JP2002323767A - Positive photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive composition which has a wide defocus latitude when ring-zone lighting is used and which hardly generates the side lobes when a pattern is formed by using a halftone phase shift mask, and moreover, to provide a positive photosensitive composition which hardly produces particles during stored with time. SOLUTION: The positive photosensitive composition contains (A) an acid producing agent which produces acids by irradiation of active rays or radiation, (B) a resin which has a monocyclic or polycyclic alicyclic hydrocarbon structure and is decomposed by the effect of acids to increase the solubility in an alkali developer, (C) a basic compound and (D) a fluorine and/or silicon-based surfactant. The acid producing agent (A) is a mixture containing at least one kind of triaryl sulfonium salt and at least one kind of compound having a phenacyl sulfonium salt structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive composition used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal and a thermal head, and other photofabrication processes. . More specifically, the present invention relates to a positive photosensitive composition suitable for use as a light source for exposure to far ultraviolet rays of 250 nm or less.

[0002]

2. Description of the Related Art A chemically amplified positive resist composition generates an acid in an exposed portion by irradiation with radiation such as far ultraviolet light.
This acid-catalyzed reaction changes the solubility of the irradiated portion and the non-irradiated portion of the active radiation in a developing solution, and is a pattern forming material for forming a pattern on a substrate.

[0003] When a KrF excimer laser is used as an exposure light source, absorption having a small absorption mainly in a 248 nm region is obtained.
High sensitivity, high resolution and good pattern are formed by using resin having poly (hydroxystyrene) as the main skeleton as a main component, and it is a better system than conventional naphthoquinonediazide / novolak resin system. ing. However, when an even shorter wavelength light source, for example, an ArF excimer laser (193 nm) is used as an exposure light source,
Since the compound having an aromatic group essentially shows large absorption in the 193 nm region, the above-mentioned chemical amplification system was not sufficient. Further, as a polymer having a small absorption in a wavelength region of 193 nm, the use of poly (meth) acrylate is described in J. Am. Va
c. Sci. Technol. , B9, 3357 (19
91). However, this polymer has a problem that resistance to dry etching generally performed in a semiconductor manufacturing process is lower than that of a conventional phenol resin having an aromatic group.

JP-A-2000-292917 discloses a mixed acid generator comprising a specific sulfonium salt (anion having 1 to 15 carbon atoms) and a triarylsulfonium salt.
JP-A No. 00-275845 discloses a combination of a triphenylsulfonium salt of perfluoroalkanesulfonic acid having 4 to 8 carbon atoms and 2-alkyl-2-adamantyl (meth) acrylate, and EP1041442A discloses a specific sulfonium salt (anion of anion). A mixed acid generator comprising a triphenylsulfonium salt or an iodonium salt of perfluoroalkanesulfonic acid having 1 to 8 carbon atoms and 4 to 8 carbon atoms is described.

In order to cope with further miniaturization of the pattern, it is common to use a modified illumination method or a phase shift mask. The line and space pattern has an annular illumination, and the contact hole has a halftone phase. Shift masks are often used. When using annular illumination, it was desired that the defocus latitude be wide. The fact that the defocus latitude is wide means that the fluctuation of the line width due to defocus is small. When a halftone phase shift mask is used, there is a problem of a side lobe in which a pattern portion is dissolved by a small amount of transmitted light, and this solution has been desired. Further, the P-hydroxystyrene-based resin used in the KrF excimer laser resist interacts with an acid generator, particularly an ionic compound such as an onium salt, and improves the solubility of the acid generator. The resin having a structure has a very high hydrophobicity, so that interaction with an ionic compound such as an onium salt is unlikely to occur, so that the solubility of the acid generator becomes low. There was a problem that it easily occurred.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a wide defocus latitude when using annular illumination, and it is difficult to generate side lobes when a pattern is formed using a halftone phase shift mask. Another object of the present invention is to provide a positive photosensitive composition and, in addition, a positive photosensitive composition in which particles are hardly generated during storage over time.

[0007]

Means for Solving the Problems The present invention is a positive photosensitive composition having the following constitution, thereby achieving the above object of the present invention.

(1) (A) an acid generator that generates an acid upon irradiation with actinic rays or radiation; (B) a monocyclic or polycyclic alicyclic hydrocarbon structure, which is decomposed by the action of an acid to form an alkali A resin which increases solubility in a developer, (C) a basic compound, and (D) a fluorine and / or silicon surfactant, and (A) an acid generator contains a triarylsulfonium salt. A positive photosensitive composition comprising a mixture containing at least one compound and at least one compound having a phenacylsulfonium salt structure. (2) The positive photosensitive composition according to (1), further comprising (E) a mixed solvent obtained by mixing a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group. (3) The basic compound (C) contains at least one compound having a structure selected from an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, and an aniline structure (1) or (2). 4. The positive photosensitive composition according to item 1. (4) (F) It further has a group which is decomposed by the action of an acid to increase the solubility in an alkali developer, and has a molecular weight of 3,000.
The positive photosensitive composition according to any one of (1) to (3), comprising the following dissolution inhibiting low molecular weight compound.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Acid Generator The acid generator used in the present invention comprises at least one triarylsulfonium salt which generates an acid upon irradiation with actinic rays or radiation and phenacylsulfonate. A mixture containing at least one compound having a sodium salt structure (hereinafter referred to as (A)
Component or acid generator).

The triarylsulfonium salt which generates an acid upon irradiation with actinic rays or radiation is a salt having triarylsulfonium as a cation. The aryl group of the triarylsulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The three aryl groups of the triarylsulfonium cation may be the same or different. Each aryl group may have an alkyl group (for example, having 1 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group as a substituent. Preferred substituents are an alkyl group having 4 or more carbon atoms and an alkoxy group having 4 or more carbon atoms, and most preferred are a t-butyl group and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted on any one of the three aryl groups, or may be substituted on all three. The substituent is preferably substituted at the p-position of the aryl group.
The anion of the triarylsulfonium salt is a sulfonic acid anion, preferably an alkanesulfonic acid anion substituted at the 1-position with a fluorine atom, or a benzenesulfonic acid substituted with an electron-withdrawing group, and more preferably a benzenesulfonic acid. To 8 perfluoroalkanesulfonic acid anions, most preferably perfluorobutanesulfonic acid anion and perfluorooctanesulfonic acid anion. By using these, the decomposition rate of the acid-decomposable group is improved, the sensitivity is excellent, and the diffusivity of the generated acid is controlled to improve the resolving power. The triarylsulfonium structure may have a plurality of triarylsulfonium structures linked to another triarylsulfonium structure via a linking group such as -S-. As the electron-withdrawing group, a fluorine atom,
Examples include a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkoxycarbonyl group, an acyloxy group, and an acyl group. Hereinafter, specific examples of the triarylsulfonium salt that can be used in the present invention are shown, but the present invention is not limited thereto.

[0011]

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[0012]

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The compound having a phenacylsulfonium salt structure capable of generating an acid upon irradiation with actinic rays or radiation includes, for example, a compound represented by the following general formula (III).

[0014]

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R _{1c to} R _5c each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. R
_6c and R _7c each independently represent a hydrogen atom, an alkyl group, or an aryl group. Rx and Ry each independently represent an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group. R _{1c to} R _7c
Any two or more of them and Rx and Ry may be bonded to each other to form a ring structure, and this ring structure may include an oxygen atom, a sulfur atom, an ester bond, and an amide bond. X ^- represents a sulfonic acid, carboxylic acid, or sulfonyl imide anions.

The alkyl group as R _{1c to} R _5c is a straight-chain,
It may be branched or cyclic, for example, having 1 to 1 carbon atoms.
10 alkyl groups, preferably linear and branched alkyl groups having 1 to 5 carbon atoms (eg, methyl, ethyl, linear or branched propyl, linear or branched butyl, linear or branched pentyl) And a cyclic alkyl group having 3 to 8 carbon atoms (e.g., cyclopentyl group, cyclohexyl group). The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, and may be, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (E.g., a methoxy group, an ethoxy group, a linear or branched propoxy group, a linear or branched butoxy group, a linear or branched pentoxy group), a cyclic alkoxy group having 3 to 8 carbon atoms (e.g., a cyclopentyloxy group,
Cyclohexyloxy group). Preferably, any one of R _{1c to} R _{5c is} a linear, branched, or cyclic alkyl group, or a linear, branched, or cyclic alkoxy group,
More preferably, the sum of the carbon numbers of R _1c to R _5c is 2 to 15. Thereby, the solvent solubility is further improved, and the generation of particles during storage is suppressed.

As the alkyl group for R _6c and R _7c , the same alkyl groups as R _{1c to} R _5c can be exemplified. Examples of the aryl group include an aryl group having 6 to 14 carbon atoms (for example, a phenyl group). The alkyl group as Rx and Ry is represented by R _1c
It can be the same as those of the alkyl group as to R _5c. 2-oxoalkyl group include a group having> C = O at the 2-position of the alkyl group as R _1c to R _5c. As the alkoxy group in the alkoxycarbonylmethyl group, those similar to the alkoxy groups for R _{1c to} R _5c can be exemplified. Examples of the group formed by combining Rx and Ry include a butylene group and a pentylene group.

The compound of the formula (III) forms a ring
The three-dimensional structure is more fixed, and the optical resolution is improved. R_1c~
R_7cWhen any two of the above combine to form a ring structure
For R_1c~ R_5cAny one of and R_6cAnd R_7c
Is bonded to form a single bond or a linking group,
Preferably, a ring is formed, and in particular, R_5cAnd R_6cOr R _7c
Is bonded to form a single bond or a linking group to form a ring
Is preferred. The linking group may have a substituent
Alkylene group and alkenylene which may have a substituent
Group, -O-, -S-, -CO-, -CONR- (R is
A hydrogen atom, an alkyl group, an acyl group), and these
And a group formed by combining two or more of
An optionally substituted alkylene group, an oxygen atom
An alkylene group containing a child or an alkylene group containing a sulfur atom
preferable. As the substituent, an alkyl group (preferably a carbon
An aryl group (preferably having 6 to 1 carbon atoms)
0, for example, a phenyl group), an acyl group (for example, having 2 carbon atoms)
To 11). Also, methylene
Group, ethylene group, propylene group, -CH_Two-O-, -C
H_TwoA linking group forming a 5- to 7-membered ring such as -S- is preferred.
, Ethylene group, -CH_Two-O-, -CH_Two-S- etc.
A linking group forming a 6-membered ring as described above is particularly preferred. 6 members
By forming a ring, the carbonyl plane and the C--S + signal
Coupling becomes more vertical, and the orbital interaction
The resolution is improved. Also, R_1c~ R_7cAnd either Rx or Ry
At any position, linked via a single bond or a linking group,
It may be a compound having two or more structures of (III).
No.

X ^- is preferably a sulfonic acid anion, more preferably an alkanesulfonic acid anion substituted at the 1-position with a fluorine atom, or benzenesulfonic acid substituted with an electron-withdrawing group. The alkane portion of the alkanesulfonic acid anion may be substituted with a substituent such as an alkoxy group (for example, having 1 to 8 carbon atoms) or a perfluoroalkoxy group (for example, having 1 to 8 carbon atoms). Examples of the electron-withdrawing group include a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, an alkoxycarbonyl group, an acyloxy group, and an acyl group.
X ⁻ is more preferably a perfluoroalkanesulfonic acid anion having 1 to 8 carbon atoms, particularly preferably a perfluorooctanesulfonic acid anion, most preferably a perfluorobutanesulfonic acid anion or a trifluoromethanesulfonic acid anion. . By using these, the decomposition rate of the acid-decomposable group is improved, the sensitivity is excellent, and the diffusivity of the generated acid is controlled to improve the resolving power. Hereinafter, specific examples of the compound having a phenacylsulfonium salt structure that can be used in the present invention are shown, but the present invention is not limited thereto.

[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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The composition of the present invention contains the above triarylsulfonium salt and phenacylsulfonium salt, and preferably satisfies the following conditions. (1) 0.4 to 4% by weight, preferably 0.8 to 3% by weight of the triarylsulfonium salt based on the total solid content in the composition.
The content is 5% by weight, more preferably 1 to 3% by weight. (2) The composition contains a phenacylsulfonium salt in an amount of 1% by weight or more, preferably 2 to 12% by weight, more preferably 3 to 8% by weight based on the total solids in the composition. (3) The total amount of the two acid generators is at least 1.1% by weight, preferably 1.5 to 12% by weight, more preferably 3 to 10% by weight, based on the total solids in the composition. I do. (1)
It is preferable that one or more conditions of (1) to (3) are satisfied, more preferably, two or more conditions of (1) to (3) are satisfied, and most preferably all of the conditions of (1) to (3) are satisfied. Is preferred. If none of these conditions is satisfied, the amount of generated acid tends to be small, and the sensitivity tends to decrease. From the viewpoint of side lobe margin, the ratio (weight ratio) of the triarylsulfonium salt to the phenacylsulfonium salt is preferably from 20/80 to 80/2.
0, more preferably 25/75 to 75/25, particularly preferably 30/70 to 70/30.

Acid-generating compound which can be used in combination other than component (A) In the present invention, in addition to component (A) as a mixture,
A compound which decomposes upon irradiation with actinic rays or radiation to generate an acid may be used in combination. The amount of the photoacid generator that can be used in combination with the component (A) of the present invention is usually 100/0 to 20/80, preferably 100/0, in molar ratio (component (a) / other acid generator). ~ 40/60, more preferably 100
/ 0 to 50/50. Such photoacid generators that can be used together are used in photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, or microresists. Known compounds that generate an acid upon irradiation with actinic rays or radiation and mixtures thereof can be appropriately selected and used.

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

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

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

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

[0032]

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

[0034]

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[0035]

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

[0037]

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

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. However, at least one is a substituted or unsubstituted alkyl group, and at least one is a substituted or unsubstituted aryl group. For example, the aryl group includes an aryl group having 6 to 14 carbon atoms, and the alkyl group includes an alkyl group having 1 to 8 carbon atoms. Preferred substituents include an aryl group, an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group,
A carboxyl group, a hydroxy group and a halogen atom, and an alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group and an alkoxycarbonyl group.

[0040] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^-, etc. perfluoroalkane sulfonate anion, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes Examples include, but are not limited to:

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

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

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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

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

[0053]

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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.

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

[0061]

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

[0063]

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Particularly preferred combined acid generators in the present invention include the following.

[0065]

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{(B) Resin whose dissolution rate in an alkaline developer is increased by the action of an acid (also referred to as "acid-decomposable resin")}

As the acid-decomposable resin (B) of the present invention, any resin may be used as long as it has a monocyclic or polycyclic alicyclic hydrocarbon structure and the dissolution rate in an alkali developing solution is increased by the action of an acid. Or any of the general formulas (pI) to (pVI)
It is preferable that the resin contains at least one selected from the group consisting of a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by and a repeating unit represented by the general formula (II-AB).

[0068]

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(Wherein R ₁₁ is a methyl group, an ethyl group, n
-Represents a propyl group, isopropyl group, n-butyl group, isobutyl group or sec-butyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. R _{12 to} R ₁₆ each independently represent a group having 1 to 4 carbon atoms;
It represents a linear or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R _{12 to} R ₁₄ , or any of R ₁₅ and R ₁₆ represents an alicyclic hydrocarbon group. R
_{17 to} R ₂₁ each independently represent a hydrogen atom, a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{17 to} R ₂₁ Represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms. R _{22 to} R ₂₅ are each independently
It represents a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{22 to} R ₂₅ represents an alicyclic hydrocarbon group. Also, R ₂₃ and R
₂₄ may combine with each other to form a ring. )

[0070]

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In the formula (II-AB), R ₁₁ ′ and R ₁₂ ′ each independently represent 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 may have a substituent and has two bonded carbon atoms (C—C).

Further, the general formula (II-AB) is more preferably the following general formula (II-A) or general formula (II-B).

[0073]

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In the formulas (II-A) and (II-B): R ₁₃ ′ to R _13
16 ′ is each independently 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. Further, 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;

[0075]

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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.)

In the general formulas (pI) to (pVI), R
The alkyl group for _{12 to} R ₂₅ represents a linear or branched alkyl group having 1 to 4 carbon atoms, which may be substituted or unsubstituted. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,
Examples include a sec-butyl group and a t-butyl group. Further, as a further substituent of the above alkyl group, one having 1 carbon atom
And 4 to 4 alkoxy groups, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxy group, alkoxycarbonyl group, nitro group and the like.

The alicyclic hydrocarbon group represented by R _{11 to} R _{25 or} the alicyclic hydrocarbon group formed by Z and a carbon atom may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The number of carbon atoms is preferably from 6 to 30, particularly preferably from 7 to 25. These alicyclic hydrocarbon groups may have a substituent. Below, the structural example of an alicyclic part among alicyclic hydrocarbon groups is shown.

[0079]

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[0080]

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[0081]

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In the present invention, preferred examples of the alicyclic moiety include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, and a cyclohexyl group. , Cycloheptyl group, cyclooctyl group,
Examples thereof include a cyclodecanyl group and a cyclododecanyl group. More preferred are an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.

Examples of the substituent of these alicyclic hydrocarbon groups include an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group and an alkoxycarbonyl group. The alkyl 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 a methyl group, an ethyl group, a propyl group, and a substituent selected from the group consisting of an isopropyl group. Represent. 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.

The above resins represented by the general formulas (pI) to (pV)
The structure represented by I) can be used for protecting an alkali-soluble group. Examples of the alkali-soluble group include various groups known in this technical field. Specific examples include a carboxylic acid group, a sulfonic acid group, a phenol group, and a thiol group, and a carboxylic acid group and a sulfonic acid group are preferable. General formula (pI) to above resin
The alkali-soluble group protected by the structure represented by (pVI) is preferably the following general formulas (pVII) to (pVII).
XI).

[0085]

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Here, R _{11 to} R ₂₅ and Z are the same as defined above. In the above resin, as the repeating unit having an alkali-soluble group protected by the structure represented by any of formulas (pI) to (pVI), a repeating unit represented by the following formula (pA) is preferable.

[0087]

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Here, R represents a hydrogen atom, a halogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of Rs may be the same or different. A is singly or two or more selected from the group consisting of a single bond, 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. Represents a combination of groups. Ra represents any one of the above formulas (pI) to (pVI).

Hereinafter, specific examples of the monomer corresponding to the repeating unit represented by formula (pA) will be shown.

[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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In the general formula (II-AB), R ₁₁ ′ and R ₁₁ ′
₁₂ ′ each independently represents 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 may have a substituent and has two bonded carbon atoms (C—C).

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

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, an acyloxy group and the like. 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 skeleton of the formed alicyclic hydrocarbon include those represented by the following structures.

[0100]

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[0101]

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Preferable bridged alicyclic hydrocarbon skeletons 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 above 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. Further, 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.

In the resin according to the present invention, the acid-decomposable group may be contained in the above-mentioned —C (＝ O) —XA′-R ₁₇ ′ or Z ′ in the general formula (II-AB) May be included as a substituent. The structure of the acid-decomposable group is -C (= O) -X ₁
-R ₀ . In the formula, R ₀ represents a tertiary alkyl group such as a t-butyl group, a t-amyl group, an isobornyl group, a 1-ethoxyethyl group, a 1-butoxyethyl group,
1-alkoxyethyl groups such as isobutoxyethyl group and 1-cyclohexyloxyethyl group, alkoxymethyl groups such as 1-methoxymethyl group and 1-ethoxymethyl group, 3
-Oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3
-Oxocyclohexyl ester group, 2-methyl-2-
An adamantyl group, a mevalonic lactone residue and the like can be mentioned. X ₁ has the same meaning as X described above.

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.
It is six linear or branched alkyl groups, 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 a 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-
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, a tetracyclododecanyl group, and the like can be given. As the ring formed by bonding at least two of R ₁₃ ′ to R ₁₆ ′, 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 can 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. The alkyl 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 selected from a methyl group, an ethyl group, a propyl group and an isopropyl group. 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.

In the resin according to the present invention, the groups decomposed by the action of an acid are represented by the general formulas (pI) to (pV).
A repeating unit having a partial structure containing an alicyclic hydrocarbon represented by I), a repeating unit represented by the general formula (II-AB), and at least one kind of a repeating unit of a copolymer component described below. Can be contained.

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

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

[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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The acid-decomposable resin of the present invention may further contain a repeating unit having a lactone structure represented by the following general formula (IV).

[0135]

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[0136] In the general formula (IV), R ₁ a represents a hydrogen atom or a methyl group. W ₁ represents a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, or a combination of two or more groups selected from the group consisting of an ester group. _{Ra 1, Rb 1, Rc 1} , Rd 1, Re 1 each independently represents 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;
Is 2 or more and 6 or less.

Examples of the alkyl group having 1 to 4 carbon atoms of Ra _{1 to} Re ₁ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a t-butyl group. Can be mentioned.

[0138] In formula (IV), the alkylene group of W _1, can be a group represented by the following formula. — [C (Rf) (Rg)] r ₁ — In the above formula, Rf and Rg 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. Good. The alkyl 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 selected from 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. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r ₁ is an integer of ₁ to 10.

Further substituents on the above alkyl group include carboxyl group, acyloxy group, cyano group, alkyl group, substituted alkyl group, halogen atom, hydroxyl group, alkoxy group, substituted alkoxy group, acetylamide group, alkoxycarbonyl group, An acyl group is exemplified. 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. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the substituent of the substituted alkoxy group include 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 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.

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

[0141]

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[0142]

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[0143]

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In the specific example of the above general formula (IV), (IV-17) to (IV-17)
(IV-36) is preferred. Further, as the structure of the general formula (IV), those having an acrylate structure are preferable from the viewpoint that edge roughness is improved.

Further, the following general formulas (V-1) to (V-4)
And a repeating unit having a group represented by any of the above.

[0146]

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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 which may have a substituent. 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, and 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, -Butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group. The cycloalkyl group in R _{1b to} R _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, a cyclooctyl group and the like. The alkenyl group in R _{1b to} R _5b is preferably an alkenyl group having 2 to 6 carbon atoms such as a vinyl group, a propenyl group, a butenyl group, and a hexenyl group. Examples of the ring formed by combining two members out of R _{1b to} R _5b 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. The general formula (V-1)
R _{1b to} R _5b in (V-4) may be connected to any of the carbon atoms constituting the cyclic skeleton.

Preferred substituents which the alkyl group, cycloalkyl group and alkenyl group may have are an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom). Atom), an acyl group having 2 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, a cyano group, a hydroxyl group, a carboxy group, an alkoxycarbonyl group having 2 to 5 carbon atoms, and a nitro group.

The repeating units having groups represented by formulas (V-1) to (V-4) include those represented by formula (II-
A) or (II-B) wherein at least one of R ₁₃ ′ to R ₁₆ ′ has a group represented by the above general formulas (V-1) to (V-4) (for example, -COOR ₅ R ₅ is a group represented by the general formula (V-
1) to (V-4)), or a repeating unit represented by the following general formula (AI).

[0151]

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In the general formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. Preferred substituents which the alkyl group of _Rb0 may have are those represented by the general formulas (V-1) to (V-1).
Preferred examples of the substituent which may be possessed by the alkyl group as R _1b in (V-4) include those exemplified above. Examples of the halogen atom for R _b0 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R
_b0 is preferably a hydrogen atom. A ′ represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or a divalent group obtained by combining these. B ₂ represents a group represented by any one of formulas (V-1) to (V-4). In A ′, examples of the combined divalent group include those represented by the following formulas.

[0153]

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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. The alkyl 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 selected from 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 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.

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

[0156]

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[0157]

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[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, the acid-decomposable resin of the present invention may further contain a repeating unit represented by the following general formula (VI).

[0164]

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In the general formula (VI), A ₆ is a single bond, an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group or an ester group, or a combination of two or more groups. Represents R _6a represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, or a halogen atom.

In formula (VI), examples of the alkylene group represented by A ₆ include groups represented by the following formula. -[C (Rnf) (Rng)] r- In the above formula, Rnf and Rng are a hydrogen atom, an alkyl group,
Represents a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, which may be the same or different. The alkyl 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 selected from 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. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r is an integer of 1 to 10. General formula (VI)
In the above, examples of the cycloalkylene group for A ₆ include those having 3 to 10 carbon atoms, and a cyclopentylene group,
Examples thereof include a cyclohexylene group and a cyclooctylene group.

The bridged alicyclic ring containing Z ₆ may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms), an alkoxycarbonyl group (preferably having 1 to 5 carbon atoms), an acyl group (eg, a formyl group and a benzoyl group), and an acyloxy group ( For example, a propylcarbonyloxy group, a benzoyloxy group), an alkyl group (preferably having 1 to 4 carbon atoms), a carboxyl group, a hydroxyl group, an alkylsulfonylsulfamoyl group (such as —CONHSO ₂ CH ₃ ) are exemplified. still,
The alkyl group as a substituent may be further substituted with a hydroxyl group, a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms), or the like.

In the general formula (VI), the oxygen atom of the ester group bonded to A ₆ may be bonded at any position of the carbon atom constituting the bridged alicyclic ring structure including Z _6. Good.

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

[0170]

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[0171]

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Further, it may contain a repeating unit having a group represented by the following formula (VII).

[0173]

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[0174] In the general formula _{(VII), R 2 c~R 4} c represents a hydrogen atom or a hydroxyl group independently. Provided that at least one of R ₂ c to R ₄ c represents a hydroxyl group.

The group represented by the general formula (VII) is preferably a dihydroxy form or a monohydroxy form, more preferably a dihydroxy form.

The repeating unit having a group represented by the general formula (VII) includes the above-mentioned general formula (II-A) or (II-
B) wherein at least one of R ₁₃ ′ to R ₁₆ ′ has a group represented by the general formula (VII) (for example, —COO
R ₅ of R ₅ represents a group represented by formulas (V-1) to (V-4)), or a repeating unit represented by the following formula (AII).

[0177]

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[0178] In formula (AII), R ₁ c represents a hydrogen atom or a methyl group. R ₂ c~R ₄ c represents a hydrogen atom or a hydroxyl group independently. Provided that at least one of R ₂ c to R ₄ c represents a hydroxyl group.

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

[0180]

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Further, it may contain a repeating unit having a group represented by the following formula (VIII).

[0182]

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[0183 general formula (VIII) in: Z ₂ is, -O- or -
N (R ₄₁ )-. Here, R ₄₁ is 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.

In the general formula (VIII), Z ₂ represents-
Represents O- or -N ( _R41 )-. Here, R ₄₁ represents 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 methyl, ethyl, propyl, isopropyl, 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.

[0186] alkyl and haloalkyl group as R ₄₁ and R _42, a cycloalkyl group or a 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, etc., an acyl group (preferably having 2 to 5 carbon atoms, for example, a formyl group, an acetyl group, etc.), 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 (VIII) include the following [I'-1] to [I'-7], but the present invention is limited to these specific examples. Not something.

[0188]

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[0189]

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The acid-decomposable resin as the component (B) is, in addition to the above-mentioned repeating structural units, dry etching resistance, suitability for a standard developing solution, substrate adhesion, 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, but are not limited to, repeating structural units corresponding to the following monomers. Thereby, the performance required for the acid-decomposable resin, in particular, (1) solubility in a coating solvent, (2) film-forming property (glass transition point),
Fine adjustment of (3) alkali developability, (4) film loss (hydrophobicity, selection of alkali-soluble group), (5) adhesion of unexposed portion to substrate, (6) dry etching resistance, etc. becomes possible. . As such monomers, for example, acrylates, methacrylates, acrylamides,
Examples thereof include compounds having one addition-polymerizable unsaturated bond selected from methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like.

Specific examples include the following monomers. Acrylic esters (preferably alkyl acrylate having an alkyl group having 1 to 10 carbon atoms): methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylic 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.

Methacrylic esters (preferably alkyl methacrylate having an alkyl group having 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,
A 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 (for example, 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;

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 the standard developer, the substrate adhesion, the resist profile, and the resolving power, heat resistance, which is a general required performance of the resist. It is set as appropriate to adjust properties, sensitivity, and the like.

Preferred embodiments of the acid-decomposable resin of the present invention include the following. (1) Those containing a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the above general formulas (pI) to (pVI) (side chain type) (2) In the general formula (II-AB) Those containing a repeating unit represented (main chain type). However, in (2), for example,
Further, the following may be mentioned. (3) Having a repeating unit represented by the general formula (II-AB), a maleic anhydride derivative and a (meth) acrylate structure (hybrid type)

In the acid-decomposable resin, the compounds represented by the general formulas (pI) to (pV)
The content of the repeating unit having a partial structure containing an alicyclic hydrocarbon represented by I) is 30 to
70 mol% is preferable, more preferably 35 to 65 mol%, and still more preferably 40 to 60 mol%. In the acid-decomposable resin, the content of the repeating unit represented by the general formula (II-AB) is preferably from 10 to 60 mol%, more preferably from 15 to 55 mol%, even more preferably from 20 to 70 mol% of all the repeating structural units. ５０50 mol%.

The content of the repeating structural unit based on the monomer of the further copolymer component in the resin can be appropriately set according to the desired resist properties. Based on the total number of moles of the repeating structural unit having a partial structure containing an alicyclic hydrocarbon represented by any one of the formulas (pI) to (pVI) and the repeating unit represented by the general formula (II-AB) It is preferably at most 99 mol%, more preferably at most 90 mol%, even more preferably at most 80 mol%. When the composition of the present invention is for ArF exposure,
From the viewpoint of transparency to ArF light, the resin preferably has no aromatic group.

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 this is reacted with a reaction solvent as necessary, for example, ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, 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, and then homogenized. Under an inert gas atmosphere, if necessary, heating is performed, and polymerization is started using a commercially available radical initiator (such as an azo initiator or a peroxide).
If desired, an initiator is added or added in portions, and after completion of the reaction, the mixture is poured into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. Reaction concentration is 20% by weight
It is preferably at least 30% by weight, more preferably at least 40% by weight. 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 from 1,000 to 200,000 in terms of polystyrene according to 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, the developability is deteriorated and the viscosity becomes extremely high, so that the film forming property is deteriorated. And so on, which produces very unfavorable results.

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.

{(C) Basic Compound} The positive photosensitive composition of the present invention preferably contains (C) a basic compound in order to reduce a change in performance over time from exposure to heating. As preferred structures, the following formulas (A) to
The structure shown by (E) can be mentioned.

[0210]

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Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵⁰ and R ²⁵¹ are bonded to each other to form a ring. Good.

[0212]

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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). 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 Examples include morpholine, substituted or unsubstituted aminoalkyl morpholine, and the like, and include mono, di, trialkylamine, substituted or unsubstituted aniline, substituted or unsubstituted piperidine, mono and diethanolamine, and the like. Preferred substituents are an amino group, 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 compounds include guanidine,
1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylamino Pyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethyl Pyridine, 4
-Aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N-
(2-aminoethyl) piperidine, 4-amino-2,
2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl -1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5
-Methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N-
(2-aminoethyl) morpholine, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 2,4,4
5-triphenylimidazole, tri (n-butyl) amine, tri (n-octyl) amine, N-phenyldiethanolamine, N-hydroxyethylpiperidine,
2,6-diisopropylaniline, N-cyclohexyl-N′-morpholinoethylthiourea and the like,
It is not limited to this.

Further preferred compounds include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted amino Examples thereof include morpholine, substituted or unsubstituted aminoalkylmorpholine, substituted or unsubstituted piperidine, and compounds having an imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, or aniline structure.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole and the like. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] noner 5-ene, and 1,8-diazabicyclo [5,4,0]. Undeca 7-en and the like. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and a sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, and tris (t-butylphenyl) sulfonium. Hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide and the like. The compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion moiety has become a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate. As the aniline compound,
Examples thereof include 2,6-diisopropylaniline and N, N-dimethylaniline. Neither is limited to the illustrated example.

These basic compounds (C) may be used alone or in combination of two or more. The amount of the basic compound (C) used is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the solid content of the photosensitive resin composition.
% By weight. If the amount is less than 0.001% by weight, the effect of the addition of the 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.

{(D) Fluorine and / or Silicon Surfactant} The positive photosensitive resin composition of the present invention comprises a fluorine and / or silicon surfactant (fluorine and silicon surfactant). Surfactant or a surfactant containing both a fluorine atom and a silicon atom), or two or more kinds. When the positive photosensitive composition of the present invention contains the surfactant (D) described above, when using an exposure light source of 250 nm or less, particularly 220 nm or less, it has good sensitivity and resolution, and has good adhesion and development defects. It is possible to provide a small number of resist patterns. These (D) surfactants include, for example, those described in
-36663, JP-A-61-226746, JP-A-61-226745,
JP-A-62-170950, JP-A-63-34540, JP-A-7-23016
No. 5, JP-A-8-62834, JP-A-9-54432, JP-A-9-598
No. 8, U.S. Pat.No. 5,405,720, No. 5360692, No. 5529881,
5296330, 5436098, 5576143, 5294511
And No. 5824451. The following commercially available surfactants can also be used as they are. As commercially available surfactants that can be used, for example, F-top EF301, EF303, (manufactured by Shin-Akita Chemical Co., Ltd.), Florad FC
430, 431 (Sumitomo 3M Limited), Mega Fuck F171,
F173, F176, F189, R08 (manufactured by Dai Nippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troysol S-366 (Troy Chemical Co., Ltd.) )) Or a silicon-based surfactant. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant.

The amount of the surfactant used is preferably 0.000 to the total amount of the positive photosensitive composition (excluding the solvent).
The content is 1 to 2% by weight, more preferably 0.001 to 1% by weight.

{(E) Organic Solvent} The photosensitive composition of the present invention is used by dissolving the above components in a predetermined organic solvent. Examples of usable organic solvents include, for example, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl Ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N -Dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like.

In the present invention, it is preferable to use, as the organic solvent, a mixed solvent obtained by mixing a solvent containing a hydroxyl group in the structure and a solvent not containing a hydroxyl group. This can reduce generation of particles during storage of the resist solution. As the solvent containing a hydroxyl group, for example,
Ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate and the like, among which propylene glycol monomethyl ether and ethyl lactate are particularly preferred preferable. Examples of the solvent containing no hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethylsulfoxide and the like. Among these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone,
γ-butyrolactone, cyclohexanone, and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, and 2-heptanone are most preferred. The mixing ratio (weight) of the solvent containing a hydroxyl group to the solvent not containing a hydroxyl group is from 1/99 to
The ratio is 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. A mixed solvent containing 50% by weight or more of a solvent containing no hydroxyl group is particularly preferable from the viewpoint of coating uniformity.

{(F) Acid-decomposable dissolution-inhibiting compound} The positive photosensitive composition of the present invention has a group which is decomposed by the action of (F) acid to increase the solubility in an alkaline developer. ,
Dissolution inhibiting low molecular weight compounds having a molecular weight of 3000 or less (hereinafter, referred to as
"(F) acid-decomposable dissolution inhibiting compound"). Proceeding of SPIE, 2724,355 (1996)
An alicyclic or aliphatic compound containing an acid-decomposable group, such as the cholic acid derivative containing an acid-decomposable group described in (1), is preferred as the acid-decomposable dissolution inhibiting compound (F). Examples of the acid-decomposable group and the alicyclic structure include the same as those described for the acid-decomposable resin. (F) The amount of the acid-decomposable dissolution-inhibiting compound to be added is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, based on the solid content of the whole positive photosensitive composition. . Specific examples of (F) the acid-decomposable dissolution inhibiting compound are shown below, but the invention is not limited thereto.

[0223]

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{(G) Alkali-Soluble Resin} The positive photoresist composition of the present invention contains (D) a resin which is insoluble in water and soluble in an alkali developing solution and which does not contain an acid-decomposable group. And thus the sensitivity is improved. In the present invention, a novolak resin having a molecular weight of about 1,000 to 20,000 and a polyhydroxystyrene derivative having a molecular weight of about 3,000 to 50,000 can be used as such a resin. However, these resins have large absorption for light having a wavelength of 250 nm or less. It is preferable to use a partially hydrogenated product or to use it in an amount of 30% by weight or less of the total resin amount. Further, a resin containing a carboxyl group as an alkali-soluble group can also be used. The resin containing a carboxyl group preferably has a monocyclic or polycyclic alicyclic hydrocarbon group for improving dry etching resistance. Specifically, a copolymer of a methacrylic acid ester having an alicyclic hydrocarbon structure and a non-acid-decomposable structure and a (meth) acrylic acid or a (meth) acrylic acid ester of an alicyclic hydrocarbon group having a terminal carboxyl group And the like.

{Other Additives} The positive photosensitive composition of the present invention may further contain, if necessary, a dye, a plasticizer, a surfactant other than the above-mentioned component (D), a photosensitizer, and a developer. And the like which promote the solubility of the compound. The compound capable of accelerating dissolution in a developer that can be used in the present invention is a low molecular compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. When it has a carboxy group, an alicyclic or aliphatic compound is preferable for the same reason as described above. The preferred addition amount of these dissolution promoting compounds is 2 to 50% by weight, more preferably 5 to 50% by weight, based on the resin which is decomposed by the action of the acid (B) and has increased solubility in an alkali developer.
30% by weight. An addition amount exceeding 50% by weight is not preferable because new development defects such as development residue deterioration and pattern deformation during development occur.

A phenol compound having a molecular weight of 1,000 or less can be prepared by those skilled in the art by referring to the methods described in, for example, JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and EP 219294. It can be easily synthesized. Specific examples of the alicyclic group having a carboxyl group or an aliphatic compound include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, and lithocholic acid, adamantanecarboxylic acid derivatives, adamantanedicarboxylic acid, cyclohexanecarboxylic acid, and cyclohexane. Examples include, but are not limited to, dicarboxylic acids.

In the present invention, a surfactant other than the (D) fluorine-based and / or silicon-based surfactant may be added. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether and the like Polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate,
Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate,
Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate, and the like. These surfactants may be added alone or in some combination.

{Method of Use} The photosensitive composition of the present invention is used by dissolving the above-mentioned components in a predetermined organic solvent, preferably in the above-mentioned mixed solvent, and coating it on a predetermined support as follows.
That is, the photosensitive composition is applied on a substrate (eg, silicon / silicon dioxide coating) such as used in the production of precision integrated circuit devices by a suitable application method such as a spinner or a coater. After coating, exposure through a predetermined mask,
Bake and develop. By doing so, a good resist pattern can be obtained. Here, the exposure light is preferably 250 nm or less, more preferably 220 nm or less.
It is far ultraviolet light having a wavelength of less than nm. Specifically, KrF
Excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 n)
m), X-rays, electron beams and the like.

In the developing step, a developing solution is used as follows. As the developer of the photosensitive composition, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as ammonia water, ethylamine, primary amines such as 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 above alkaline aqueous solution for use.

[0230]

EXAMPLES The present invention will now be described in detail with reference to examples, but the scope of the present invention is not at all limited by the examples.

<Synthesis example of acid generator> Synthesis example (1) Synthesis of acid generator (I-3) 50 g of diphenyl sulfoxide was dissolved in 800 ml of benzene, and 200 g of aluminum chloride was added thereto.
Refluxed for 4 hours. The reaction solution was slowly poured into 2 L of water, and 400 ml of concentrated sulfuric acid was added thereto, followed by heating at 70 ° C. for 10 minutes. This aqueous solution was washed with 500 ml of ethyl acetate, filtered, and then a solution prepared by dissolving 200 g of ammonium iodide in 400 ml of water was added. The precipitated powder was collected by filtration, washed with water, washed with ethyl acetate and dried to obtain 70 g of triphenylsulfonium iodide. 17.6 g of triphenylsulfonium iodide was dissolved in 1000 ml of methanol, and 12.5 g of silver oxide was added to this solution.
Stirred for hours. The solution was filtered, and to this was added 25 g of a solution of perfluoro-n-octanesulfonic acid in methanol.
The reaction solution was concentrated, and the precipitated oil was dissolved in ethyl acetate, washed with water, dried and concentrated to obtain 20.5 g of the desired product.

Synthesis Example (2) Synthesis of Acid Generator (I-5) Di (t-butylphenyl) sulfide (80 mmol)
l), a mixture of di (t-butylphenyl) iodonium perfluoro-n-butanesulfonate (20 mmol) and copper benzoate (4 mmol) was added at 130 ° C. under a nitrogen stream at 4 ° C.
Stirred for hours. The reaction solution was allowed to cool, and ethanol 10
0 ml was added to remove precipitates. The filtrate was concentrated, and 200 ml of ether was added thereto to precipitate a powder. The powder was collected by filtration, washed with ether, and dried to obtain the desired product.

Triphenylsulfonium perfluorobutanesulfonate and triphenylsulfonium triflate were manufactured by Midori Kagaku. Other acid generators (I) were
Synthesized by the same method as above.

Synthesis Example (3): Phenacyltetrahydrothiophenium perfluorobutanesulfonate (III-
Synthesis of 1) 53.2 g of tetrahydrothiophene was added to acetonitrile 4
Of phenacyl bromide 1
A solution prepared by dissolving 00 g in acetonitrile (300 ml) was slowly added. After stirring at room temperature for 3 hours, powder was deposited. The reaction solution was poured into 1500 ml of ethyl acetate, and the powder was collected by filtration and dried to obtain 137 g of phenacyltetrahydrothiophenium bromide. 60 g of potassium perfluorobutanesulfonate was added to 200 ml of water and 200 m of methanol.
of phenacyltetrahydrothiophenium bromide dissolved in 300 ml of water. This aqueous solution is mixed with chloroform 2
The mixture was extracted twice with 00 ml, and the organic phase was washed with water and concentrated to obtain a crude product. 300 ml of distilled water is added to this and 10
After heating at 0 ° C. for 30 minutes and cooling, a solid precipitated. The solid was collected by filtration and reslurried with diisopropyl ether to obtain 77 g of phenacyltetrahydrothiophenium perfluorobutanesulfonate.

Synthesis Example (4): Phenacyltetrahydrothiophenium perfluorooctanesulfonate (III
Synthesis of -3) Phenacyltetrahydrothiophenium bromide was synthesized by performing salt exchange with perfluorooctanesulfonic acid by performing the same operation as described above. Synthesis Example (5): Synthesis of phenacyltetrahydrothiophenium trifluoromethanesulfonate (III-2) By subjecting phenacyltetrahydrothiophenium bromide to salt exchange with trifluoromethanesulfonic acid by performing the same operation as described above. Synthesized. Other compounds were also synthesized by reacting the corresponding phenacylhalogenide with a sulfide compound to synthesize phenacylsulfonium halogenide, followed by salt exchange with sulfonic acid (salt).

<Synthesis example of resin> Synthesis example (1) Synthesis of resin (1) (side chain type) 2-ethyl-2-adamantyl methacrylate and butyrolactone methacrylate were charged at a ratio of 55/45, and methyl ethyl ketone / tetrahydrofuran = 5/45. 5 to prepare 100 mL of a 20% solids solution. To this solution, 2 mol% of V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added, and this was added dropwise to 10 mL of methyl ethyl ketone heated to 60 ° C. over 4 hours under a nitrogen atmosphere. After the addition was completed, the reaction solution was heated for 4 hours, 1 mol% of V-65 was added again, and the mixture was stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and 3 L of a mixed solvent of distilled water / ISO propyl alcohol = 1/1 was used.
The resin (1) as a white powder crystallized and precipitated was recovered. The polymer composition ratio determined from C ¹³ NMR was 46/54.
Met. The weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 10,700.

Resins (2) to (15) were synthesized in the same manner as in Synthesis Example (1). The following resin (2) to
The composition ratio and molecular weight of (15) are shown. (Repeat unit 1,
2, 3, and 4 are the order from the left of the structural formula. )

[0238]

[Table 1]

The structures of the resins (1) to (15) are shown below.

[0240]

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[0241]

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[0242]

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[0243]

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Synthesis Example (2) Synthesis of Resin (16) (Main Chain Type) Norbornene carboxylic acid t-butyl ester, norbornene carboxylic acid butyrolactone ester and maleic anhydride (molar ratio 40/10/50) and THF (reaction temperature 6)
0% by weight) was placed in a separable flask and heated at 60 ° C. under a nitrogen stream. When the reaction temperature was stabilized, 2 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. Heat for 12 hours. After diluting the obtained reaction mixture twice with tetrahydrofuran, hexane /
It was poured into a mixed solution of isopropyl alcohol = 1/1 to precipitate a white powder. Filter out the precipitated powder,
Drying yielded the desired resin (16). When the molecular weight analysis of the obtained resin (16) by GPC was attempted, it was 8300 (weight average) in terms of polystyrene. From the NMR spectrum, it was confirmed that the molar ratio of norbornene carboxylic acid t-butyl ester / norbornene carboxylic acid butyrolactone ester / maleic anhydride repeating unit of the resin (1) was 42/8/50.

Resins (17) to (27) were synthesized in the same manner as in Synthesis Example (2). The following resin (1)
The composition ratios and molecular weights of 7) to (27) are shown. (Alicyclic olefin units 1, 2, and 3 are in order from the left in the structural formula.)

[0246]

[Table 2]

The following resins (16) to (27)
The structure of is shown.

[0248]

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[0249]

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Synthesis Example (3) Synthesis of Resin (28) (Hybrid Type) Norbornene, maleic anhydride, t-butyl acrylate, 2-methylcyclohexyl-2-propyl acrylate was reacted at a molar ratio of 35/35/20/10. The solution was charged in a container and 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 (28) was obtained. When the molecular weight analysis of the obtained resin (28) by GPC was tried, it was 1 in terms of polystyrene.
2,100 (weight average). From the NMR spectrum, the composition of the resin (1) was as follows: norbornene / maleic anhydride / t-butyl acrylate / 2-methylcyclohexyl-2-propyl acrylate of the present invention in a molar ratio of 32 /
39/19/10.

In the same manner as in Synthesis Example (3), Resins (29) to (41) were synthesized. The following resin (2)
The composition ratios and molecular weights of 9) to (41) are shown.

[0252]

[Table 3]

The following resins (28) to (41)
The structure of is shown.

[0254]

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[0255]

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[0256]

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[0257]

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Synthesis Example (4) Synthesis of Resin (42) (Hybrid Type) 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, dissolve in methyl ethyl ketone / tetrahydrofuran = 1/1 solvent, solid content 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 to obtain the desired resin (42) by drying. When the molecular weight analysis (RI analysis) of the obtained resin (42) by GPC was attempted, it was 11 in terms of polystyrene.
600 (weight average), the amount of residual monomer was 0.4%. From the NMR spectrum, the composition of the resin (1) was found to be the norbornene / maleic anhydride / 2-methyl-
The molar ratio of 2-adamantyl acrylate / norbornene lactone acrylate was 18/23/34/25.

In the same manner as in Synthesis Example (4), Resins (43) to (66) were synthesized. The following resin (4)
The composition ratios and molecular weights of 3) to (66) are shown.

[0260]

[Table 4]

The following resins (42) to (66)
The structure of is shown.

[0262]

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[0263]

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[0264]

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[0265]

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[0266]

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<Preparation of Resist> [Examples 1 to 80 and Comparative Examples 1 to 4] The materials shown in Tables 5 to 8 were dissolved to prepare a solution having a solid content of 12% by weight, and this was then dissolved in Teflon (0.1 μm). (Registered trademark) filter to prepare a photosensitive composition. The prepared compositions were evaluated by the following methods, and the results are shown in Tables 9 to 12.

[0268]

[Table 5]

[0269]

[Table 6]

[0270]

[Table 7]

[0271]

[Table 8]

The abbreviations in Tables 5 to 8 are as follows. DBN; 1,5-diazabicyclo [4.3.0] nona-
5-ene TPI; 2,4,5-triphenylimidazole TPSA; triphenylsulfonium acetate HEP; N-hydroxyethylpiperidine DIA; 2,6-diisopropylaniline DCMA; dicyclohexylmethylamine LCB; t-butyl lithocholic acid

W-1: Megafax F176 (Dainippon Ink Co., Ltd.) (fluorine) W-2: Megafax R08 (Dainippon Ink Co., Ltd.)
(Fluorine and silicon type) W-3; Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon type) W-4; Troysol S-366 (Troy Chemical Co., Ltd.)
Made)

The abbreviations for the solvents are as follows. In addition, the ratio in the case of multiple use in Tables 5-8 is a weight ratio. A1: propylene glycol methyl ether acetate A2; 2-heptanone A3; ethyl ethoxypropionate A4; γ-butyrolactone A5; cyclohexanone A6; butyl acetate B1: propylene glycol methyl ether B2; ethyl lactate

<Image Evaluation Method> (1) DOF (Defocus Latitude) Evaluation An antireflection film ARC25 manufactured by Brewer Science Co. was uniformly applied on a silicon substrate that had been subjected to hexamethyldisilazane treatment by a spin coater to 600 angstroms. After drying on a hot plate at 100 ° C. for 90 seconds, heat drying was performed at 190 ° C. for 240 seconds. afterwards,
Each photosensitive composition was applied by a spin coater,
Drying was performed for 0 seconds to form a 0.40 μm resist film. The resist film is passed through a mask through an ArF excimer laser stepper (NA = 0.6 (σ, manufactured by ISI)).
= 0.75, 2/3 annular illumination)) and heated on a hot plate at 140 ° C. for 90 seconds immediately after exposure. Further, the resist was developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and dried to obtain a resist line pattern. A 0.13 μm defocus latitude at an exposure amount that reproduces a 0.13 μm line and space (1/1) was observed.

(2) Evaluation of Sidelobe Margin An antireflection film ARC25 manufactured by Brewer Science Co. was uniformly applied on a silicon substrate that had been subjected to hexamethyldisilazane treatment with a spin coater at 600 Å, and was placed on a hot plate at 100 ° C. for 90 seconds. , And heat-dried at 190 ° C. for 240 seconds. afterwards,
Each photosensitive composition was applied by a spin coater and was applied at 140 ° C for 9 hours.
Drying was performed for 0 seconds to form a 0.40 μm resist film. The resist film is exposed with an ArF excimer laser stepper (NA = 0.6, manufactured by ISI) using a halftone phase shift mask having a transmittance of 6%, and immediately after exposure, heated on a hot plate at 140 ° C. for 90 seconds. did. Further, the film was developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and then dried to obtain a contact hole pattern. Duty ratio 1: 2, mask size 0.20
The exposure amount for opening a contact hole having a dimension of 0.18 μm is defined as the optimal exposure amount Eop, and the relationship with the exposure amount Es at which side lobes occur when over-exposure is performed from the optimal exposure amount is calculated by the following equation. The lye lobe margin was used. A higher value indicates higher sidelobe resistance. Side lobe margin (%) = [(Es−Eop) / E
op] × 100

(3) Evaluation of Particles After the prepared photosensitive composition was allowed to stand at 4 ° C. for one week, the number of particles having a particle diameter of 0.2 μm or more present in the solution was counted using a particle counter manufactured by Rion.

[0278]

[Table 9]

[0279]

[Table 10]

[0280]

[Table 11]

[0281]

[Table 12]

The following is clear from the results shown in Tables 9 to 12. The compositions of Examples 1 to 80 have a wide defocus latitude, excellent side lobe resistance, and hardly generate particles. On the other hand, the compositions of Comparative Examples 1 to 4 are inferior to the compositions of Examples in defocus latitude, sidelobe resistance, and generation of particles.

[0283]

The positive photosensitive composition according to the present invention comprises:
The defocus latitude is wide when ring-shaped illumination is used, side lobes are hardly generated when a pattern is formed using a halftone phase shift mask, and particles are hardly generated when stored over time.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 503 G03F 7/004 503A 504 504 H01L 21/027 H01L 21/30 502R F-term (Reference) 2H025 AB16 AB17 AC04 AC08 AD03 BE00 BE07 BE10 BG00 CC03 CC04 CC20 FA03 FA12 FA17 4J002 BG031 BG071 BK001 EJ019 EL099 EN067 ER027 EU047 EU077 EU117 EU137 EU186 EU226 EV296 FD318 GP03

Claims (4)

[Claims] (A) an acid generator which generates an acid upon irradiation with actinic rays or radiation, (B) a monocyclic or polycyclic alicyclic hydrocarbon structure, which is decomposed by the action of an acid to develop an alkali A resin having increased solubility in a liquid, (C) a basic compound,
And (D) a fluorine- and / or silicon-based surfactant, and (A) the acid generator contains at least one triarylsulfonium salt and at least one compound having a phenacylsulfonium salt structure. A positive photosensitive composition, which is a mixture comprising: 2. The positive photosensitive composition according to claim 1, comprising (E) a mixed solvent obtained by mixing a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group. (C) the basic compound is an imidazole structure, a diazabicyclo structure, an onium hydroxide structure,
The positive photosensitive composition according to claim 1, comprising at least one compound having a structure selected from an onium carboxylate structure and an aniline structure. 4. The composition according to claim 1, further comprising (F) a dissolution inhibiting low molecular weight compound having a group capable of decomposing under the action of an acid to increase solubility in an alkaline developer and having a molecular weight of 3000 or less. Item 4. The positive photosensitive composition according to any one of Items 1 to 3.