JP2002255930A - Optically acid-generating compound and positive-working photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound useful for a chemical amplification-type image-forming material and to provide a chemical amplification-type positive- working photoresist composition having high sensitivity and high resolution, having good adhesiveness to a substrate, and improved in edge roughness of a pattern. SOLUTION: This new compound comprises a specified onium salt compound. The chemical amplification-type positive-working photoresist composition contains the onium salt compound and a resin which is decomposed by the action of the onium salt compound and a specific acid so that its solubility in an alkali is increased.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel compound capable of generating an acid upon irradiation with actinic rays or radiation, in particular
The present invention relates to a novel acid-generating compound having high light transmittance in a far ultraviolet region of not more than nm and high acid generation efficiency by photolysis. Further, the present invention relates to a positive resist composition used in a super microlithography process such as the production of a super LSI and a high capacity micro chip, and other photofabrication processes. More specifically, a deep ultraviolet region including excimer laser light, particularly 250 nm
The present invention relates to a positive resist composition capable of forming a high-definition pattern using light having the following wavelengths.

[0002]

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

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

The above-mentioned chemically amplified resist is suitable for a photoresist for irradiating ultraviolet rays or far ultraviolet rays, but among them, it is necessary to further meet the required characteristics in use. As a photoresist composition for an ArF light source, a resin into which an alicyclic hydrocarbon site has been introduced for the purpose of imparting dry etching resistance has been proposed. As such a resin, a monomer having a carboxylic acid moiety such as acrylic acid or methacrylic acid or a monomer having a hydroxyl group or a cyano group in a molecule is copolymerized with a monomer having an alicyclic hydrocarbon group. Resin.

On the other hand, besides the method of introducing an alicyclic hydrocarbon moiety into the side chain of the acrylate monomer, a method of imparting dry etching resistance utilizing an alicyclic hydrocarbon moiety as a polymer main chain has also been studied. ing. In addition, Japanese Patent Application Laid-Open
-73173, JP-A-9-90637 and JP-A-10
JP-A-161313 discloses the use of an alkali-soluble group protected by a structure containing an alicyclic group, and an acid-sensitive compound containing a structural unit capable of leaving the alkali-soluble group with an acid to render it alkali-soluble. Resist material is described. Further, a resin in which a hydrophilic 5- or 6-membered lactone group is introduced into the resin having an alicyclic group for the purpose of improving the affinity for an alkali developing solution and the adhesion to a substrate is disclosed in JP-A-9-90637, JP-A-10-20769, JP-A-10-274852
And JP-A-10-239846. Even with the techniques described above, in photoresist compositions (particularly photoresists for deep ultraviolet exposure), there are still improvements due to resins containing acid-decomposable groups, and further improvements in sensitivity, resolution, and molecular There are still many insufficient points such as improvement in adhesion to a substrate due to simultaneous inclusion of an aliphatic cyclic hydrocarbon group therein, and improvement is desired.

Further, in recent years, with the demand for miniaturization of semiconductor chips, the fine semiconductor design pattern has been reduced to 0.13.
It reaches a fine region of about 0.35 μm. However, these compositions have a problem that the resolution of the pattern is hindered by factors such as the edge roughness of the line pattern. Here, the edge roughness refers to when the pattern is viewed from directly above because the top and bottom edges of the resist line pattern fluctuate irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. Means that the edge looks uneven.

As one of the methods for reducing the edge roughness, it is effective to increase the amount of the photoacid generator to be added, but at the same time, the light transmittance of the resist film is reduced, so that the pattern profile becomes tapered. Problems arise. To achieve both edge roughness and pattern profile, it is effective to use an acid generator that is transparent to exposure light. 220nm
Examples of the following light-transparent acid generators are disclosed in
-28846, JP-A-7-28237, JP-A-7-28
92675, JP-A-8-27102, JP-A-10-
13371 and compounds described in JP-A-11-228534. However, an acid generator that is transparent to exposure light, on the other hand, has a problem in that the efficiency of acid generation by a photoreaction, that is, the sensitivity, is reduced because the absorption efficiency of exposure light is reduced. Therefore, development of an acid generator which is transparent to exposure light and has a higher acid generation efficiency is desired.

[0008]

As described above, according to the known techniques of the conventional photoresist composition, sensitivity, resolution,
Since the adhesion to the substrate does not meet the recent required performance, the edge of the pattern has roughness, and a stable pattern cannot be obtained. Therefore, further improvement has been desired. Accordingly, an object of the present invention is to provide a structure having a thickness of 220 nm or less, particularly, A
An object of the present invention is to provide a compound having high transmittance at 193 nm of rF excimer laser light and high acid generation efficiency. Further, an object of the present invention is to provide a chemically amplified positive resist composition having high sensitivity, high resolution, good adhesion to a substrate, and improved pattern edge roughness by using this compound. Is to provide.

[0009]

Means for Solving the Problems The present inventors diligently studied the structure of an acid-generating compound, and as a result, found a compound having a specific structure and used a resist composition using the compound. It was found that the object of the present invention for improving the resist performance was achieved, and the present invention was achieved. That is, the above object is achieved by the following compounds and the following constitutions.

(1) Formula (Ia) or (Ib)
A compound represented by the formula:

[0011]

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In the formula, R ₁ and R ₂ may be the same or different and each represents an alkyl group, a haloalkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group which may have a substituent. , R ₃ and R ₄ may be the same or different, and may be a hydrogen atom, which may have a substituent, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an acyl group, alkoxycarbonyl group, a halogen atom, a -S-R _5.
However, at least one of R ₃ and R ₄ is a group other than a hydrogen atom. R ₅ represents an alkyl group, a haloalkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or an aralkyl group which may have a substituent. R ₆ and R ₇ may be the same or different, and may be a hydrogen atom, which may have a substituent, an alkyl group, a haloalkyl group, a cycloalkyl group,
Alkenyl group, aryl group, aralkyl group, acyl group,
An alkoxycarbonyl group, an -S-R _5. R ₈ , R ₉
May be the same or different and represent a hydrogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an acyl group, or an alkoxycarbonyl group which may have a substituent. R ₁₀ represents an alkyl group, a haloalkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an -O-R _5. n shows 0 or the integer of 1-3. The general formula (I-
two of R ₁ to R ₅ in a), R ₁ and of (I-b) ~R
Two of the _ten may combine to form a ring. X ^- represents an anion of a sulfonic acid.

(2) (A) The above-mentioned general formula (Ia) or (I-) which generates an acid upon irradiation with actinic rays or radiation.
a positive resist comprising: a compound represented by b); and (B) a resin having an alicyclic group and an acid-decomposable group, and decomposed by the action of an acid to increase solubility in alkali. Composition.

(3) The resin of (B) is represented by the following general formula (p)
(2) The above-mentioned (2), which contains a repeating unit having an alkali-soluble group protected by at least one of the groups having an alicyclic hydrocarbon structure represented by (I) to (pVI). 4. The positive resist composition according to item 1.

[0015]

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In the general formulas (pI) to (pVI), R ₁₁ is
Represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. Represents R _{12 to} R ₁₆ each independently represent a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that R _{12 to} R ₁₄
And at least one of R ₁₅ and R ₁₆ represents an alicyclic hydrocarbon group. R ₁₇ to R ₂₁ each independently represent a hydrogen atom, 1 to 4 carbon atoms, a straight-chain or branched alkyl group or an alicyclic hydrocarbon group, provided that, R ₁₇
At least one of to R ₂₁ represents an alicyclic hydrocarbon group. Further, any one of R ₁₉ and R ₂₁ has 1 to 4 carbon atoms,
Represents a linear or branched alkyl group or an alicyclic hydrocarbon group. R _{22 to} R ₂₅ each independently represent 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 is an aliphatic group; Represents a cyclic hydrocarbon group.

(4) The general formulas (pI) to (pVI)
The positive resist composition according to the above (3), wherein the group having an alicyclic hydrocarbon structure represented by the following formula (II) or (III):

[0018]

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In the formula, R _{26 to} R ₂₈ may be the same or different and represent an alkyl group which may have a substituent.
R _{29 to} R ₃₁ may be the same or different, and may have a hydroxy group, a halogen atom, a carboxy group, or a substituent; an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group; Or an acyl group. p, q, and r are each independently 0 or 1
Represents an integer of 1 to 3.

(5) The positive type resin according to any one of the above (2) to (4), wherein the resin (B) contains a repeating unit represented by the following general formula (a). Resist composition.

[0021]

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In the general formula (a), R represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. R ₃₂ to R ₃₄ may be the same or different, represent a hydrogen atom or a hydroxyl group. At least one of R ₃₂ to R ₃₄ represents a hydroxyl group.

(6) The resin (B) contains a repeating unit having a group represented by at least one of the following general formulas (IV) to (VII). The positive resist composition according to any one of (5).

[0024]

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In the formula, R _{35 to} R ₃₉ may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. R ₃₅
Two of to R ₃₉ may be bonded to form a ring.

Preferred embodiments will be described below. (7) The positive resist composition as described in any of (2) to (6) above, further comprising (C) an acid diffusion inhibitor. (8) In addition to the compound of (A), a compound of the general formula (Ia)
Or a positive type according to any one of the above (2) to (7), further comprising (A ′) other than the general formula (Ib), a compound which generates an acid upon irradiation with actinic rays or radiation. Resist composition.

(9) The positive resist composition as described in (8) above, wherein the compound (A ′) is a sulfonium or iodonium sulfonate compound. (10) The positive resist composition as described in (8) above, wherein the compound (A ′) is a sulfonate compound of N-hydroxyimide. (11) The above (2) to (10), wherein far-ultraviolet light of 150 nm to 220 nm is used as the exposure light.
A positive resist composition according to any one of the above.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compound of the present invention will be described in detail. [1] A compound represented by the general formula (Ia) or (Ib) and capable of generating an acid upon irradiation with actinic rays or radiation The acid-generating compound of the present invention is far ultraviolet light having a wavelength of 220 nm or less, particularly It is a sulfonium salt compound having a small absorption at 193 nm light. Structurally, it is preferable that the number of aryl groups, aralkyl groups, aromatic groups based on alkenyl groups, and olefin structures in the molecule of the cation portion be two or less,
More preferably, it is a compound having no or only one. In addition, such a sulfonium salt imparts highly efficient photoreactivity and further secures stability over time, so that an electron-withdrawing group at the α-position of the sulfonium group, preferably an α-substituted ester group, or a lactone is used. Substituting groups is effective. That is, the compound of the present invention has the general formula (Ia)
Or a compound represented by (Ib).

[0029]

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In the formula, R ₁ and R ₂ may be the same or different and each represents an alkyl group, a haloalkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group which may have a substituent. , R ₃ and R ₄ may be the same or different, and may be a hydrogen atom, which may have a substituent, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an acyl group, alkoxycarbonyl group, a halogen atom, a -S-R _5.
However, at least one of R ₃ and R ₄ is a group other than a hydrogen atom. R ₅ represents an alkyl group, a haloalkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or an aralkyl group which may have a substituent. R ₆ and R ₇ may be the same or different, and may be a hydrogen atom, which may have a substituent, an alkyl group, a haloalkyl group, a cycloalkyl group,
Alkenyl group, aryl group, aralkyl group, acyl group,
An alkoxycarbonyl group, an -S-R _5. R ₈ , R ₉
May be the same or different and represent a hydrogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an acyl group, or an alkoxycarbonyl group which may have a substituent. R ₁₀ represents an alkyl group, a haloalkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an -O-R _5. n shows 0 or the integer of 1-3. In addition, the general formula (I-
two of R ₁ to R ₅ in a), R ₁ and of (I-b) ~R
Two of the _ten may combine to form a ring. X ^- represents an anion of a sulfonic acid.

As described above, the general formulas (Ia) and (I-
In the cation portion in b), the total number of aromatic groups and olefin groups in R _{1 to} R ₁₀ is preferably 2 or less, more preferably 1 or 0. The number of aromatic groups and olefin groups is preferably 3 or less in the entire compound represented by the general formula (Ia) or (Ib), including the anion portion.

Here, as the alkyl group of R _{1 to} R ₁₀ ,
For example, an alkyl group having 1 to 12 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group,
Preferable examples include a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a decyl group, and a dodecyl group. The haloalkyl group of R _{1 to} R ₁₀ is preferably an alkyl group having 1 to 8 carbon atoms substituted by a fluorine atom, a chlorine atom or a bromine atom, for example, a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a bromomethyl group , Fluoroethyl, pentafluoroethyl, chloroethyl, bromoethyl, fluoropropyl, heptafluoropropyl, chloropropyl, bromopropyl, fluorobutyl, nonafluorobutyl,
Examples thereof include a chlorobutyl group and a bromobutyl group. R ₁
The cycloalkyl group of ~ R ₁₀ may be monocyclic,
It may be polycyclic. Preferred examples of the monocyclic type include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group each having 3 to 8 carbon atoms. Preferred examples of the polycyclic type include an adamantyl group, a norbornyl group, an isobornyl group, a dicyclopentyl group, an a-pinel group, and a tricyclodecanyl group.

The alkenyl group represented by R _{1 to} R ₁₀ is, for example, an alkenyl group having 2 to 8 carbon atoms, and specific examples thereof include a vinyl group, an allyl group, a butenyl group and a cyclohexenyl group. it can. The aryl group of R _{1 to} R ₁₀ is, for example, an aryl group having 6 to 15 carbon atoms, and specifically, a phenyl group, a tolyl group, a dimethylphenyl group, a 2,4,6-trimethylphenyl group, A naphthyl group, an anthryl group and the like can be preferably mentioned. The aralkyl group for R _{1 to} R ₁₀ is, for example, an aralkyl group having 7 to 12 carbon atoms, and specific examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

As the halogen atom for R ₃ and R _4, a fluorine atom, a chlorine atom, a bromine atom and the like can be preferably exemplified. As the acyl group for R ₃ , R ₄ and R _{6 to} R ₉ ,
For example, it is an acyl group having 2 to 10 carbon atoms, and specific preferred examples include an acetyl group, a propanoyl group, a butanoyl group and a pivaloyl group. R ₃ , R ₄ , R
The alkoxycarbonyl group of _{6 to} R ₉ is, for example, an alkoxycarbonyl group having 2 to 10 carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group,
Preferable examples include a propoxycarbonyl group, a hexyloxycarbonyl group, a cyclohexylcarbonyl group, and a 2-ethylhexylcarbonyl group.

The ring formed by bonding two of R _{1 to} R ₅ of (Ia) and two of R _{1 to} R ₁₀ of (Ib) is preferably 3 to An 8-membered ring, specifically a ring in which a sulfur atom on a 5-membered tetrahydrothiophene ring is a cation, a ring in which one sulfur atom on a 5-membered dithiolane ring is a cation, or a 6-membered ring Ring in which the sulfur atom on the thiane ring has become a cation, and 1 on the 6-membered dithiane ring
A ring in which two sulfur atoms have become cations, a β-lactone ring,
γ-lactone ring, δ-lactone ring, ε-caprolactone ring, cyclobutane ring, cyclohexane ring and the like.

The substituents substituted on these groups include those having active hydrogen such as amino group, amide group, ureido group, urethane group, hydroxyl group, carboxyl group and the like, and halogen atoms (fluorine atom, chlorine atom , A bromine atom, an iodine atom), an alkoxy group (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an octyloxy group, etc.), a thioether group, an acyl group (an acetyl group, a propanoyl group, a pivaloyl group, etc.), and an acyloxy group (acetoxy group) Group, propanoyloxy group, pivaloyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, etc.), cyano group, nitro group and the like.

[0037] X ^- represents an anion of a sulfonic acid. Specifically, an alkyl sulfonic acid which may have a substituent,
Cycloalkyl sulfonic acid, perfluoroalkyl sulfonic acid, aryl sulfonic acid (for example, optionally substituted benzene sulfonic acid, naphthalene sulfonic acid,
Anions such as anthracenesulfonic acid). Preferred substituents for substituting these groups include an alkyl group (methyl group, ethyl group, i-propyl group, t-butyl group, etc.), a haloalkyl group (fluoromethyl group, chloromethyl group, bromomethyl group, trifluoromethyl group, Methyl group, pentafluoroethyl group, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, octyloxy group, etc.), amino group, amide group, ureido group, urethane group, hydroxyl group, carboxyl group, halogen Atoms (fluorine, chlorine, bromine,
Iodine atom), thioether group, acyl group (acetyl group,
Propanoyl group, pivaloyl group, etc.), acyloxy group (acetoxy group, propanoyloxy group, pivaloyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, etc.), cyano group, nitro group, etc. Can be

The compounds represented by the following general formulas (Ia) and (I-
Specific examples of the compound represented by b) are shown, but the present invention is not limited thereto.

[0039]

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[0040]

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[0041]

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[0042] In specific examples, X ^- is an anion of a sulfonic acid, in particular _{^{CF 3 SO 3 -, C 4}} F 9 SO 3 -, C 8 F 17
SO ₃ ^- represents a.

The compounds represented by the above general formulas (Ia) and (I-
The compound represented by b) can be suitably used as a material for forming an image by using a compound that generates an acid upon irradiation with energy rays. In these image forming materials, the compounds represented by the above general formulas (Ia) and (Ib) may be used alone or in combination of two or more. The addition amount is 0.05 to 2 with respect to the total solid content of the composition.
It is used in an amount of 0% by weight, preferably 0.2 to 10% by weight, more preferably 1 to 8% by weight.

Hereinafter, the positive resist composition of the present invention will be described in detail. [2] Resin of the present invention (B) The resin as the component (B) is a resin having a monocyclic or polycyclic alicyclic group and an acid-decomposable group. Examples of the basic skeleton of the resin having an alicyclic group include an acrylate resin having the alicyclic group in a side chain, a ring-opening polymerization type resin of a cyclic olefin having the alicyclic group in a main chain, and an addition polymerization type resin. Or a copolymerizable resin with maleic anhydride. The monocyclic or polycyclic alicyclic group is preferably an alicyclic group such as bicyclo, tricyclo, tetracyclo or the like having 5 or more carbon atoms which may have a substituent, and is preferably a substituted or unsubstituted alicyclic group. And represents a polycyclic alicyclic group having 6 to 30 carbon atoms which may have a group, more preferably 7 to 25 carbon atoms which may have a substituent. Representative structures of these alicyclic moieties include, for example, those shown below.

In the present invention, a repeating structural unit having an alicyclic group and an acid-decomposable group can be preferably used. In the present invention, the resin (B) is an alkali-soluble group protected by at least one group selected from the groups having an alicyclic hydrocarbon structure represented by the general formulas (pI) to (pVI). It is preferable to contain a repeating unit having the following formula, since the effects of the present invention become more remarkable. The general formula (p
In I) to (pVI), the alkyl group for R _{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,
n-butyl group, isobutyl group, sec-butyl group, t-
Butyl group and the like. Further, as a further substituent of the alkyl group, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group,
Examples include a carboxy group, an alkoxycarbonyl group, and a nitro group. The alicyclic hydrocarbon group in R _{11 to} R _{25 or} the alicyclic hydrocarbon group formed by Z and a carbon atom may be monocyclic or polycyclic. In particular,
Examples thereof include a group having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The number of carbon atoms is preferably 6 to 30, especially 7 to 25.
Are preferred. These alicyclic hydrocarbon groups may have a substituent. Hereinafter, structural examples of the alicyclic portion of the group containing the alicyclic hydrocarbon structure will be described.

[0046]

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[0047]

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[0048]

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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.

The substituents of these alicyclic hydrocarbon groups include an alkyl group, a substituted alkyl group, a cycloalkyl group,
Examples include an alkenyl group, an acyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. As the alkyl group, a methyl group, an ethyl group,
A lower alkyl group such as a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, and more preferably
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. An alkoxy group (including an alkoxy group of an alkoxycarbonyl group) includes a methoxy group,
C1-C1 such as ethoxy, propoxy and butoxy groups
Four things can be mentioned. Examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like. Examples of the alkenyl group include alkenyl groups having 2 to 6 carbon atoms, and specific examples include a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. Examples of the acyl group include an acetyl group, an ethylcarbonyl group, and a propylcarbonyl group. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom.

Among the structures represented by the general formulas (pI) to (pVI), (pI) and (pII) are preferable.
More preferred are groups represented by the above general formulas (II) and (III). Alkyl groups of R _{26 to} R _{28 in} the general formulas (II) and (III), halogen atoms of R _{29 to} R ₃₁ , alkyl groups, cycloalkyl groups, alkenyl groups, alkoxy groups,
Examples of the alkoxycarbonyl group and the acyl group include those described above as the substituents of the alicyclic hydrocarbon group.

The resins represented by the general formulas (pI) to (pV)
Examples of the alkali-soluble group protected by the structure represented by I) include various groups known in this technical field. Specific examples include a carboxylic acid group, a sulfonic acid group, a phenol group, a thiol group and the like, and preferred are a carboxylic acid group and a sulfonic acid group. The alkali-soluble group protected by the structure represented by the general formulas (pI) to (pVI) in the above resin is preferably the following general formula (pVI)
Groups represented by I) to (pXI).

[0053]

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

[0055]

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In the general formula (pA), 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. Examples of the halogen atom and the alkyl group for R include the same examples as those for R in the general formula (a) described below. A ′ is A ′ of the general formula (AI) described below.
Is synonymous with Ra represents any one of the above formulas (pI) to (pVI).

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

[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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The resin (B) may further contain another repeating unit. The resin (B) in the present invention preferably contains, as another copolymerization component, a repeating unit represented by the general formula (a). Thereby, the developability and the adhesion to the substrate are improved. The alkyl group of R in the general formula (a) is an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, and a butyl group). Examples of the halogen atom for R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R of the general formula (a)
At least one of ₃₂ to R ₃₄ is a hydroxyl group, preferably a dihydroxy form or a monohydroxy form, more preferably monohydroxy body.

Further, the resin (B) in the present invention contains a repeating unit having a group represented by the above general formulas (IV) to (VII). In the general formulas (IV) to (VII), R ₃₅ to
_Examples of the alkyl group for R ₃₉ include a linear or branched alkyl group, and may have a substituent. As the linear or branched alkyl group, a linear or branched alkyl group having 1 to 12 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable. And more preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl Group. As the cycloalkyl group for R _{35 to} R ₃₉ , 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 are preferable.

The alkenyl group for R _{35 to} R ₃₉ 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. In addition, R ₃₅ ~
Examples of the ring formed by combining two members out of R ₃₉ 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. In the general formulas (IV) and (V), R _{35 to} R
₃₉ may be linked to any of the seven carbon atoms constituting the cyclic skeleton.

Further, as the further substituent of the above-mentioned alkyl group, cycloalkyl group and alkenyl group, those having 1 to carbon atoms are preferable.
Examples include four 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.

Preferred examples of the repeating unit having a group represented by any of formulas (IV) to (VII) include a repeating unit represented by the following formula (AI).

[0069]

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In the general formula (AI), R has the same meaning as R in the aforementioned general formula (a). 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 represents a group represented by any one of formulas (IV) to (VII). In A ′, the combined divalent group includes:
For example, the following formula can be used.

[0071]

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In the above formula, Ra, Rb, and r1 have the same meanings as described below. m represents an integer of 1 to 3.

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

[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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Further, the resin (B) in the present invention comprises, as another copolymerization component, the following general formulas (VIII-a) to (VIII-
It preferably contains the repeating unit represented by d). Thereby, the resolution of the contact hole pattern is improved.

[0082]

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In the above formula, R ₀₁ is a group represented by R in the aforementioned general formula (a).
Is synonymous with R _{05 to} R ₀₁₂ each independently represent a hydrogen atom or an alkyl group which may have a substituent. Expression (VI
R in II-b) represents a hydrogen atom or an optionally substituted alkyl group, cyclic alkyl group, aryl group or aralkyl group. m represents an integer of 1 to 10. X
Is a single bond, or an optionally substituted alkylene group, a cyclic alkylene group, an arylene group, or an ether group, a thioether group, a carbonyl group, an ester group,
A single group selected from the group consisting of an amide group, a sulfonamide group, a urethane group, and a urea group, or a combination of at least two or more of these groups and represents a divalent group that is not decomposed by the action of an acid. Z is a single bond, an ether group,
It represents an ester group, an amide group, an alkylene group, or a divalent group obtained by combining these. R ₀₁₃ represents a single bond, an alkylene group, an arylene group, or a divalent group obtained by combining these. R ₀₁₅ is an alkylene group, an arylene group,
Or a divalent group obtained by combining them. R ₀₁₄ represents an _optionally substituted alkyl group, cyclic alkyl group, aryl group or aralkyl group. R ₀₁₆ represents a hydrogen atom or an _optionally substituted alkyl group, cyclic alkyl group, alkenyl group, aryl group or aralkyl group. A represents any of the functional groups shown below.

[0084]

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The alkyl groups represented by R _{05 to} R ₀₁₂ , R, R ₀₁₄ and R ₀₁₆ include linear and branched alkyl groups, which may have a substituent. The linear or branched alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, more preferably 1 to 12 carbon atoms.
10 linear or branched alkyl groups, more preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, Hexyl group, heptyl group, octyl group, nonyl group and decyl group. R, R
The cyclic alkyl group represented by ₀₁₄ or R ₀₁₆ has 3 to 3 carbon atoms.
0 things, specifically, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, tricyclodecanyl group, dicyclopentenyl group, nobornane epoxy group,
Menthyl, isomenthyl, neomenthyl, tetracyclododecanyl, steroid residues and the like can be mentioned.

The aryl group for R, R ₀₁₄ and R ₀₁₆ is
Those having 6 to 20 carbon atoms may be mentioned, and may have a substituent. Specific examples include a phenyl group, a tolyl group, and a naphthyl group. _Examples of the aralkyl group represented by R, R ₀₁₄ and R ₀₁₆ include those having 7 to 20 carbon atoms, such as a benzyl group, a phenethyl group and a cumyl group which may have a substituent. _Examples of the alkenyl group represented by R ₀₁₆ include an alkenyl group having 2 to 6 carbon atoms, specifically, a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclopentenyl group, and a cyclohexenyl group. , 3-oxocyclohexenyl group, 3-oxocyclopentenyl group, 3-oxoindenyl group and the like. Among these, the cyclic alkenyl group may contain an oxygen atom.

As the linking group X, an alkylene group, a cyclic alkylene group, an arylene group or an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group which may have a substituent. A group selected from the group consisting of urea groups, or a combination of at least two or more of these groups;
Examples include divalent groups that do not decompose under the action of an acid. Z
Represents a single bond, an ether group, an ester group, an amide group, an alkylene group, or a divalent group obtained by combining these.
R ₁₃ represents a single bond, an alkylene group, an arylene group, or a divalent group obtained by combining these. R ₁₅ represents an alkylene group, an arylene group, or a divalent group obtained by combining them.

In X, R ₀₁₃ and R ₀₁₅ , the arylene group includes those having 6 to 10 carbon atoms and may have a substituent. Specific examples include a phenylene group, a tolylene group, and a naphthylene group. Examples of the cyclic alkylene group for X include those in which the above-mentioned cyclic alkyl group is divalent. _Examples of the alkylene group for X, Z, R ₀₁₃ , and R ₀₁₅ include groups represented by the following formulas. -[C (Ra) (Rb)] r1- wherein Ra and Rb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group;
Both may be the same or different. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. As the substituent of the substituted alkyl group,
Examples include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r1 represents an integer of 1 to 10.

Specific examples of the linking group X are shown below, but the present invention is not limited thereto.

[0090]

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Further substituents in the above alkyl group, cyclic alkyl group, alkenyl group, aryl group, aralkyl group, alkylene group, cyclic alkylene group and arylene group include carboxyl group, acyloxy group, cyano group,
Alkyl group, substituted alkyl group, halogen atom, hydroxyl group,
Examples include an alkoxy group, an acetylamide group, an alkoxycarbonyl group, and an acyl group. Here, examples of the alkyl group include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group. 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 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 structure of the terminal excluding X are shown below as specific examples of the structure of the side chain in the general formula (VIII-b), but the present invention is not limited thereto. .

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Hereinafter, specific examples of the monomer corresponding to the repeating structural unit represented by formula (VIII-c) will be shown, but the content of the present invention is not limited thereto.

[0094]

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[0095]

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[0096]

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Hereinafter, specific examples of the repeating structural unit represented by formula (VIII-d) are shown, but the present invention is not limited thereto.

[0098]

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[0099]

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[0100]

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In the general formula (VIII-b), R _{05 to} R
_{As 012} , a hydrogen atom and a methyl group are preferable. R is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m is preferably 1 to 6. In Formula (VIII-c), R ₀₁₃ is preferably a single bond, an alkylene group such as a methylene group, an ethylene group, a propylene group, or a butylene group, and R ₀₁₄ is a group having 1 carbon atom such as a methyl group or an ethyl group. 10 to 10 alkyl groups, cyclopropyl group, cyclohexyl group, cyclic alkyl group such as camphor residue, naphthyl group,
A naphthylmethyl group is preferred. Z is a single bond, an ether bond, an ester bond, an alkylene group having 1 to 6 carbon atoms,
Alternatively, a combination thereof is preferable, and a single bond or an ester bond is more preferable. In Formula (VIII-d), R ₀₁₅ is preferably an alkylene group having 1 to 4 carbon atoms. As R ₀₁₆ , an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a neopentyl group, an octyl group, and a cyclohexyl group which may have a substituent; Adamantyl group, norbornyl group, boronyl group, isobornyl group,
Menthyl, morpholino, 4-oxocyclohexyl, and optionally substituted phenyl, toluyl, mesityl, naphthyl, and camphor residues are preferred. As these further substituents, a halogen atom such as a fluorine atom, an alkoxy group having 1 to 4 carbon atoms and the like are preferable. In the present invention, general formulas (VIII-a) to (VIII-a)
Among d), general formula (VIII-b) and general formula (VIII-
The repeating unit represented by d) is preferred.

In addition to the above, the resin (B) controls dry etching resistance, suitability for a standard developing solution, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, and the like, which are general requirements for a resist. It can be used as a copolymer with various monomer repeating units for the purpose.

Examples of such a repeating unit include, but are not limited to, repeating units corresponding to the following monomers. Thereby, the performance required for the resin, particularly (1) solubility in a coating solvent, (2) film forming property (glass transition point), (3)
Alkali developability, (4) film loss (hydrophilic / hydrophobic, alkali-soluble group selection), (5) adhesion of unexposed portion to substrate,
(6) Fine adjustment of dry etching resistance becomes possible.
Examples of such a copolymerizable monomer include, for example, an acrylate, a methacrylate, an acrylamide, a methacrylamide, an allyl compound, a vinyl ether, and an addition-polymerizable unsaturated bond selected from vinyl esters. And the like.

Specifically, for example, acrylates such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (for example, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylate-
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, etc.);

Methacrylic esters, for example, alkyl (alkyl having preferably 1 to 10 carbon atoms) methacrylate (for example, 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, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.); acrylamides such as acrylamide, N-alkylacrylamide , (Alkyl groups having 1 to 1 carbon atoms
0, for example, methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl, cyclohexyl, hydroxyethyl and the like. ), N,
N-dialkylacrylamide (an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group,
There are a butyl group, an isobutyl group, an ethylhexyl group, a cyclohexyl group and the like. ), N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N
-Acetylacrylamide and the like;

Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (alkyl having 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl) Groups, etc.), N, N-dialkyl methacrylamide (an alkyl group such as ethyl group, propyl group, butyl group, etc.), N-hydroxyethyl-N-methyl methacrylamide, etc .; allyl compounds, for example, allyl esters ( For example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate and the like, allyloxyethanol and the like; vinyl ethers such as alkyl vinyl ether (for example, Hexy Vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether,
1-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, etc.);

Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, Vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, etc .; dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); dialkyl esters of fumaric acid (eg, dibutyl) Fumarate etc.) or monoalkyl esters; other acrylic acid, methacrylic acid,
Examples thereof include crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, and maleilenitrile. In addition, any addition-polymerizable unsaturated compound copolymerizable with the above various repeating units may be used. In the resin (B), the molar ratio of each repeating unit structure is determined by the acid value, the dry etching resistance of the resist, the suitability for a standard developer, the substrate adhesion, the dependency of the resist profile on the density of the resist, and the general requirements of the resist. It is set appropriately in order to adjust the resolution, heat resistance, sensitivity and the like.

The content of the repeating unit having an alicyclic group in the resin (B) is adjusted depending on the required dry etching resistance.
80 mol%, preferably 25 to 75 mol%, more preferably 30 to 65 mol%. In the resin of (B),
The content of the repeating unit having an acid-decomposable group is preferably from 20 to 75 mol%, preferably from 25 to 70 mol%, more preferably from 30 to 65 mol%, based on all repeating units.
Mol%. In the resin (B), the compounds represented by the general formulas (IV) to (VI)
The content of the repeating unit having a group represented by I) is from 0 to 70 mol% of all the repeating units, and is preferably 10 mol%.
５０50 mol%, more preferably 15-35 mol%. Further, the content of the repeating unit having a group represented by any one of formulas (pI) to (pVI) is usually 20 to 75 mol%, preferably 25 to 70 mol%, more preferably, of all the repeating units. 30-65 mol%. (B) In the resin, the content of the repeating unit represented by the general formula (a) is usually 0 mol% to 70 mol% in all monomer repeating units.
, Preferably 10 to 40 mol%, more preferably 15 to 30 mol%. In the resin (B), the content of the repeating units represented by the general formulas (VIII-a) to (VIII-d) is usually 0.1 mol% to 30 mol in all monomer repeating units. %, Preferably 0.5 to 25 mol%, more preferably 1 to 20 mol%.

The content of the repeating unit based on the monomer of the further copolymer component in the resin can be appropriately set according to the desired resist properties. A repeating unit containing a group represented by any one of (IV) to (VII), and general formulas (pI) to (pVI)
Is preferably 99 mol% or less, more preferably 9 mol% or less based on the total number of moles of the repeating units having the group represented by
0 mol% or less, more preferably 80 mol% or less.

The weight average molecular weight (Mw) of the resin (B) is preferably from 1,000 to 1,000, as determined by gel permeation chromatography, using polystyrene standards.
000, more preferably 1,500 to 500,000,
It is more preferably in the range of 2,000 to 200,000, and particularly preferably in the range of 2,500 to 100,000. As the weight average molecular weight increases, heat resistance and the like improve, while developability and the like decrease. It is adjusted to a preferable range by the balance of. The resin (B) used in the present invention can be synthesized according to a conventional method, for example, by a radical polymerization method.

The following are specific examples of the resin (B) of the present invention, but the present invention is not limited thereto.

[0112]

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[0113]

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[0114]

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[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]

[Of 60]

In the above formula, R is a hydrogen atom or a methyl group. In the above formula, m, n, p and n1, n
2 and n3 each represent a molar ratio of the number of repetitions. (IV)
N represents a repeating unit having a group represented by any one of (VII) to (VII);
And so on. The repeating unit having a group containing an alicyclic hydrocarbon structure represented by (pI) to (pVI) is indicated by m. The repeating units represented by the general formulas (VIII-a) to (VIII-d) are represented by p. General formula (VIII-a)
When a repeating unit represented by (VIII-d) is included, m /
n / p is (25-70) / (25-65) / (3-4
0). When no repeating unit represented by any of the general formulas (VIII-a) to (VIII-d) is contained, m / n is (30 to
70) / (70-30). It may be a block copolymer or a random copolymer. It may be a regular polymer or an irregular polymer.

In the positive resist composition of the present invention,
The amount of the resin (B) added to the entire composition is preferably 40 to 99.99% by weight, more preferably 50 to 99.97% by weight, based on the total resist solids.

[3] Compound (A ') which is used in combination with a compound represented by formula (Ia) or (Ib) to generate an acid upon irradiation with actinic rays or radiation. The compound (A ′) used in combination with the compound (a) or (Ib), which generates an acid upon irradiation with actinic rays or radiation, includes a photoinitiator for photocationic polymerization and a photoinitiation for photoradical polymerization. Known light (400-200 nm ultraviolet light, far ultraviolet light, particularly preferably g-line, h-line, i-line, KrF) Excimer laser light), ArF excimer laser light, electron beam, X-ray,
A compound that generates an acid by a molecular beam or an ion beam and a mixture thereof can be appropriately selected and used. Other photoacid generators used in the present invention include, for example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, organic halogen compounds, and organic metal / organic compounds. Halides, photoacid generators having an o-nitrobenzyl-type protecting group, compounds that generate sulfonic acid upon photolysis typified by iminosulfonate, disulfone compounds, diazoketosulfones, diazodisulfone compounds, and the like. Can be. Further, a group in which an acid is generated by such light or a compound in which a compound is introduced into a main chain or a side chain of a polymer can be used.

Furthermore, V. N. R. Pilai, Syn
thesis, (1), 1 (1980); Abad
et al, Tetrahedron Lett. , (4
7) 4555 (1971); H. R. Barton
et al. Chem. Soc. , (C), 329
(1970), U.S. Pat. No. 3,779,778, European Patent 126,712, and the like, which can generate an acid by light can also be used.

Among the compounds capable of decomposing upon irradiation with actinic rays or radiation to generate an acid, those which are particularly effectively used are described below.

(1) An oxazole derivative represented by the following general formula (PAG1) or an S-triazine derivative represented by the general formula (PAG2) substituted by a trihalomethyl group.

[0134]

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In the formula, R ²⁰¹ represents a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C (Y) ₃
Show Y represents a chlorine atom or a bromine atom.

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

[0137]

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

[0139]

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Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. R ²⁰³ , R ²⁰⁴ , R
²⁰⁵ is each independently a substituted or unsubstituted alkyl group,
Indicates an aryl group. And Z ^- represents an anion of a sulfonic acid. Specifically, alkyl sulfonic acid optionally having a substituent, cycloalkyl sulfonic acid, perfluoroalkyl sulfonic acid, aryl sulfonic acid (for example, benzene sulfonic acid optionally having a substituent, naphthalene sulfonic acid, Anions such as anthracenesulfonic acid). Preferred substituents for substituting these groups include an alkyl group (methyl group, ethyl group, i-propyl group, t-butyl group, etc.), a haloalkyl group (fluoromethyl group, chloromethyl group, bromomethyl group, trifluoromethyl group, Methyl group, pentafluoroethyl group, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, octyloxy group, etc.), amino group, amide group, ureido group, urethane group, hydroxyl group, carboxyl group, halogen Atoms (fluorine, chlorine, bromine,
Iodine atom), thioether group, acyl group (acetyl group,
Propanoyl group, pivaloyl group, etc.), acyloxy group (acetoxy group, propanoyloxy group, pivaloyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, etc.), cyano group, nitro group, etc. Can be Further, two of R ²⁰³ , R ²⁰⁴ , and R ²⁰⁵ and Ar ¹ , Ar ²
May be bonded via each single bond or a substituent.

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

[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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The onium salts represented by the general formulas (PAG3) and (PAG4) are known. W. Kn
apczyketal, J.A. Am. Chem. So
c. , 91, 145 (1969); L. Mayco
ketal, J.M. Org. Chem. , 35,253
2, (1970); Goethaetal, Bu
ll. Soc. Chem. Belg. , 73, 546,
(1964); M. Leicester, J.A. Am
e. Chem. Soc. , 51, 3587 (192)
9); V. Crivello et al, J. Mol. Po
lym. Chem. Ed. , 18, 2677 (198
0), U.S. Pat. Nos. 2,807,648 and
No. 47,473, JP-A-53-101,331 and the like.

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

[0151]

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In the formula, Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
It represents an unsubstituted alkyl group or aryl group. A is a substitution
Or unsubstituted alkylene, alkenylene, arylene
Shows a substituent group.

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

[0154]

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[0155]

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[0156]

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

[0158]

[Of 75]

Here, R represents a linear, branched or cyclic alkyl group or an optionally substituted aryl group.

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

[0161]

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In the present invention, as the photoacid generator, a sulfonium or iodonium sulfonate compound (particularly preferably, a compound represented by (PAG3) or (PAG4)) and an N-hydroxyimide sulfonate compound (particularly preferable) Is a compound represented by (PAG6) or a disulfonyldiazomethane compound (particularly preferably (P
AG7). Thereby, the sensitivity and the resolving power are excellent, and the edge roughness of a fine pattern is also excellent.

The amount of the photoacid generator (A ′) that can be used in combination is usually 0.03% based on the solid content in the composition.
It is used in the range of 1 to 20% by weight, preferably 0.1 to
It is used in an amount of 10% by weight, more preferably 0.5 to 5% by weight.

The positive resist composition of the present invention may further contain, if necessary, an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer,
A surfactant, a photosensitizer, an organic basic compound, and a compound that promotes solubility in a developer can be contained. The positive resist composition of the present invention may contain a fluorine-based and / or silicon-based surfactant.
The positive resist composition of the present invention may contain any one of fluorine-based surfactants, silicon-based surfactants, and surfactants containing both fluorine atoms and silicon atoms, or two or more thereof. .

As these surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, and JP-A-62-170950.
JP-A-63-34540, JP-A-7-23016
5, JP-A-8-62834, JP-A-9-54432
And the surfactants described in JP-A-9-5988, and the following commercially available surfactants can be used as they are. Examples of commercially available surfactants that can be used include, for example, F-Top EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florado FC430 and 431 (manufactured by Sumitomo 3M Limited), Megafac F171 and F173.
F176, F189, R08 (Dainippon Ink Co., Ltd.)
Manufactured), Surflon S-382, SC101, 102, 1
03, 104, 105, and 106 (manufactured by Asahi Glass Co., Ltd.) and Troisol S-366 (manufactured by Troy Chemical Co., Ltd.). In addition, polysiloxane polymer KP-341
(Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

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

Examples of other surfactants that can be used include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether. Alkyl ethers, polyoxyethylene alkyl allyl ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate Fatty acid esters such as sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene Nonionics such as polyoxyethylene sorbitan fatty acid esters such as bitane monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Surfactants and the like can be mentioned. The amount of these other surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention.

The acid diffusion inhibitor (C) which can be used in the present invention is preferably added from the viewpoint of suppressing fluctuations in sensitivity and resolution over time from exposure to heating and development, and preferably an organic base. Compound. Examples of the organic basic compound include a nitrogen-containing basic compound having the following structure.

[0169]

Embedded image

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

[0171]

Embedded image

Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶
Are the same or different and represent an alkyl group having 1 to 6 carbon atoms.) Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule,
Particularly preferred are compounds containing both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom, or compounds having an alkylamino group. Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazol, substituted or unsubstituted Pyrazole, substituted or unsubstituted pyrazine,
Substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted aminomorpholine, substituted or unsubstituted amino And alkyl morpholine. Preferred substituents are an amino group, an aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group,
A hydroxyl group and a cyano group.

Preferred specific compounds are guanidine, 1,1-dimethylguanidine, 1,1,3,3,-
Tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine,
-Amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-amino Pyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-imino Piperidine, 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,
-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,
3,4,5-triphenylimidazole, N-methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethylthiourea (CHMETU)
Grade morpholine derivatives, hindered amines described in JP-A-11-52575 (for example, [0005]
), But is not limited thereto.

Particularly preferred specific examples are 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2 2.2.2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines, CHMETU
And tertiary morpholines, and hindered amines such as bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebagate. Among them, 1,5-
Diazabicyclo [4,3,0] non-5-ene, 1,8
-Diazabicyclo [5,4,0] undec-7-ene,
1,4-diazabicyclo [2,2,2] octane, 4-
Dimethylaminopyridine, hexamethylenetetramine,
CHMETU, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebagate is preferred.

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

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

Of the above, preferred solvents are 2-
Heptanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate , N-methylpyrrolidone and tetrahydrofuran. Such a positive resist composition of the present invention is applied on a substrate to form a thin film. The thickness of this coating film is preferably from 0.2 to 1.2 μm.
In the present invention, if necessary, a commercially available inorganic or organic antireflection film can be used.

As the antireflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon and α-silicon, and an organic film type comprising a light absorbing agent and a polymer material can be used. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation. As the organic antireflection film, for example, Japanese Patent Publication No. 7-69
611, a condensate of a formaldehyde-modified melamine resin with a diphenylamine derivative, an alkali-soluble resin,
A light absorbing agent or a reaction product of a maleic anhydride copolymer and a diamine type light absorbing agent described in US Pat. No. 5,294,680;
JP-A-6-118631, containing a resin binder and a methylolmelamine-based thermal crosslinking agent;
Acrylic resin type antireflection film having a carboxylic acid group, an epoxy group and a light absorbing group in the same molecule described in 18656, a film comprising a methylolmelamine and a benzophenone-based light absorbing agent described in JP-A-8-87115, and a method described in JP-A-8-179509 Examples thereof include those obtained by adding a low-molecular-weight light absorbing agent to a polyvinyl alcohol resin. Also, as an organic anti-reflection film,
DUV30 series manufactured by Brewer Science,
DUV-40 series, Shipley's AC-2, AC
-3 can also be used.

The resist solution is coated on a substrate (eg, a silicon / silicon dioxide coating) used for manufacturing precision integrated circuit devices (on a substrate provided with the antireflection film as required), a spinner, a coater, and the like. After coating by an appropriate coating method such as that described above, exposure through a predetermined mask, baking and development can provide a good resist pattern. Here, the exposure light is preferably 150
It is light having a wavelength of nm to 250 nm. Specifically, Kr
F excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157
nm), X-rays, electron beams and the like. Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; diethylamine;
Secondary amines such as -butylamine, triethylamine,
Tertiary amines such as methyldiethylamine; alcoholamines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; and cyclic amines such as pyrrole and pichelidine. An alkaline aqueous solution can be used. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0180]

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

Synthesis Example 1 Synthesis of Resin (1) of the Present Invention 2-Methyl-2-adamantyl methacrylate and 6-e
ndo-hydroxybicyclo [2.2.1] heptane-
5-exo of 2-endo-carboxylic acid-γ-lactone
-Methacrylate was charged at a molar ratio of 50/50, dissolved in N, N-dimethylacetamide / tetrahydrofuran = 5/5, and 100 m of a solution having a solid concentration of 20% was prepared.
1 was adjusted. 6-endo-hydroxybicyclo [2.2.1] heptane-2-endo-carboxylic acid-
5-exo-methacrylate of γ-lactone is 6-e
ndo-hydroxybicyclo [2.2.1] heptane-
After the 2-endo-carboxylic acid was acetoxy-lactonized, the one synthesized by alkali-hydrolyzing the acetoxy group to a hydroxy group and further esterifying with methacrylic acid chloride was used. J. Chem. Soc. ,
227 (1959), Tetrahedron, 21,
1501 (1965). 3 mol% of V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added to this solution, and this was added dropwise to 10 ml of N, N-dimethylacetamide heated to 60 ° C. over 3 hours in a nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated for 3 hours, and 1 mol /% of V-65 was added again.
Stir for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and white powder crystallized and precipitated in 3 L of distilled water was recovered.
The polymer composition determined from C ¹³ NMR was 51/49. The weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 7,200.

Synthesis Examples 2 to 10. Synthesis of Resin of the Present Invention Resins (2) to (10) having composition ratios and molecular weights shown in Table 1 were contained in the same manner as in Synthesis Example 1.

[0183]

[Table 1]

Among the resins synthesized in Synthesis Examples 1 to 10, the n component (center component) of the resins (20) and (23) has R as a hydrogen atom and the resins (25) and (29) have the same structure. In the p component (the component on the right side), R is a hydrogen atom, and all R in the remaining portion are those of a methyl group.

Synthesis Example 11 Compound (I) of the present invention (A)
Synthesis of -19) 10.6 g (0.12 mol) of tetrahydrothiophene was dissolved in 80 ml of acetonitrile, and stirred at room temperature for 2 hours.
16.5 g (0.10 mol) of -bromo-γ-butyrolactone were added. Stirring was further continued for one day. 100 ml of ethyl acetate was added to the reaction mixture, and the precipitated solid was separated by filtration.
By drying, 10.2 g of a bromide salt of 2-thiophenium-γ-butyrolactone was obtained. Next, 10.0 g (0.030 mol) of potassium nonafluorobutanesulfonate was added to methanol / ion-exchanged water = 100 ml / 500.
Then, a solution of 7.3 g (0.029 mol) of the above bromide salt of 2-thiophenium-γ-butyrolactone in 50 ml of methanol was added at room temperature with stirring. After stirring for 3 hours, the mixture was extracted with chloroform, washed with water, and the extract was concentrated. Ethyl acetate was added to the oily concentrate to precipitate a powder, which was separated by filtration and washed with diisopropyl ether to obtain 6.9 g of a white powder. NMR confirmed that the powder was Compound (I-19) of the present invention.

Synthesis Example 12 Compound (I) of the present invention (A)
Synthesis of -31) In place of 2-bromo-γ-butyrolactone in Synthesis Example 11, 19.5 g (0.10 mol) of ethyl bromopyruvate was used, and the reaction and post-treatment were carried out in the same manner as in Synthesis Example 11. Was. 10.6 g of a white powder was obtained, and confirmed to be the compound (I-31) of the present invention by NMR. Hereinafter, the compound (A) of the present invention was synthesized in the same manner.

Synthesis of Compound of Comparative Example In place of 2-bromo-γ-butyrolactone of Synthesis Example 11, 19.3 g of bromomethyl-amyl ketone (0.10 g) was used.
), And the reaction and post-treatment were carried out in the same manner as in Synthesis Example 11. 10.7 g of a white powder was obtained, and it was confirmed by NMR that it was the compound (a) of the following comparative example.

[0188]

Embedded image

Examples 1 to 11 and Comparative Examples 1 and 2 [Adjustment and Evaluation of Positive Resist Composition] The compound (A) of the present invention was added as a photoacid generator to 1.4 g of the resin obtained in the above synthesis. 0.08 g was added, and 0.002 g of 1,5-diazabicyclo [4,3,0] -5-nonene and 0.001 g of Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.) as a surfactant were mixed. And dissolved in propylene glycol monomethyl ether acetate at a ratio of 14%.
Examples 1 to 1 were filtered through a 0.1 μm microfilter.
1. The positive resists of Comparative Examples 1 and 2 were prepared. Table 2 shows the resin of the present invention and the photoacid generator used.

[0190]

[Table 2]

[0191] Compounds of the present invention described in Table. 2 (A) all counteranion C ₄ F ₉ SO ₃ ^- was used ones.

(Evaluation Test) The obtained positive resist solution was applied on a silicon wafer using a spin coater.
After drying at 130 ° C. for 90 seconds, a positive photoresist film having a thickness of about 0.4 μm was formed and exposed to an ArF excimer laser (exposed with an ISI ArF stepper having a wavelength of 193 nm and NA = 0.6). A heat treatment after the exposure was performed at 120 ° C. for 90 seconds, developed with a 2.38% aqueous solution of tetramethylammonium hydroxide, and rinsed with distilled water to obtain a resist pattern profile. With respect to these, sensitivity, resolution, edge roughness, and pattern profile were evaluated as follows. Table 3 shows the evaluation results.

[Sensitivity] Sensitivity was evaluated at the minimum exposure amount that reproduced a 0.15 μm line and space pattern.

[Resolving power] The resolving power was evaluated by a limit resolving power which can be reproduced at the minimum exposure amount for reproducing a 0.15 μm line and space pattern.

[Edge Roughness] The edge roughness was measured at the edge roughness of an isolated pattern using a length-measuring scanning electron microscope (SEM), and a line pattern edge was detected at a plurality of positions in a measurement monitor. The variance (3σ) of the variation in the detection position is used as an index of the edge roughness, and the smaller the value, the more preferable.

[Pattern profile shape]: The obtained resist pattern profile was observed with a scanning electron microscope.

[0197]

[Table 3]

As is evident from the results in Table 3, the positive resist compositions of the present invention are all at satisfactory levels. That is, it is suitable for lithography using far ultraviolet rays such as ArF excimer laser exposure.

[0199]

The present invention can provide a positive resist composition which is suitable for far ultraviolet light, particularly ArF excimer laser light, has excellent sensitivity, resolution, and edge roughness, and has an excellent resist pattern profile.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C07D 339/06 C07D 339/08 339/08 409/04 409/04 C08K 5/36 C08K 5/36 C08L 101/02 C08L 101/02 G03F 7/004 503A G03F 7/004 503 7/039 601 7/039 601 C07D 307/32 MF term (reference) 2H025 AA01 AA02 AA03 AA14 AB16 AC04 AC08 AD03 BE07 BE10 BG00 CB14 CB41 FA17 4C023 JA05 4C063 CC92 DD73 EE10 4H006 AA01 AB92 TN60 4J002 AA031 BH021 BK001 CE001 EV296 FD206 GP03

Claims (6)

[Claims] 1. A compound represented by the general formula (Ia) or (Ib). Embedded image Wherein, R _1, R ₂ may be the same or different, it may have a substituent, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, R ₃ , R ₄ may be the same or different,
A hydrogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an acyl group, an alkoxycarbonyl group, a halogen atom, and —S—R ₅ which may have a substituent. However, R ₃ , R ₄
Is a group other than a hydrogen atom. R ₅ represents an alkyl group, a haloalkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or an aralkyl group which may have a substituent. R ₆ and R ₇ may be the same or different, and may be a hydrogen atom, which may have a substituent, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an acyl group, an alkoxy group. carbonyl group, a -S-R _5. R ₈ and R ₉ may be the same or different, and may be a hydrogen atom, which may have a substituent, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an acyl group, an alkoxy group. Represents a carbonyl group. R ₁₀ represents an alkyl group, a haloalkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an -O-R _5. n
Represents an integer of 0 or 1 to 3. Further, two of R _{1 to} R ₅ of the general formula (Ia) and two of R _{1 to} R ₁₀ of (Ib) may combine to form a ring. X ^- represents an anion of a sulfonic acid. (A) a compound represented by the above general formula (Ia) or (Ib) which generates an acid upon irradiation with actinic rays or radiation, (B) an alicyclic group and acid decomposition Having a functional group,
A positive resist composition comprising a resin that decomposes under the action of an acid to increase the solubility in alkali. 3. The resin of (B) has the following general formula (pI):
The positive according to claim 2, further comprising a repeating unit having an alkali-soluble group protected by at least one of groups having an alicyclic hydrocarbon structure represented by (pVI). -Type resist composition. Embedded image In formulas (pI) to (pVI), R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group;
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 linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{12 to} R ₁₄ , or Either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon group. R _{17 to} R ₂₁ each independently represent a hydrogen atom,
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 _{17 to} R ₂₁ represents an alicyclic hydrocarbon group. Also, R ₁₉ ,
Any of R ₂₁ represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. R ₂₂ ~R
₂₅ independently 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. 4. The group containing an alicyclic hydrocarbon structure represented by the general formulas (pI) to (pVI) is represented by the following general formula (II):
4. The positive resist composition according to claim 3, wherein the group is represented by (III). Embedded image In the formula, R _{26 to} R ₂₈ may be the same or different and represent an alkyl group which may have a substituent. R _{29 to} R ₃₁ may be the same or different, and may have a hydroxy group, a halogen atom, a carboxy group, or a substituent; an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group; Or an acyl group. p, q, and r each independently represent an integer of 0 or 1 to 3. 5. The resin of the above (B) is represented by the following general formula (a)
The positive resist composition according to claim 2, further comprising a repeating unit represented by the formula: Embedded image In the general formula (a), R represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. R ₃₂ to R ₃₄ may be the same or different, represent a hydrogen atom or a hydroxyl group. At least one of R ₃₂ to R ₃₄
One represents a hydroxyl group. 6. The resin of the above (B) is represented by the following general formula (IV)
The positive resist composition according to claim 2, further comprising a repeating unit having a group represented by at least one of (VII) to (VII). Embedded image In the formula, R _{35 to} R ₃₉ may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. Two of R _{35 to} R ₃₉ may combine to form a ring.