6098, No. 5576143, No. 5294511, No. 5824451, and the following commercially available surfactants can be used as they are. As commercially available surfactants that can be used, for example, F-top EF301, EF303, (manufactured by Shin-Akita Kasei Co., Ltd.), Florado FC430, 431 (manufactured by Sumitomo 3M Limited), Megafac F171, F173, F176, F189, R08
(Dai Nippon Ink Co., Ltd.), Surflon S-382, SC10
1, 102, 103, 104, 105, and 106 (manufactured by Asahi Glass Co., Ltd.), and Troisol S-366 (manufactured by Troy Chemical Co., Ltd.). Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

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

Examples of the surfactant which can be used in addition to the above include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether and the like. Polyoxyethylene alkyl allyl ethers such as ethylene alkyl ethers, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostea Fatty acid esters such as sorbitan monosorbate, sorbitan trioleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene Nonions such as polyoxyethylene sorbitan fatty acid esters such as rubitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Surfactants and the like. The amount of these other surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention.

Preferred organic basic compounds that can be used in the present invention are compounds that are more basic than phenol. Among them, a nitrogen-containing basic compound is preferable.

[0270]

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Here, R²⁵⁰, R²⁵¹And R²⁵²Are each
Independently, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
1-6 aminoalkyl group, C1-6 hydroxy
Alkyl group or substituted or unsubstituted 6 to 20 carbon atoms
An aryl group, where R ²⁵¹And R²⁵²Are connected to each other
To form a ring.

[0272]

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(Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R
²⁵⁶ independently 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. A compound containing both a substituted or unsubstituted amino group and a ring structure containing 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 indersol, substituted or unsubstituted Pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted amino Morpholine, substituted or unsubstituted aminoalkylmorpholine and the like. 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, a cyano group It is.

Preferred specific examples of the nitrogen-containing basic compound include guanidine, 1,1-dimethylguanidine,
1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine,
-Dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-
Amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-amino Ethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) Pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-
3-methyl-1-p-tolylpyrazole, pyrazine, 2
-(Aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-
Aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4.3.0] nona
5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2]
Octane, 2,4,5-triphenylimidazole, N
-Methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethylthiourea (CHMET
U) and other tertiary morpholine derivatives, JP-A-11-5257
No. 5 hindered amines (for example, those described in the gazette [0005]) and the like, but are not limited thereto.

Particularly preferred specific examples are 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2] Tertiary morpholines such as octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines, CHMETU, etc., and bis Hindered amines such as (1,2,2,6,6-pentamethyl-4-piperidyl) sebagate and the like can be mentioned. Among them, 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-
Diazabicyclo [5.4.0] undec-7-ene,
1,4-diazabicyclo [2.2.2] octane, 4-
Dimethylaminopyridine, hexamethylenetetramine,
CHMETU, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebagate is preferred.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is generally 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the total solid content of the photosensitive resin composition. If it is less than 0.001% by weight, the effect of the addition of the nitrogen-containing basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed portion tends to deteriorate.

The positive resist composition of the present invention is applied to a support by dissolving the above components in a solvent capable of dissolving the above components. As the solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone,
γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, lactic acid Ethyl, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-
Dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

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

The positive resist composition of the present invention is applied on a substrate to form a thin film. The thickness of this coating film is preferably from 0.2 to 1.2 μm. The inorganic substrate that can be used in the present invention is a normal BareSi substrate, SO
Examples of the substrate include a G substrate and a substrate having an inorganic antireflection film described below. In the present invention, a commercially available inorganic or organic antireflection film can be used, if necessary.

As the antireflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon and α-silicon, and an organic film type comprising a light absorbing agent and a polymer material can be used. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation. As the organic antireflection film, for example, Japanese Patent Publication No. 7-69
No. 611, consisting of a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin, an alkali-soluble resin, and a light absorbing agent; a reaction product of a maleic anhydride copolymer and a diamine type light absorbing agent described in US Pat. No. 5,294,680; No. 6,118,631 containing a resin binder and a methylol melamine-based thermal crosslinking agent; Japanese Patent Application Laid-Open No. 6-118656, an acrylic resin type antireflection film having a carboxylic acid group, an epoxy group and a light absorbing group in the same molecule; JP-A-8-87115, comprising a methylolmelamine and a benzophenone-based light-absorbing agent;
No. 79509 in which a low molecular weight light absorbing agent is added to a polyvinyl alcohol resin. Also, as an organic anti-reflection film, DUV3 manufactured by Brewer Science Co., Ltd.
0 series, DUV-40 series, ARC25, Shipley's AC-2, AC-3, AR19, AR20
Etc. can also be used.

The above-mentioned resist solution is coated on a substrate (eg, silicon / silicon dioxide coating) used for manufacturing precision integrated circuit devices (on a substrate provided with the above antireflection film if necessary), a spinner, a coater and the like. After coating by an appropriate coating method such as that described above, exposure through a predetermined mask, baking and development can provide a good resist pattern. Here, the exposure light is preferably 150
It is light having a wavelength of nm to 250 nm. Specifically, Kr
F excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157
nm), X-rays, electron beams and the like.

Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia;
Primary amines such as ethylamine and n-propylamine;
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 hydroxide and the like An alkaline aqueous solution such as a quaternary ammonium salt, a cyclic amine such as pyrrole, or pyrhelidine can be used. Further, an appropriate amount of an alcohol or a surfactant may be added to the alkaline aqueous solution.

[0283]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

Synthesis Example (1) Synthesis of Resin (1) Norbornene, maleic anhydride, tbutyl acrylate, and 2-methylcyclohexyl-2-propyl acrylate were charged into a reaction vessel at a molar ratio of 35/35/20/10. It was dissolved in tetrahydrofuran to prepare a solution having a solid content of 60%. This was heated at 65 ° C. under a stream of nitrogen. When the reaction temperature was stabilized, 1 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 8 hours, the reaction mixture was diluted twice with tetrahydrofuran, and then poured into 5 times the volume of hexane of the reaction mixture to precipitate a white powder. The precipitated powder was taken out by filtration, dissolved in methyl ethyl ketone, reprecipitated in a 5-fold volume hexane / t-butyl methyl ether = 1/1 mixed solvent, and the precipitated white powder was collected by filtration, dried and dried. As a result, a resin (1) was obtained. When the molecular weight analysis of the obtained resin (1) by GPC was attempted, it was found to be 121 in terms of polystyrene.
00 (weight average). From the NMR spectrum, the composition of the resin (1) was determined to be norbornene / maleic anhydride / t-butyl acrylate / 2-methylcyclohexyl-2-propyl acrylate in a molar ratio of 32/39.
/ 19/10.

In the same manner as in Synthesis Example (1), Resins (2) to (14) were synthesized. The following resin (2) to
The composition ratio and molecular weight of (14) are shown.

[0286]

[Table 1]

The structures of the resins (1) to (14) are shown below.

[0288]

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[0289]

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[0290]

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[0291]

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Synthesis Example (2) Synthesis of Resin (15) Norbornene carboxylic acid t-butyl ester, maleic anhydride, 2-methyl-2-adamantyl acrylate, norbornene lactone acrylate in a molar ratio of 20/20.
/ 35/25, and dissolved in a solvent of methyl ethyl ketone / tetrahydrofuran = 1/1 to obtain a solid content of 6
A 0% solution was prepared. This was heated at 65 ° C. under a stream of nitrogen. When the reaction temperature was stabilized, 3 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 12 hours, the reaction mixture was poured into 5 times the amount of hexane to precipitate a white powder. The precipitated powder was dissolved again in a solvent of methyl ethyl ketone / tetrahydrofuran = 1/1 and poured into a 5-fold amount of hexane / methyl tBu ether to precipitate a white powder, which was filtered and taken out. This operation was repeated again, and drying was performed to obtain the target resin (15). The molecular weight analysis (RI analysis) of the obtained resin (15) by GPC was attempted.
600 (weight average) and the amount of residual monomer was 0.4%. From the NMR spectrum, the composition of the resin (15) was 18/23/34/25 in a molar ratio of norbornene / maleic anhydride / 2-methyl-2-adamantyl acrylate / norbornene lactone acrylate of the present invention.

Resins (16) to (39) were synthesized in the same manner as in Synthesis Example (2). The following resin (1)
The composition ratios and molecular weights of 6) to (39) are shown.

[0294]

[Table 2]

The following resins (15) to (39)
The structure of is shown.

[0296]

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[0297]

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[0298]

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[0299]

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[0300]

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Synthesis Example (3) Synthesis of Acid Generator [Ia-1] 50 g of diphenyl sulfoxide was added to 800 mL of benzene.
And 200 g of aluminum chloride was added thereto, followed by stirring at 80 ° C. for 24 hours. After the completion of the reaction, the reaction solution was slowly poured into 2 L of ice. 400m concentrated hydrochloric acid
L was added and heated at 70 ° C. for 10 minutes. After cooling to room temperature, the reaction solution was washed with ethyl acetate and filtered. A solution prepared by dissolving 200 g of ammonium iodide in 400 mL of distilled water was added to the filtrate. The precipitated powder was collected by filtration, washed with water, washed with ethyl acetate, and dried to obtain 62 g of sulfonium iodide.
48 g of the obtained sulfonyl iodide was added to methanol 30
The solution was dissolved in 0 mL, and 32 g of silver oxide was added thereto, followed by stirring for 4 hours. The reaction solution was filtered and then reacted with bis (trifluoromethylsulfonyl) imide to recover 32 g of the desired product [Ia-1].

Synthesis Example (4) Synthesis of Photoacid Generator [IIb-1] 60 g of t-amylbenzene, 40 g of potassium iodate,
Mix 81 g of acetic anhydride and 170 mL of dichloromethane,
While cooling in an ice bath, 66.8 g of concentrated sulfuric acid was added dropwise over 2 hours. After the reaction solution was stirred as it was for 2 hours, it was stirred overnight at room temperature to complete the reaction. After completion of the reaction, distilled water (50 mL) was added dropwise to the reaction solution while cooling in an ice bath, extraction was performed, the organic layer was washed with water, sodium bicarbonate water, and water. The obtained organic layer was concentrated, and di (t-amylphenyl) was added. 4) Iodonium sulfate
0 g was obtained. By subjecting the obtained sulfate and potassium bis (trifluoromethylsulfonyl) imide to a salt exchange reaction, the target product [IIb-1] was obtained.

Examples 1 to 39 and Comparative Examples 1 and 2 (Preparation and Evaluation of Positive Resist Composition) The components shown in Tables 3 and 4 synthesized in the above Synthesis Examples were blended, and each had a solid content of 14% by weight. %, Dissolved in propylene glycol monomethyl ether acetate, and filtered through a 0.1 μm microfilter to prepare positive resist compositions of Examples 1 to 39 and Comparative Examples 1 and 2.

[0304]

[Table 3]

[0305]

[Table 4]

As the surfactant, W1: Megafac F176 (manufactured by Dainippon Ink and Chemicals, Inc.)
(Fluorine-based) W2: Megafac R08 (Dai Nippon Ink Co., Ltd.)
(Fluorine and silicone type) W3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) W4: Polyoxyethylene nonylphenyl ether W5: Troysol S-366 (Troy Chemical Corporation)
Manufactured).

As the amine, 1 represents 1,5-diazabicyclo [4.3.0] -5-nonene (DBN), and 2 represents bis (1,2,2,6,6-pentamethyl-4). −
Piperidyl) sebagate 3, tri-n-butylamine 4, triphenylimidazole 5, antipyrine 6, and 2,6-diisopropylaniline.

(Evaluation Test) First, Brewer Sci
ARC-25 manufactured by ence Co., Ltd. was coated on a silicon wafer with a spin coater at 78 nm and dried, and then the obtained positive photoresist composition solution was coated on the silicon wafer using a spin coater and dried at 150 ° C. for 90 minutes. After drying for 2 seconds, a positive photoresist film of about 0.4 μm was formed, and an ArF excimer laser stepper (I
(NA = 0.6, manufactured by SI). A heat treatment after the exposure was performed at 130 ° C. for 90 seconds, developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, and rinsed with distilled water to obtain a resist pattern profile. For these, the resolving power and the exposure margin were evaluated as follows. Tables 5 and 6 show the evaluation results.

Resolving power: Indicates the limiting resolving power at the exposure dose for reproducing a mask pattern of 0.14 μm. Exposure margin: The exposure amount for reproducing a 0.14 μm line-and-space (1/1) mask pattern is defined as the optimum exposure amount, and the exposure width for reproducing a line width of 0.14 μm ± 10% is divided by the optimum exposure amount. The value was expressed as a percentage (%). The larger the number, the smaller the line width change with respect to the change in exposure.

[0310]

[Table 5]

[0311]

[Table 6]

As is clear from the results shown in Tables 5 and 6, it can be seen that the positive resist composition of the present invention has excellent resolution and exposure margin.

[0313]

According to the present invention, a positive resist composition having excellent resolution and exposure margin can be provided. Therefore, the positive resist composition of the present invention can be suitably used for microfabrication using far ultraviolet light, particularly ArF excimer laser light.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08K 5/34 C08K 5/34 5/36 5/36 C08L 33/04 C08L 33/04 45/00 45/00 G03F 7 / 004 501 G03F 7/004 501 504 504 H01L 21/027 H01L 21/30 502R F term (reference) 2H025 AA00 AA02 AB16 AC04 AC08 AD03 BE00 BG00 CC04 CC20 FA03 FA12 FA17 4J002 BG041 BG051 BG071 EU027 BG1310 EU127 EU137 EU147 EU186 EU207 EU216 EU237 EV216 EV236 EV266 EV296 EV306 FD206 FD207 GP03 4J100 AJ02T AK32Q AL04R AL08R AL08S AL08T AM47Q AM47T AR09P AR11P BA02P BA02R BA02T BA03P BA03Q BA03S BA04P BA11P BA11P BA11P BA11P BA11P BA11P BA11P BA58T BB07Q BC04P BC07P BC07Q BC07T BC08T BC09P BC09S BC12P BC23T BC53P BC53S CA03 CA06 JA38

Claims (5)

[Claims] (1) An acid having an aliphatic cyclic hydrocarbon group (A)
Increases the dissolution rate in alkaline developer
Resin, and (B) acid by irradiation with actinic ray or radiation.
Positive resist compositions containing compounds that generate
And the resin of (A) is a resin represented by the following general formula (I).
A repeating structural unit represented by the general formula (II)
And a repeating structural unit represented by the general formula (III)
A compound having the following general formula (I)
a) or a compound represented by the general formula (IIb)
A positive resist composition comprising: Embedded imageIn the formula (I): R₁₁', R₁₂'Each independently represents a hydrogen atom,
Represents a cyano group, a halogen atom, or an alkyl group. Z '
Contains two bonded carbon atoms (C-C) and has a substituent
Group for forming an alicyclic structure optionally having
Represents Embedded imageIn the general formula (II): Z_TwoIs -O- or -N (R₄₁)-
Represents Where R₄₁Represents a hydrogen atom, a hydroxyl group, an alkyl
Group, haloalkyl group, or -OSO_Two-R₄₂Represents R
₄₂Represents an alkyl group, a haloalkyl group, a cycloalkyl group
Or a camphor residue. Embedded imageIn the general formula (III): R₉₁Is a hydrogen atom, lower alkyl
Represents a group, a halogen atom or -CN. X_FiveIs -O-,
-S-, -NR₉₃-Or -NR₉₃SO_TwoRepresents-. R
₉₃Represents a hydrogen atom, a chain or a cyclic alkyl group. B
Represents a single bond or a linking group. R₉₂Is a hydrogen atom, a chain
Or cyclic alkyl group, alkoxy group, hydroxyl group, carbo
Xy group, cyano group, -COOR₉₄Or the following general formula (I
V) represents a group represented by any of (X) to (X). R₉₄Is
Represents a hydrogen atom, or a chain or cyclic alkyl group. Embedded image-N⁺(R₉₅) (R₉₆) (R₉₇) ・ X^- (VIII) -R₉₈-A₅₀-R₉₉ (IX) -SO_ThreeR₁₀₀ (X) In the formula (IV), Ra₁, Rb₁, Rc₁, Rd₁, And
And Re₁Are each independently a hydrogen atom or a group having 1 to 4 carbon atoms.
Represents an alkyl group. m and n each independently represent an integer of 0 to 3
M + n is 2 or more and 6 or less. Formula (V-1)
In (V-4), R_1b~ R_5bIs, independently of each other, hydrogen
Atom, alkyl group, cycloalkyl group or alkenyl group
Represents R_1b~ R_5bTwo of which combine to form a ring
You may. In the formula (VII), R_1d~ R_8dIs German
In addition, it represents a hydrogen atom or an alkyl group. R_d0Is a hydrogen source
Child, chain or cyclic alkyl group, aryl group or aral
Represents a kill group. m represents an integer of 1 to 10. Equation (VII
I) Medium, R₉₅~ R₉₇Are each independently a hydrogen atom or a chain
Or a cyclic alkyl group, an alkenyl group, an aryl group, or
Represents an aralkyl group. Where R₉₅~ R ₉₇Are connected to each other
May form a non-aromatic ring or an aromatic ring. X^-Is R-S
O_Three ^-Represents R is an aliphatic hydrocarbon group or an aromatic hydrocarbon
Represents a group. In the formula (IX), R₉₈Is a single bond, alkylene
Group, arylene group or divalent group combining these
Represents A₅₀Represents any of the functional groups shown below. Embedded imageR₉₉Represents a hydrogen atom or an alkyl group. Formula (X)
Medium, R₁₀₀Is a chain or cyclic alkyl group, aryl group or
Represents an aralkyl group. Embedded image(In the above formula, R₁~ R_FiveEach independently has a substituent
Represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group
You. Where R₁~ R_ThreeAre bonded to each other to form a ring
And R_FourAnd R_FiveIs connected to each other
A ring may be formed. X^-Is any of the following anions
Represents. )(In the above formula, R₆~ R_TenEach independently has a substituent
Represents an optionally substituted aliphatic hydrocarbon group. Where R₆And R₇
May be bonded to each other to form a ring;₈
~ R_TenTwo of which may combine with each other to form a ring
No. ) 2. Z ′ in the general formula (I) contains two bonded carbon atoms (CC) and forms a bridged alicyclic structure which may have a substituent. The positive resist composition according to claim 1, wherein 3. The compound represented by the following general formula (II)
The positive resist composition according to claim 1, wherein the positive resist composition is A) or the general formula (II-B). Embedded image In the formulas (II-A) and (II-B), R ₁₃ ′ to R ₁₆ ′ each independently represent a hydrogen atom, a halogen atom, a cyano group, —COO
H, -COOR _5, is decomposed by the action of acid, -C
(= O) represents the -X-A'-R ₁₇ ', or may have a substituent alkyl or cyclic hydrocarbon group. Here, R ₅ is an alkyl group which may have a substituent,
Represents a cyclic hydrocarbon group or the following -Y group. X represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or -NHS
Representing the O ₂ NH-. A ′ represents a single bond or a divalent linking group. Also, at least two of R ₁₃ ′ to R ₁₆ ′ may combine to form a ring. n represents 0 or 1. R ₁₇ '
Is, -COOH, -COOR _5, -CN, a hydroxyl group, an alkoxy group which may have a substituent, -CO-NH-R
₆ represents a -CO-NH-SO ₂ -R ₆ or -Y group shown below. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. —Y group; (In the —Y group, R ₂₁ ′ to R ₃₀ ′ each independently represent a hydrogen atom or an alkyl group which may have a substituent. A, b
Represents 1 or 2. ) 4. The positive resist composition according to claim 1, further comprising a fluorine-based and / or silicon-based surfactant. 5. The positive resist composition according to claim 1, further comprising an organic basic compound.