JP2002251011A - Positive photoresist composition for exposure with far ultraviolet ray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photoresist composition for exposure with far UV excellent in aptness for a halftone phase shift mask in the production of a semiconductor device and to provide a positive photoresist composition for exposure with far UV excellent also in sensitivity and profile. SOLUTION: Each of the positive photoresist compositions contains (A) a polymer having a group which is decomposed by the action of an acid having a specified structure, (B) a specified dissolution inhibitor and (C) an imidosulfonate acid generating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photoresist composition for microfabrication of semiconductor devices and the like which is sensitive to far ultraviolet rays, and more particularly, to a halftone phase shift mask suitable (side-rope light resistance). The present invention relates to a positive photoresist composition for deep-ultraviolet exposure, which has good resist performance and excellent resist performance.

[0002]

2. Description of the Related Art A positive photoresist is applied on a substrate such as a semiconductor wafer, glass, ceramics or metal by a spin coating method or a roller coating method to a thickness of 0.5 to 2 μm. Thereafter, the film is heated and dried, and a circuit pattern or the like is baked by ultraviolet irradiation or the like through an exposure mask. If necessary, the film is baked after exposure and then developed to form a positive image. Further, by performing etching using the positive image as a mask, a pattern-like processing can be performed on the substrate. Typical application fields include semiconductor manufacturing processes such as ICs, manufacturing of circuit boards such as liquid crystals and thermal heads, and other photofabrication processes.

Conventionally, it has been advantageous to use a resist having a high contrast (γ value) in order to enhance the resolution and obtain an image with good pattern shape, and technical development of a resist composition suitable for such purpose has been carried out. I have been. There are numerous publications disclosing such techniques. In particular, a number of patent applications have been filed with respect to the monomer composition, molecular weight distribution, synthesis method, and the like of the resin, which is a main part of the positive photoresist, and have achieved certain results. Also, as for the photosensitive material, which is another main component, compounds having many structures which are effective for increasing the contrast have been disclosed. If these techniques are used to design a positive photoresist, it has become possible to develop an ultra-high resolution resist capable of resolving a pattern having a size comparable to the wavelength of light.

However, the degree of integration of integrated circuits is increasing, and in the production of semiconductor substrates such as VLSIs, processing of ultrafine patterns having a line width of 0.5 μm or less is required. It is becoming.

On the other hand, various attempts have been made to further increase the resolving power by a super-resolution technique such as an exposure technique or a mask technique. Various super-resolution techniques have been studied for the light source plane, the mask plane, the pupil plane, and the image plane. On the light source surface, there is a technique for improving the resolving power by forming a light source called a modified illumination method, that is, a shape different from a conventional circular shape. On the mask surface, there has been reported a technique in which a phase is also controlled using a phase shift mask, that is, a phase difference is given to light transmitted through the mask, and a high resolution is obtained by making good use of the interference. (For example,
Tokuhisa Ito: Stepper Optics (1) to (4), Optical Technology Contact, Vol.27, No.12, 762 (1988), Vol.28, No.1,59 (199)
0), Vol. 28, No. 2, 108 (1990), Vol. 28, No. 3, 165 (1990),
JP-A-58-173744, JP-A-62-50811, JP-A-62-67514, JP-A-1-14
7458, 1-283925, 2-221451, etc.)

As described in JP-A-8-15851, a resist exposure method using a halftone type phase shift mask is particularly noted as a practical technique for improving the spatial image and contrast of a projected image. But
In the light intensity distribution of the exposure light reaching the resist, a so-called sub-peak occurs in addition to the main peak, and the portion of the resist that should not be exposed is exposed. In particular, the higher the coherence degree (σ), the more the sub-peak becomes. growing. When such a sub-peak is generated, unevenness due to the sub-peak is formed in the resist after exposure and development in the positive resist, which is not preferable.

As described above, the projection optical system of the optical lithography has been devised with various miniaturizations, and the combination of various super-resolution techniques has been actively studied (for example, a half-tone type phase shift mask and the like). Annular lighting:
CNAhnetal; SPIE, Vol. 2440, 222 (1995), T. Ogawa et.
al; SPIE, Vol.2726, 34 (1996).

However, when the above-mentioned super-resolution technique is applied, the resolution of the conventional positive type photoresist deteriorates, the exposure margin and exposure latitude become insufficient, and unevenness (film reduction) occurs. There have been reports of performance degradation. For example, CLLin et al. Reported that the use of the modified illumination method deteriorated the pattern density dependence due to the optical proximity effect (SPIE, vol. 2726, 437 (1996)), and N. Samarakone et al. And IBHur et al. Point out that when a contact hole pattern is formed using a halftone phase shift mask, the periphery of the hole pattern becomes uneven due to the influence of side lobe light (SPIE, Vol. .2440,61
(1995), SPIE, Vol. 2440,278 (1995)). In order to reduce the influence of side lobe light, some measures such as surface treatment of the positive resist with alkali after exposure have been made (TY
asuzato etal; SPIE, Vol. 2440, 804 (1995)) There is a problem that the process becomes complicated.

JP-A-10-10739 discloses an energy-sensitive resist containing a polymer obtained by polymerizing a monomer having an alicyclic structure such as a norbornene ring in its main chain, maleic anhydride, and a monomer having a carboxyl group. Is disclosed. Japanese Patent Application Laid-Open No. H10-111569 discloses that
A radiation-sensitive resin composition containing a resin having an alicyclic skeleton in the main chain and a radiation-sensitive acid generator is disclosed. JP-A-11-109632 describes that a resin containing a polar group-containing alicyclic functional group and an acid-decomposable group is used for a radiation-sensitive material.

EP1048983A1 has a storage stability,
For the purpose of improving transparency, dry etching property, sensitivity, resolution, pattern shape, etc., a repeating unit composed of norbornene having a specific acid-decomposable group, a repeating unit composed of anhydride, and a repeating unit having an alicyclic group A composition comprising a resin having the formula: JP-A-11-
No. 202491 discloses a polymer containing a repeating unit derived from a norbornene derivative, an acid generator, an androstan-17-carboxylate ester from the viewpoint of transparency to radiation, dry etching resistance, resolution, pattern shape, sensitivity and the like. Compositions containing the compounds have been proposed.

However, even when these resist materials are used, the resistance due to side lobe light when a contact hole pattern is formed using a halftone type phase shift mask is insufficient, and improvement has been desired. In addition, a positive photoresist composition for deep ultraviolet exposure which is excellent in resist performance such as sensitivity and profile has been desired.

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a positive type photoresist composition for exposure to deep ultraviolet light which is suitable for a halftone phase shift mask in the manufacture of semiconductor devices. An object of the present invention is to provide an excellent positive photoresist composition for deep ultraviolet exposure.

[0013]

Means for Solving the Problems The present inventors have conducted intensive studies on the constituent materials of a resist composition in a positive-type chemical amplification system, and as a result, by using a specific acid-decomposable resin and a specific additive, the present invention has been developed. The inventors have found that the object of the invention has been achieved, and have reached the present invention. That is, the above object is achieved by the following constitutions.

(1) (A) having at least one of repeating units represented by the following general formulas (Ia) and (Ib) and a repeating unit represented by the following general formula (II), and A polymer having a group that decomposes under the action of an acid,
(B) a dissolution inhibitor represented by the following general formula (CI) or (CII); and (C) an imidosulfonate acid generator represented by the general formula (PAG6). Positive photoresist composition for deep ultraviolet exposure.

[0015]

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In the formula (Ia): R ₁ and R ₂ are each independently
Hydrogen atom, cyano group, hydroxyl group, -COOH, -COOR
₅ represents a _{-CO-NH-R 6, -CO} -NH-SO 2 -R 6, which may be substituted, an alkyl group, an alkoxy group, a cyclic hydrocarbon group, or the following -Y group. X is an oxygen atom,
Sulfur atom, -NH -, - NHSO ₂ - or -NHSO ₂ N
Represents H-. Here, R ₅ represents an optionally substituted alkyl group, cyclic hydrocarbon group or the following —Y group. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. A represents a single bond or a divalent linking group. A —Y group;

[0017]

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(In the —Y group, R _{21 to} R ₃₀ are each independently
Represents a hydrogen atom or an alkyl group which may have a substituent. a and b represent 1 or 2. ) Formula (Ib) in: Z ₂ is, -O- or -N (R ₃₎ - represents a. Here, R ₃ represents a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OSO ₂ —R ₄ . R ₄ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue. In the formula (II), 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 two bonded carbon atoms (C
-C) and represents an atomic group for forming an alicyclic structure which may have a substituent.

[0019]

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In the general formula (CI), X represents an oxygen atom, a sulfur atom, —N (R ₅₃ ) —, or a single bond. R ₅₁ , R ₅₂
And R ₅₃ each independently represent a hydrogen atom or an alkyl group which may have a substituent, and R ′ is —C (＝ O) —O
-R 'represents a group constituting an acid-decomposable group. R represents a bridged hydrocarbon, a saturated cyclic hydrocarbon or a naphthalene ring-containing n
Represents a monovalent residue. n1 represents an integer of 1 to 4, and q1 represents an integer of 0 to 10. In the general formula (CII), R ₆₀ is
R ₆₁ represents an alkyl group or a halogen atom which may have a substituent, and R ₆₁ represents a group constituting an acid-decomposable group by —O—R ₆₁ . m1 represents an integer of 0 to 4. p1 represents an integer of 1 to 4.

[0021]

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R ²⁰⁶ is a linear chain which may have a substituent,
A branched or cyclic alkyl group, an optionally substituted aralkyl group, a substituted or unsubstituted aryl group, and a camphor group. A ² is a linear or branched alkylene group which may have a substituent, a monocyclic or polycyclic alkylene group which may have a substituent and may contain a hetero atom, Linear or branched alkenylene group which may be substituted, monocyclic or polycyclic alkenylene group which may be substituted and which may contain a hetero atom, arylene group which may be substituted, aralkylene which may be substituted Represents a group.

(2) The positive photoresist composition for deep ultraviolet exposure according to the above (1), further comprising a sulfonium salt. (3) The positive photoresist composition for deep ultraviolet exposure according to the above (2), wherein the sulfonium salt is a compound represented by the general formula (SI).

[0024]

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In the general formula (SI), Rs _{4 to} Rs ₆ each independently represent an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, a nitro group, a halogen atom, a hydroxyl group, or Represents a carboxyl group. 1: 1-5 m: 0-5 n: 0-5. When l + m + n = 1, Rs ₄ represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, or an acyloxy group. Xs ⁻ : R—SO ₃ ⁻ , R: represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

Further, preferred embodiments include the following embodiments. (4) An atomic group for forming a bridged alicyclic structure which may have a substituent, wherein Z in the general formula (II) contains two bonded carbon atoms (CC). The positive photoresist composition for deep ultraviolet exposure according to the above (1) to (3), wherein

(5) The repeating unit represented by the general formula (II) is represented by the following general formula (II-A) or (II-A):
The positive photoresist composition for deep ultraviolet exposure according to any one of (1) to (3), which is a repeating unit represented by B).

[0028]

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In the formulas (II-A) and (II-B): R _{13 to} R ₁₆
Is independently a hydrogen atom, a halogen atom, a cyano group,
—COOH, —COOR ₅ (R ₅ is as defined above), a group decomposed by the action of an acid, —C (＝ O) —X
-AR ₁₇ , or an alkyl group or a cyclic hydrocarbon group which may have a substituent. Further, at least two members out of R _{13 to} R ₁₆ may combine to form a ring. n represents 0 or 1. Here, X and A are as defined above. 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 (R ₅ , R
₆ each has the same meaning as described above) or the above-mentioned -Y group.

(6) The positive photoresist composition according to any one of the above (1) to (5), further comprising a nitrogen-containing basic compound. (7) The nitrogen-containing basic compound is 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo
[5.4.0] -7-undecene, 1,4-diazabicyclo
[2.2.2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines, tertiary morpholines, and hindered piperidines The positive photoresist composition for deep ultraviolet exposure according to the above (6), which is at least one compound selected from hindered amines having a skeleton. (8) The positive photoresist composition for deep ultraviolet exposure according to the above (1) to (7), further comprising a fluorine-based and / or silicon-based surfactant.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail.

[1] First, the dissolution inhibitor used as the component (B) in the present invention will be described. The positive photosensitive composition of the present invention contains a compound represented by the above general formula (CI) or (CII) as a dissolution inhibitor. In the general formula (CI), X represents an oxygen atom, a sulfur atom, —N (R ₅₃ )
-Or represents a single bond. In R ₅₁ , R ₅₂ and R ₅₃ of the formula (CI), _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, a sec-butyl group and a t-butyl group. Examples thereof include those having 1 to 8 carbon atoms such as a butyl group, a hexyl group, a 2-ethylhexyl group and an octyl group. In the general formula (CI), -C (= O) -OR 'is a group that is decomposed by the action of an acid (also referred to as an acid-decomposable group). Here, R ′ may be a tertiary alkyl group (preferably having 4 to 20 carbon atoms ) such as a t-butyl group, a methoxy t-butyl group, a t-amyl group, an isobornyl group, or a substituent. Good, 1-ethoxyethyl group, 1-butoxyethyl group,
1-alkoxyethyl groups such as 1-isobutoxyethyl group, 1-cyclohexyloxyethyl group, 1- [2- (n-butoxy) ethoxy] ethyl group (preferably having 2 to 2 carbon atoms)
10), an optionally substituted alkoxymethyl group such as a 1-methoxymethyl group and a 1-ethoxymethyl group (preferably having 2 to 10 carbon atoms), and an optionally substituted tetrahydropyrani , A tetrahydrofuranyl group which may have a substituent, a trimethylsilyl group, t-
Trialkylsilyl groups such as butyldimethylsilyl group and diisopropylmethylsilyl group (preferably having 3 to 2 carbon atoms)
0) and a 3-oxocyclohexyl group. The tertiary alkyl group for R ′ may form an alicyclic ring. As a preferred substituent which the alkoxymethyl group and the alkoxyethyl group of R ′ may have, a halogen atom,
_{- (OCH 2 CH 2) 2} OCH 3, -S (CH 2) 2 CH 3, -SC (CH 3) 3, -O- adamantane, -O-CO- adamantane. Preferred substituents that the tetrahydropyranyl group and the tetrahydrofuranyl group may have include a carbonyl group and an alkyl group having 1 to 5 carbon atoms.

R represents a bridged hydrocarbon, a saturated cyclic hydrocarbon or an n 1 -valent residue containing a naphthalene ring. Examples of the n1 valent residue containing a bridged hydrocarbon include adamantane, norbornane, tricyclodecane, tetracycloundecane, and pinene having n1 bonds.
Examples of the n1 valent residue containing a saturated cyclic hydrocarbon include terpene and steroid. N containing a naphthalene ring
Examples of the monovalent residue include a naphthalene ring having n1 bonds. The above-mentioned bridged hydrocarbon, saturated cyclic hydrocarbon or naphthalene ring may have a substituent at a position other than a bond. Preferred substituents include
Hydroxyl group, halogen atom, cyano group, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, 2 to 2 carbon atoms
5 acyl groups, C 2 to C 5 acyloxy groups, C 2 to C 5 alkoxycarbonyl groups, and C 2 to C 10 alkoxyalkyleneoxy which may be substituted by alkoxy or alkoxyalkyleneoxy. Can be q1 is an integer of 0 to 10, preferably 0 to 10
7, more preferably 0-5.

In R ₆₀ of the formula (CII), the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a sec-
Examples thereof include those having 1 to 8 carbon atoms such as a butyl group or a t-butyl group, a hexyl group, a 2-ethylhexyl group, and an octyl group. In the general formula (CII), -OR ₆₁ is a group that is decomposed by the action of an acid (also referred to as an acid-decomposable group). Here, R ₆₁ is a t-butyl group, methoxy t
A tertiary alkyl group (preferably having 4 to 20 carbon atoms) such as a -butyl group, a t-amyl group, a 1-ethoxyethyl group, a 1-butoxyethyl group, a 1-isobutoxyethyl group, a 1-cyclohexyloxyethyl group, 1- [2- (n-butoxy)
[Ethoxy] ethyl may have a substituent such as a 1-alkoxyethyl group (preferably having 2 to 10 carbon atoms), a 1-methoxymethyl group, a 1-ethoxymethyl group or the like which may have a substituent. An alkoxymethyl group (preferably having 2 to 2 carbon atoms)
10) a tertiary alkoxycarbonyl group (preferably having 4 to 20 carbon atoms) such as a t-butoxycarbonyl group and a t-amyloxycarbonyl group, a tetrahydropyranyl group which may have a substituent, And a trialkylsilyl group such as a tetrahydrofuranyl group, a trimethylsilyl group, a t-butyldimethylsilyl group, and a diisopropylmethylsilyl group, and a 3-oxocyclohexyl group. For each of q1, n1, m1, and p1,
When two or more, the plurality of residues present may be the same or different.

The synthesis of the compounds represented by the above general formulas (CI) and (CII) of the present invention is carried out by synthesizing a corresponding carboxylic acid or a carboxylic acid derivative such as acid chloride or a corresponding naphthol derivative with R′-OH. , R'-X (halogen) or a corresponding olefin, or a reaction of a naphthol derivative with a dialkoxycarbonyl ether.

In the positive photosensitive composition of the present invention, the dissolution inhibitors represented by the general formulas (CI) and (CII) may be used alone or in combination of two or more. good. In the positive photosensitive composition of the present invention, the total amount of the compounds represented by the general formula (CI) or (CII) is usually 1 to 3 with respect to the total solid content.
0% by weight, preferably 3 to 20% by weight, more preferably 5 to 15% by weight. If the amount is less than 1% by weight, the effect of the present invention may not be obtained. If the amount is more than 30% by weight, scum tends to be generated during development or development defects tend to increase.

Specific examples of the compound represented by the general formula (CI) include the following [CI-1] to [CI-10]
8] and specific examples of the compound represented by the general formula (CII) include the compounds represented by the following [CII-1] to [CII-52]. It is not limited to these.

[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[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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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[2] Next, the imidosulfonate acid generator contained as the component (C) in the composition of the present invention will be described. Examples of the imidosulfonate acid generator include a compound represented by the following general formula (PAG6).

[0063]

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R ²⁰⁶ is a linear group which may have a substituent,
A branched or cyclic alkyl group, an optionally substituted aralkyl group, a substituted or unsubstituted aryl group, and a camphor group. A ² represents a linear or branched alkylene group which may have a substituent, a monocyclic or polycyclic alkylene group which may have a substituent and may contain a hetero atom, Linear or branched alkenylene group which may be substituted, monocyclic or polycyclic alkenylene group which may be substituted and which may contain a hetero atom, arylene group which may be substituted, aralkylene which may be substituted Represents a group.

The linear, branched or cyclic alkyl group of R ²⁰⁶ includes methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, hexyl and octyl. And straight-chain or branched alkyl groups having 1 to 20 carbon atoms and cyclic alkyl groups such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group. Preferred substituents of the alkyl group include an alkoxy group, an acyl group, an acyloxy group, a chlorine atom, a bromine atom, an iodine atom, and a camphor group. The carbon number of the substituent is usually 10 or less.

The aralkyl group for R ^{206 includes} an aralkyl group having 7 to 12 carbon atoms such as a benzyl group or a phenethyl group. Preferred substituents of the aralkyl group include a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a nitro group, an acetylamino group, a halogen atom, and the like. ^Examples of the aryl group for R ²⁰⁶ include a phenyl group, a naphthyl group, and an anthranyl group.

Examples of the alkylene group represented by A ² include a linear or branched alkylene group having 1 to 10 carbon atoms and a monocyclic or polycyclic alkylene group which may contain a hetero atom. Examples of the linear or branched alkylene group include a methylene group, an ethylene group, a propylene group, and an octylene group. Preferred substituents of the alkylene group include an alkoxy group, an acyl group, a formyl group, a nitro group,
Acylamino group, sulfonylamino group, halogen atom,
Examples include an aryl group and an alkoxycarbonyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group,
1 carbon atom such as octyloxy group and dodecyloxy group
And alkoxy groups having a substituent such as 20 to 20 alkoxy groups or ethoxyethoxy groups. Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group. Examples of the acylamino group include an acetylamino group, a propionylamino group and a benzoylamino group. Examples of the sulfonylamino group include a methanesulfonylamino group, an ethanesulfonylamino group, and the like.
And substituted or unsubstituted benzenesulfonylamino groups such as .about.4 sulfonylamino groups and p-toluenesulfonylamino groups. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. Examples of the alkoxycarbonyl group include an alkoxycarbonyl group having 2 to 20 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, an ethoxyethoxycarbonyl group, an octyloxycarbonyl group, and a dodecyloxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the cyclic alkylene group include a monocyclic cycloalkylene group having 4 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group, and 7-oxabicyclo [2,2,
1] A polycyclic cycloalkylene group having 5 to 15 carbon atoms such as a heptylene group. Preferred substituents of the cycloalkylene group include an alkyl group having 1 to 4 carbon atoms, an alkoxy group, an acyl group, a formyl group, a nitro group, an acylamino group, a sulfonylamino group, a halogen atom, an aryl group, and an alkoxycarbonyl group. Can be The alkoxy group, acyl group, nitro group, acylamino group, sulfonylamino group, aryl group, and alkoxycarbonyl group mentioned herein have the same meanings as those described above. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the arylene group include a phenylene group and a naphthylene group. Preferred substituents of the arylene group include an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, a formyl group, a nitro group, an acylamino group, a sulfonylamino group, a halogen atom, an aryl group,
An alkoxycarbonyl group. The alkyl group, cycloalkyl group, alkoxy group, acyl group, formyl group, nitro group, acylamino group, sulfonylamino group, aryl group, and alkoxycarbonyl group mentioned above are the same as those described above. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkenylene group include alkenylene groups having 2 to 4 carbon atoms, such as an ethenylene group and a butenylene group. Preferred examples of the alkenylene group include an alkyl group, a cycloalkyl group, an alkoxy group and an acyl group. Group, formyl group, nitro group, acylamino group, sulfonylamino group, halogen atom, aryl group,
An alkoxycarbonyl group. The alkyl group, cycloalkyl group, alkoxy group, acyl group, formyl group, nitro group, acylamino group, sulfonylamino group, aryl group, and alkoxycarbonyl group mentioned above are the same as those described above. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the cyclic alkenylene group include a cyclopentenylene group and a cyclohexenylene group having 4 to 8 carbon atoms.
And monocyclic cycloalkenylene groups, 7-oxabicyclo [2,2,1] heptenylene groups, norbornenylene groups, and polycyclic cycloalkenylene groups having 5 to 15 carbon atoms. Examples of the aralkylene group include a tolylene group and a xylylene group, and examples of the substituent include the substituents described for the arylene group.

Specific examples include the following compounds, but are 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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The addition amount of these imidosulfonate acid generators depends on the total weight of the resist composition (excluding the coating solvent).
Is used in the range of usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 6% by weight based on If the amount of the imidosulfonate acid generator is less than 0.01% by weight, sufficient halftone suitability may not be obtained, and if the amount is more than 10% by weight, the profile tends to deteriorate. .

It is preferable to use a sulfonium salt in combination as the acid generator. Thereby, the sensitivity and the profile are improved. Examples of such a material include those represented by the following general formula (PAG4).

[0083]

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R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, it is an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or a substituted derivative thereof. Preferred substituents 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.

[0085] 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 may be bonded through a single bond or a substituent.

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

[0088]

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[0089]

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[0090]

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[0091]

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In the above, Ph represents a phenyl group.
The above onium salts represented by the general formula (PAG4) are known, and are described, for example, in U.S. Pat. Nos. 2,807,648 and 4,247,47.
No. 3, JP-A-53-101,331 and the like.

Further, the following may be mentioned as the sulfonium salts which may be used in combination.

[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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As the sulfonium salt as an acid generator to be used in combination, a compound represented by formula (SI) is particularly preferable.

Embedded image In the general formula (SI), Rs _{4 to} Rs ₆ each independently represent an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, a nitro group, a halogen atom, a hydroxyl group, or a carboxyl group. Represent. 1: 1-5 m: 0-5 n: 0-5. When l + m + n = 1, Rs ₄ represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, or an acyloxy group. Xs ⁻ : R—SO ₃ ⁻ , R: represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

In the general formula (SI), Rs _{4 to} Rs
The alkyl group of s _6, which may have a substituent, a methyl group, an ethyl group, a propyl group, n- butyl group, isobutyl group, sec- butyl group, t- butyl group, a pentyl group, a hexyl group, Those having 1 to 25 carbon atoms such as a heptyl group, an octyl group, a t-amyl group, a decanyl group, a dodecanyl group and a hexadecanyl group are exemplified. The cycloalkyl group may have a substituent and has 3 to 25 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecanyl group, and a cyclohexadecanyl group. Things. As the alkoxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, n
-Butoxy group, isobutoxy group, sec-butoxy group or t-butoxy group, pentyloxy group, t-amyloxy group, n-hexyloxy group, n-octyloxy group,
Those having 1 to 25 carbon atoms such as an n-dodecaneoxy group are exemplified.

Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group and a sec-butoxycarbonyl which may have a substituent. Group or a carbon number of 2 to 25 such as a t-butoxycarbonyl group, a pentyloxycarbonyl group, a t-amyloxycarbonyl group, an n-hexyloxycarbonyl group, an n-octyloxycarbonyl group, an n-dodecaneoxycarbonyl group, etc. One. The acyl group may have a substituent and has 1 carbon atom such as a formyl group, an acetyl group, a butyryl group, a valeryl group, a hexanoyl group, an octanoyl group, a t-butylcarbonyl group, and a t-amylcarbonyl group. To 25. Examples of the acyloxy group include an acetoxy group, an ethylyloxy group, a butyryloxy group, a t-butyryloxy group, and a t which may have a substituent.
-Amylyloxy group, n-hexanecarbonyloxy group,
Examples thereof include those having 2 to 25 carbon atoms such as an n-octanecarbonyloxy group, an n-dodecanecarbonyloxy group, and an n-hexadecanecarbonyloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The substituent for these groups is preferably an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), an acyl group having 2 to 5 carbon atoms, Examples thereof include 2 to 5 acyloxy groups, cyano groups, hydroxyl groups, carboxy groups, C 2 to C 5 alkoxycarbonyl groups, and nitro groups. When l + m + n = 1, Rs ₄ represents an alkyl group optionally having a substituent, a cycloalkyl group optionally having a substituent, an alkoxy group optionally having a substituent, a substituent Represents an alkoxycarbonyl group which may have a substituent, an acyl group which may have a substituent, and an acyloxy group which may have a substituent. In this case, Rs ₄ is
The number of carbon atoms is preferably 2 or more, more preferably 4 or more.

Among the above, alkyl groups which may have a substituent of Rs _{4 to} Rs ₆ include methyl, ethyl, propyl, isopropyl, butyl, t-
A butyl group, an n-pentyl group, a t-amyl group, an n-hexyl group, an n-octyl group, and a decanyl group are preferable.As the cycloalkyl group, a cyclohexyl group, a cyclooctyl group, which may have a substituent, A cyclododecanyl group is preferable, and as the alkoxy group, a methoxy group, an ethoxy group, an isopropoxy group, an n-
Butoxy group, sec-butoxy group, t-butoxy group, pentyloxy group, t-amyloxy group, n-hexyloxy group, n-octyloxy group, n-dodecaneoxy group is preferable, and the alkoxycarbonyl group is preferably a substituent. Methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, t-amyloxycarbonyl group, n -Hexyloxycarbonyl group, n-octyloxycarbonyl group, n-dodecaneoxycarbonyl group is preferable, and the acyl group may have a substituent, formyl group, acetyl group, butyryl group, valeryl group, hexanoyl group. , Octanoyl group, t
-Butylcarbonyl group, t-amylcarbonyl group is preferable, and the acyloxy group may have a substituent,
Acetoxy group, ethylyloxy group, butyryloxy group,
A t-butyryloxy group, a t-amylyloxy group, an n-hexanecarbonyloxy group, and an n-octanecarbonyloxy group are preferred.

Among the above substituents, more preferred R
Specific examples of s _{4 to} Rs ₆ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-pentyl group, a t-amyl group, an n-hexyl group,
n-octyl group, cyclohexyl group, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, t-butoxy group, pentyloxy group, t-amyloxy group, hexyloxy group, n-octyloxy group, methoxycarbonyl group , Ethoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, t-amyloxycarbonyl group, hexyloxycarbonyl group, n-octyloxycarbonyl group, formyl group, acetyl group, butyryl group, hexanoyl group, octanoyl group , T-butylcarbonyl group, t-amylcarbonyl group, acetoxy group, ethylyloxy group, butyryloxy group, t-butyryloxy group, t-amylyloxy group, n-hexanecarbonyloxy group, n-octanecarbonyloxy group, hydroxyl group, Chlorine atom, bromine atom, Toro group, and the like.

These groups may have a substituent. Preferred substituents are a methoxy group, an ethoxy group and a t-group.
Butoxy, chlorine, bromine, cyano, hydroxyl,
Examples include a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, and a t-amyloxycarbonyl group. Also, l, m, and n are each preferably 1 to 3.

[0107] sulfonium compound represented by the general formula (SI) used in the present invention has a counter anion, Xs ^- as a specific structure R-SO ₃ as described above ^- used sulfonic acid having a. The aliphatic hydrocarbon group for R is preferably a linear or branched alkyl group having 1 to 20 carbon atoms or a cyclic alkyl, and may have a substituent. Further, the aromatic group as R is preferably an aromatic group having 6 to 14 carbon atoms, and may have a substituent. Examples of the alkyl group for R include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group and a 2-ethylhexyl which may have a substituent. Groups, decyl group, dodecyl group, etc., as the cyclic alkyl group, may have a substituent, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclododecyl group, adamantyl group, norbornyl group, camphor group, Examples thereof include a tricyclodecanyl group and a menthyl group. Examples of the aromatic group include a phenyl group and a naphthyl group which may have a substituent. Preferred substituents have 1 to 15 carbon atoms.
Alkyl group, alkoxy group, alkoxycarbonyl group, halogen atom, etc., specifically, methyl group, t-butyl group, methoxy group, ethoxy group, t-butoxy group, chlorine atom, bromine atom, cyano group , A hydroxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, a t-amyloxycarbonyl group and the like.

As R, specifically, methyl, trifluoromethyl, ethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, n-propyl, n-butyl, nona Fluorobutyl group, n-pentyl group, n-hexyl group, n-octyl group, heptadecafluorooctyl group, 2-ethylhexyl group, decyl group,
Dodecyl, cyclopentyl, cyclohexyl, camphor, phenyl, naphthyl, pentafluorophenyl, p-toluyl, p-fluorophenyl, p-
Chlorophenyl, p-hydroxyphenyl, p-methoxyphenyl, dodecylphenyl, mesityl, triisopropylphenyl, 4-hydroxy-1-naphthyl, 6-hydroxy-2-naphthyl and the like can be mentioned. .

More preferred examples of R include a methyl group, a trifluoromethyl group, an ethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, an n-butyl group, a nonafluorobutyl group, -Hexyl group, n-
Octyl group, heptadecafluorooctyl group, 2-ethylhexyl group, camphor group, phenyl group, naphthyl group, pentafluorophenyl group, p-toluyl group, p-fluorophenyl group, p-chlorophenyl group, p-methoxyphenyl group, Dodecylphenyl group, mesityl group, triisopropylphenyl group, 4-hydroxy-1-naphthyl group,
And a 6-hydroxy-2-naphthyl group.

The total number of carbon atoms of the generated acid is preferably from 1 to 30. The number is more preferably 1 to 28, and still more preferably 1 to 25. If the total number of carbon atoms is less than 1, the pattern formation may be hindered such as a t-top shape, and if it exceeds 30, the development residue may be undesirably generated. The general formula (S
Specific examples of the compound represented by I) are shown below, but the present invention is not limited thereto. These compounds are
They are used alone or in combination of two or more.

[0111]

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[0112]

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[0113]

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[0114]

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[0115]

[Of 60]

[0116]

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The amount of the sulfonium salt or the photoacid generator represented by the general formula (SI) is determined by the above formula (PAG)
It is 200% by weight or less, preferably 15 to 150% by weight, more preferably 30 to 100% by weight, based on the photoacid generator represented by 6).

The compound represented by the general formula (SI) is obtained, for example, by reacting an aryl Grignard reagent such as arylmagnesium bromide with a substituted or unsubstituted phenyl sulfoxide, and converting the obtained triaryl sulfonium halide with a corresponding sulfonic acid. It can be synthesized by salt exchange. Further, the substituted or unsubstituted phenylsulfoxide and the corresponding aromatic compound are condensed using an acid catalyst such as methanesulfonic acid / diphosphorus pentoxide or aluminum chloride,
It can be synthesized by a method of salt exchange, a method of condensation and salt exchange between a diaryliodonium salt and a diarylsulfide using a catalyst such as copper acetate or the like. The salt exchange can be performed by a method of once converting to a halide salt and then converting it to a sulfonate using a silver reagent such as silver oxide, or by using an ion exchange resin. The sulfonic acid or sulfonic acid salt used for the salt exchange may be a commercially available one, or may be obtained by hydrolysis of a commercially available sulfonic acid halide.

A photoacid generator other than the above sulfonium salts may be used in combination. Photoacid generators that may be used in combination, other than those specified above, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes,
Known light used in photochromic agents or micro resists (ultraviolet rays of 400 to 200 nm, far ultraviolet rays,
Particularly preferably, g line, h line, i line, KrF excimer laser beam), ArF excimer laser beam, electron beam, X
Compounds that generate an acid by a beam, a molecular beam, or an ion beam, and mixtures thereof are included. The amount of the photoacid generator other than the sulfonium salt which may be used in combination is usually 100% by weight or less, and preferably 80% by weight, based on the photoacid generator represented by the general formula (PAG6). Or less, more preferably 50% by weight or less. For example, diazonium salts, ammonium salts, phosphonium salts,
Onium salts such as iodonium salts, selenonium salts and arsonium salts, organic halogen compounds, organic metals / organic halides, photodecomposition represented by photoacid generators having an o-nitrobenzyl-type protecting group, etc. to generate sulfonic acid Compounds, disulfone compounds, diazoketosulfones, diazodisulfone compounds and the like. 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.

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

Among the above-mentioned compounds generating an acid, those effectively used together will be 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).

[0122]

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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.

[0124]

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(2) An iodonium salt represented by the following general formula (PAG3).

[0126]

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Here, 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.

Z ^- represents a counter anion, for example, B
F ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ²⁻ , Cl
Condensed polynuclear aromatic sulfonic acid anions such as O ₄ ⁻ , CF ₃ SO ₃ ⁻ , pentafluorobenzene sulfonic acid anion, naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, and sulfonic acid group-containing dyes. Is not limited to these.

Further, Ar ¹ and Ar ² may be bonded to each other via a single bond or a substituent.

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

[0131]

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[0132]

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[0133]

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In the above, Ph represents a phenyl group.
The above onium salts represented by the general formula (PAG3) are known, and are described, for example, in U.S. Pat. Nos. 2,807,648 and 4,247,47.
No. 3, JP-A-53-101,331 and the like.

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

[0136]

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In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. Specific examples include the following compounds, but are not limited thereto.

[0138]

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

[0140]

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Here, each R independently 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.

[0142]

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[0143]

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[3] Next, at least one of the repeating units represented by the general formulas (Ia) and (Ib) contained in the composition of the present invention as the component (A) and the compound represented by the general formula (II) A polymer having a repeating unit represented by Formula (1) and having a group decomposable by the action of an acid (hereinafter, abbreviated as “resin according to the present invention”) will be described.

In the above formula (Ia), R ₁ , R
₂ is each independently a hydrogen atom, a cyano group, a hydroxyl group, -C
_{OOH, -COOR 5, -CO-NH} -R 6, -CO-
NH-SO ₂ -R _6, which may be substituted, an alkyl group, an alkoxy group or a cyclic hydrocarbon group, or the -
Represents a Y group. Wherein, R ₅ may have a substituent, an alkyl group, cyclic hydrocarbon group or the -Y group. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. In the above-mentioned -Y group, R ₂₁ to
R ₃₀ each independently represents a hydrogen atom or an alkyl group which may have a substituent, and a and b represent 1 or 2. 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.

In the formula (Ib), Z ₂ represents —O— or —N (R ₃ ) —. Here, R ₃ is a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OSO ₂ —R ₄
Represents R ₄ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue.

The above R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
As the alkyl group for R ₆ , R _{21 to} R ₃₀ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable. And 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 ₁ , R ₂ , R ₅ , and R ₆ include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a 2-methyl-2-adamantyl group, a norbornyl group, a boronyl group, and 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. Examples of the alkoxy group in R ₁ and R ₂ include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.
The haloalkyl group represented by R ₃ and R ₄ can be exemplified trifluoromethyl, nano-fluoro butyl group, pentadecafluorooctyl group, a trichloromethyl group and the like. Examples of the cycloalkyl group for R ₄ include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

Examples of further substituents of 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 and an acyloxy group. 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.

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

Specific examples of the repeating unit represented by formula (Ia) include the following [I-1] to [I-65], but the present invention is not limited to these specific examples. Absent.

[0151]

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[0152]

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[0153]

[Of 75]

[0154]

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[0155]

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[0156]

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

[0158]

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[0159]

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In the above formula (II), R ₁₁ , R
Each ₁₂ 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 containing two bonded carbon atoms (C-C) and forming an alicyclic structure which may have a substituent.

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. The alkyl group for R ₁₁ and R ₁₂ is preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, more preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms. More preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
t-butyl group.

Further substituents on the alkyl groups of R ₁₁ and R ₁₂ 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 and an iodine atom, and 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. And formyl group as acyl group,
An acetyl group and the like can be mentioned, and an acyloxy group can be an acetoxy group and the like.

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 in the resin, and in particular, a bridged group An atomic group for forming a bridged alicyclic structure forming a repeating unit of the alicyclic hydrocarbon is preferable. Examples of the skeleton of the formed alicyclic hydrocarbon include those represented by the following structures.

[0164]

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[0165]

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

The skeleton of the alicyclic hydrocarbon may have a substituent. Examples of such a substituent include R _{13 to} R ₁₆ in the general formula (II-A) or (II-B). Among the repeating units having a bridged alicyclic hydrocarbon, a repeating unit represented by the above general formula (II-A) or (II-B) is more preferable. In the above general formula (II-A) or (II-B), R ₁₃
To R ₁₆ are each independently a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR ₅ (where R ₅ may have a substituent, an alkyl group, a cyclic hydrocarbon group, or the above general formula ( represents the same group -Y as in I)), group decomposable by the action of an acid, -C (= O) -X- a-R 17, or optionally substituted alkyl group or cyclic hydrocarbon Represents a hydrogen group. n represents 0 or 1. X is an oxygen atom,
Sulfur atom, -NH -, - NHSO ₂ - or -NHSO ₂
Represents NH-. R ₁₇ are, -COOH, -COOR _5, -
CN, hydroxyl, optionally substituted alkoxy _{group, -CO-NH-R 6,} -CO-NH-SO 2 -R 6
(R ₅ and R ₆ have the same meanings as described above) or the above-mentioned general formula (I
a) represents a -Y group. A represents a single bond or a divalent linking group.

In the resin according to the present invention, the acid-decomposable group
Is -C (= O) -XA-R ₁, -C (= O)-
XAR_TwoMay be included, or of Z in the general formula (II)
It may be included as a substituent. As the structure of the acid-decomposable group
Is -C (= O) -X₁-R₀It is represented by Where R₀
Are tertiary alkyl groups such as t-butyl group and t-amyl group.
Group, isobornyl group, 1-ethoxyethyl group, 1-butyl
Toxylethyl group, 1-isobutoxyethyl group, 1-cycl
1-alkoxyethyl group such as rohexyloxyethyl group,
Alkyls such as 1-methoxymethyl group and 1-ethoxymethyl group
Coxymethyl group, tetrahydropyranyl group, tetrahydride
Lofuranyl group, trialkylsilyl ester group, 3-O
Oxocyclohexyl ester group, 2-methyl-2-ada
Mantyl group, mevalonic lactone residue, 2- (γ-butyl
Tyrolactonyloxycarbonyl) -2-propyl group, etc.
Can be mentioned. X₁Has the same meaning as X described above.

Examples of the halogen atom for R _{13 to} R ₁₆ include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom.

The alkyl group for R _{13 to} R ₁₆ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. And more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a t-butyl group.

Examples of the cyclic hydrocarbon group for R _{13 to} R ₁₆ include a cyclic alkyl group and a bridged hydrocarbon group, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a 2-methyl-2-adamantyl. Group, norbornyl group, boronyl group, isobornyl group,
Examples include a tricyclodecanyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, and a tetracyclododecanyl group. The ring formed by combining at least two of the above R _{13 to} R ₁₆ includes cyclopentene, cyclohexene, cycloheptane, cyclooctane and the like having 5 to 1 carbon atoms.
And 2 rings.

As the alkoxy group for R ₁₇ ,
Examples thereof 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 on the above-mentioned 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 and an acyloxy group. As the halogen atom, a chlorine atom, a bromine atom, a fluorine atom,
And iodine 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 acyl group include a formyl group and an acetyl group. Examples thereof include an acetoxy group.

Examples of the divalent linking group of A include a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, and a carbonyl group, similarly to the divalent linking group of A in formula (Ia). , An ester group, an amide group,
A single one selected from the group consisting of a sulfonamide group, a urethane group, and a urea group, or a combination of two or more groups is exemplified. As the alkylene group and the substituted alkylene group in the above A, 2 of A in the above general formula (Ia)
Examples are the same as those of the valent linking group.

In the resin according to the present invention, the group decomposed by the action of an acid is a repeating unit represented by the general formula (Ia), a repeating unit represented by the general formula (Ib) or a repeating unit represented by the general formula (II) It can be contained in at least one of the repeating units represented and the repeating units of the copolymer component described below.

The formula (II-A) or (II
The various substituents of R _{13 to} R ₁₆ in —B) may be an atomic group for forming an alicyclic structure in the above general formula (II) or an atomic group Z for forming a bridged alicyclic structure. It also serves as a substituent.

The formula (II-A) or (II
-B) As specific examples of the repeating unit represented by the following [II]
-1] to [II-166], but the present invention is not limited to these specific examples.

[0178]

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[0179]

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[0180]

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[0181]

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[0182]

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[0183]

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[0184]

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[0185]

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[0186]

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[0187]

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[0188]

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[0189]

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[0190]

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[0191]

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[0192]

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[0193]

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[0194]

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The resin according to the present invention comprises at least one of the repeating units represented by the general formula (Ia) and the general formula (Ib), and the resin represented by the general formula (II) (general formula (II-
A) and one or more kinds of repeating units represented by general formula (II-B)), in addition to dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resist For the purpose of adjusting the resolving power, heat resistance, sensitivity and the like, which are the general requirements of the above, copolymers containing repeating units of various monomers can be prepared. Preferred copolymerization components are those represented by the following general formula (IV)
') And (V').

[0196]

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Here, in the formula, Z is an oxygen atom, -NH-,-
_{N (-R 50) -, -} N (-OSO 2 R 50) - represents, R
₅₀ also has the same meaning as the above (substituted) alkyl group and (substituted) cyclic hydrocarbon group. The general formulas (IV ′) and (V
') The following [IV'
-9] to [IV'-16], [V'-9] to [V'-1]
6], but is not limited to these specific examples.

[0198]

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[0199]

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In the resin according to the present invention, the following monomers may be further copolymerized to give a repeating unit constituting the resin as long as the effects of the present invention are effectively obtained. However, it is not limited 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, and (4) film loss (hydrophobicity, alkali (Selection of a soluble group), (5) adhesion of the unexposed portion to the substrate, and (6) dry etching resistance can be finely adjusted. Examples of such a comonomer include acrylates, methacrylates,
Examples thereof include compounds having one addition-polymerizable unsaturated bond selected from acrylamides, methacrylamides, allyl compounds, vinyl ethers, 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 acid esters such as alkyl (preferably having 1 to 10 carbon atoms in the alkyl group) methacrylate (eg, 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, for example, acrylamide, N-alkylacrylamide, wherein the alkyl group has 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl Group, cyclohexyl group, hydroxyethyl group, etc.), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, Cyclohexyl group, etc.), N-
Hydroxyethyl-N-methylacrylamide, N-2
-Acetamidoethyl-N-acetylacrylamide and the like;

Methacrylamides, 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-dialkylmethacrylamide (an alkyl group includes an ethyl group, a propyl group, a butyl group, etc.), N-hydroxyethyl-N-methylmethacrylamide and the like;

Allyl compounds such as allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxy Ethanol, etc .;

Vinyl ethers such as 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, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl Butyl 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 and the like;

Dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); acrylic acid, methacrylic acid, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile and the like.

In the resin according to the present invention, the compound represented by the general formula (I)
a) and / or a repeating unit represented by the general formula (Ib) and a repeating unit represented by the general formula (II) (including the general formulas (II-A) and (II-B)) The amount should be appropriately set in consideration of the desired dry etching resistance of the resist, sensitivity, prevention of pattern cracking, substrate adhesion, resist profile, and resolution, heat resistance, etc. which are necessary requirements of general resists. Can be. In general, the resin represented by the general formula (I)
a) and / or the content of the repeating unit represented by the general formula (Ib) and the repeating unit represented by the general formula (II) is 25 mol% in the total monomer repeating units of the resin.
The above is suitable, preferably at least 30 mol%, more preferably at least 35 mol%.

Further, in the resin according to the present invention, the content of the repeating unit (general formula (IV ′) or general formula (V ′)) derived from the above-mentioned preferable comonomer in the resin is also within a desired range. Although it can be appropriately set according to the performance of the dist, in general, the repeating unit represented by the general formula (Ia) and / or the general formula (Ib) and the repeating unit represented by the general formula (II) 99 for the total number of moles
It is preferably at most 90 mol%, more preferably at most 90 mol%, even more preferably at most 80 mol%. In addition, the content of the repeating unit based on the monomer of the further copolymerization component in the resin can also be appropriately set according to the desired dist performance, but generally, the general formula (Ia) and the general formula (Ia) /
Alternatively, it is preferably 99 mol% or less, more preferably 90 mol%, based on the total number of moles of the repeating unit represented by the general formula (Ib) and the repeating unit represented by the general formula (II).
Mol% or less, more preferably 80 mol% or less.
When the amount of the repeating unit based on the monomer of the further copolymer component exceeds 99 mol%, the effect of the present invention is not sufficiently exhibited, so that it is not preferable.

In the resin according to the present invention, the group decomposed by the action of an acid is represented by a repeating unit represented by the general formula (Ia) and / or the general formula (Ib) or a general formula (II) May be contained in any of the repeating units based on the monomer of the copolymer component, but the content of the repeating unit containing a group that is decomposed by the action of an acid may be contained in the total repeating units of the resin. The amount is suitably from 8 to 60 mol%, preferably from 10 to 55 mol%, and more preferably from 12 to 50 mol%. In addition, the present composition is A
When used for rF exposure, the resin preferably does not have an aromatic ring from the viewpoint of transparency to ArF light.

The resin according to the present invention is obtained by copolymerizing a monomer corresponding to the repeating unit represented by the general formula (II) and maleic anhydride with a monomer of the copolymer component when the copolymer component is used. Polymerized, copolymerized in the presence of a polymerization catalyst, and a repeating unit derived from maleic anhydride of the obtained copolymer is subjected to ring-opening esterification with an alcohol under basic or acidic conditions, or is hydrolyzed, It can also be synthesized by a method of converting the carboxylic acid moiety generated thereafter into a desired substituent.

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 exposure to far ultraviolet rays of the present invention, the amount of the resin according to the present invention in the entire composition is preferably 40 to 99.99% by weight, and more preferably the total solid content of the resist. Is 50 to 99.97% by weight.

The positive photoresist composition for deep ultraviolet exposure according to the present invention preferably contains (C) a fluorine-based and / or silicon-based surfactant. The fluorine-based and / or silicon-based surfactant is at least one of a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom. When the positive photoresist composition for deep ultraviolet exposure of the present invention contains the above acid-decomposable resin and the above surfactant, the sensitivity, resolution, and substrate adhesion can be reduced when using an exposure light source of 250 nm or less, particularly 220 nm or less. A resist pattern having excellent resistance and dry etching resistance and having less development defects and scum can be obtained. As these surfactants, for example, JP-A-62-36663, JP-A-61-226746
No., JP-A-61-226745, JP-A-62-170950, JP-A-63
-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, U.S. Pat.No. 5,405,720, U.S. Pat.No. 5,360,692, U.S. Pat.
No. 0, US Pat. No. 5,436,098, US Pat. No. 5,576,143, US Pat. No. 5,945,511, and US Pat. No. 5,824,451. The following commercially available surfactants can be used as they are. As commercially available surfactants that can be used, for example, F-top EF301, EF303, (Shin-Akita Kasei
Co., Ltd.), Florado FC430, 431 (Sumitomo 3M Limited)
), Megafac F171, F173, F176, F189, R08 (Dai Nippon Ink Co., Ltd.), Surflon S-382, SC101, 102,
Fluorinated surfactants such as 103, 104, 105, and 106 (manufactured by Asahi Glass Co., Ltd.) and silicon-based surfactants can be exemplified. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant.

The amount of the surfactant is usually 0.001% 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 can be used alone or in combination of two or more.

Examples of the other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene alkyl allyl ethers such as oxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate Fatty acid esters such as sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate Nonionic surfactants such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, etc. Can be mentioned. The amount of these 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. These surfactants may be added alone or in some combination.

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

[0219]

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[0220] In, R ^250, R ²⁵¹ and R ^252, which may be the same or different, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, hydroxyalkyl of 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 be bonded to each other to form a ring.

[0221]

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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] octane, 4-dimethylaminopyridine,
Hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines, tertiary morpholines such as CHMETU, bis (1,2,2,6,6-pentamethyl-
Hindered amines such as (4-piperidyl) sebagate and the like can be mentioned. By using these, the density dependency becomes excellent.

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, hexamethylene Preferred are tetramine, CHMETU, and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.

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 solid content of the entire photosensitive resin 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 photoresist composition of the present invention may further contain an acid-decomposable dissolution inhibiting compound, a dye,
A plasticizer, a sensitizer, a compound that promotes solubility in a developer, and the like can be contained.

The photosensitive composition of the present invention is dissolved in a solvent in which each of the above components is dissolved, 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, ethyl lactate, 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 include 2
-Heptanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, methyl lactate,
Examples include ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, N-methylpyrrolidone, and tetrahydrofuran.

The positive resist composition of the present invention is applied on a substrate to form a thin film. The thickness of this coating film is preferably from 0.2 to 1.2 μm. 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, α-silicon, and an organic film type formed of 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 if necessary), a spinner, a coater, and the like. After coating by an appropriate coating method such as that described above, exposure through a predetermined mask, baking and development can provide a good resist pattern. Here, the exposure light is preferably 150
It is light having a wavelength of nm to 250 nm. Specifically, Kr
F excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157
nm), X-rays, electron beams and the like.

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

[0234]

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 Example of Resins (1) to (6)) <Synthesis of Resin (1)> The reaction of methacrylic acid ester of 3-oxo-1,1-dimethylbutanol with cyclopentadientadienene was carried out. An obtained equimolar mixture of the tetracyclododecene derivative (1-1) having the following structure and maleic anhydride is dissolved in tetrahydrofuran, and the solid content is 50%.
Was prepared. This was charged into a three-necked flask and heated at 60 ° C. under a nitrogen stream. When the reaction temperature was stabilized, 5 mol% of a radical initiator V-60 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 6 hours, the reaction mixture was diluted twice with tetrahydrofuran, and then poured into a large amount of hexane to precipitate a white powder. The precipitated powder was taken out by filtration and dried to obtain the intended resin (1).

[0236]

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The molecular weight analysis of the obtained resin (1) by GPC was 6800 (weight average) in terms of polystyrene. The NMR spectrum revealed that the molar ratio of the repeating unit of tetracyclododecene and the repeating unit of maleic anhydride in the resin (1) was 50/50. Resins (2) to (6) were synthesized in the same manner as above. The structures of the synthesized resins (1) to (6) are described below.

[0238]

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[0239]

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Table 1 shows the molar ratio and weight average molecular weight of each repeating unit of the resins (2) to (6).

[0241]

[Table 1]

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.)

[0244]

[Table 2]

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

[0246]

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[0247]

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Synthesis Example (3) Synthesis of Resin (28) (Hybrid Type) Norbornene, maleic anhydride, tbutyl acrylate, and 2-methylcyclohexyl-2-propyl acrylate were 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.

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

[0250]

[Table 3]

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

[0252]

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[0253]

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[0254]

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[0255]

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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.

[0258]

[Table 4]

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

[0260]

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[0261]

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[0262]

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[0263]

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[0264]

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Examples 1 to 57 and Comparative Examples 1 and 2 (Preparation and Evaluation of Positive Photoresist Composition) As shown in Table 5, the acid-decomposable resin 1.4 synthesized in the above synthesis example was used.
g, a photoacid generator, a dissolution inhibitor, 5 mg of an organic basic compound (amine), and if necessary, 10 mg of a surfactant,
After each dissolved in a solvent at a solid content of 15% by weight,
After filtration through a 0.1 μm microfilter, positive photoresist compositions of Examples 1 to 57 shown in Table 5 were prepared. Further, as Comparative Examples 1 and 2, positive photoresist compositions shown in Table 5 were prepared in the same manner as in Examples 1 to 57, using the following resin (R1) or (R2).

[0266]

[Table 5]

[0267]

[Table 6]

[0268]

[Table 7]

Each compound in Table 5 is as follows. [Solvent] S1: Propylene glycol monomethyl ether acetate S2: Ethyl lactate S3: Butyl acetate S4: 2-Heptanone S5: Propylene glycol monomethyl ether S6: Ethyl ethoxypropionate S7: γ-butyrolactone S8: Ethylene carbonate S9: Propylene carbonate S10: Propylene glycol monoethyl ether acetate S11: Ethyl 2-hydroxypropionate

[Surfactant] W-1: Megafac F176 (manufactured by Dainippon Ink and Chemicals, Inc.) (fluorine) W-2: Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.) (fluorine) W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) W-4: Polyoxyethylene nonyl phenyl ether W-5: Troysol S-366 (Troy Chemical Co., Ltd.)
Made)

[Organic basic compound] 1: DBU (1,8-diazabicyclo [5.4.0]-
7-undecene) 2: 4-DMAP (4-dimethylaminopyridine) 3: TPI (2,4,5-triphenylimidazole) 4: 2,6-diisopropylaniline 5: antipyrine 6: tri-n-octylamine 7 ： Dicyclohexylmethylamine

[Resin used in Comparative Examples] Resin R1: Resin A-1 having the following structure and used in Example 2 of EP1048983A1

[0273]

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Resin R2: Polymer A-2 used in Example 4 of JP-A-11-202491

[0275]

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[Dissolution inhibitor used in Comparative Example 2] IH-1

[0277]

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(Evaluation Test) [Side Rope Light Resistance by Halftone Mask Exposure]
Each resist film was placed on a 4-inch Bare Si substrate in a 0.
Apply to a thickness of 30 μm and apply 140
C. and dried for 60 seconds. Next, exposure was performed using an ArF stepper manufactured by ISI via a halftone mask (transmittance: 80%) having a 0.20 μm contact hole pattern (Hole Duty ratio = 1: 3). After exposure, 140 ° C,
Heat treatment for 60 seconds, and then 2.38% TMA
After paddle development with H for 60 seconds, the image was washed with pure water for 30 seconds and spin-dried to obtain an image. At this time, the contact hole (mask) having a diameter of 0.20 μm is 0.16 μm.
The optimal exposure amount is defined as Eopt, the minimum exposure amount at which the side-rope light is transferred onto the resist substrate is defined as Elimit, and the ratio Elimit / Eopt thereof is used as an index of the side-rope light resistance. At this time, the value of Comparative Example 1 was normalized to 1, and other side-rope light resistance was shown by relative evaluation. The larger the value is, the better the side rope light resistance is, and the smaller the value is, the worse the side rope light resistance is.

[Sensitivity and Profile] Brewer
ARC-25 manufactured by Science Co., Ltd. is coated on a silicon wafer by a spin coater at 30 nm and dried, and then the obtained positive photoresist composition is coated thereon, and dried at 140 ° C. for 90 seconds. A 4 μm positive photoresist film was formed, and an ArF excimer laser (193 nm wavelength, NA = 0.6 manufactured by ISI, Inc.
Exposure was performed with a 1/2 pitch contact hole pattern (mask size 0.16 μm) using an F stepper. 1. heat treatment after exposure at 140 ° C. for 90 seconds;
The resist pattern profile was obtained by developing with a 38% by weight aqueous solution of tetramethylammonium hydroxide and rinsing with distilled water. The resist pattern on the silicon wafer thus obtained was observed with a scanning microscope, and the resist was evaluated as follows. The sensitivity is defined as the minimum exposure for reproducing a contact hole of 0.16 μm, and the relative exposure when the resist exposure of Example 1 is set to 1.0 is relative sensitivity (exposure of other resist / exposure of Example 1). Amount). (Profile) The cross section of the contact hole pattern obtained at the time of the above sensitivity evaluation was observed with a scanning microscope, and a taper shape or a case of a trumpet shape in which the surface portion of the pattern was excessively open was evaluated as ×, and the others were evaluated as ○. Was evaluated. Table 6 shows the evaluation results.

[0280]

[Table 8]

[0281]

[Table 9]

From the results shown in Table 6, it can be seen that the composition of the present invention is excellent in the resistance against side lobe light by halftone mask exposure. In addition, by using a sulfonium salt as an acid generator in combination, sensitivity and profile can be improved, and by using a sulfonium salt of the general formula (SI) in combination, the side lobe light resistance by halftone mask exposure is improved. It turns out that it becomes.

[0283]

According to the present invention, a positive photoresist composition for exposure to far ultraviolet rays which is excellent in the suitability of a halftone phase shift mask in the manufacture of semiconductor devices, and a positive photoresist composition for exposure to ultraviolet rays which is also excellent in sensitivity and profile. Type photoresist compositions can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/00 C08K 5/00 C08L 35/00 C08L 35/00 45/00 45/00 G03F 7/004 501 G03F 7/004 501 503 503A H01L 21/027 H01L 21/30 502R F term (reference) 2H025 AA01 AA02 AA03 AB16 AC04 AC08 AD03 BE00 BE07 BE10 BG00 CB08 CB10 CB41 CC20 4J002 BH021 BK001 ED0066 E066H ED001 EV237 EV298 EV308 EX036 FD200 FD206 FD207 FD208 GH00 GP03 HA05 4J100 AJ09P AK32P AL34P AL36P AL39P AL41P AM39P AM43P AM45P AM47P AR09Q AR11Q AR21Q BA02P BA02P BA04P BA04P BA02P BA02P BA02P BA02P BA02P BA02P BA02P BA02P BA02P BA58Q BB01Q BB18P BC04P BC04Q BC08P BC08Q BC09 P BC09Q BC12P BC12Q BC53P BC53Q CA04 CA05 JA38

Claims (3)

[Claims] (A) The general formula (Ia) and the general formula (Ib)
(B) a polymer having at least one of the repeating units represented by the formula (II) and a repeating unit represented by the general formula (II) and having a group decomposable by the action of an acid; A positive photoresist composition for deep ultraviolet exposure, comprising: a dissolution inhibitor represented by CII); and (C) an imidosulfonate acid generator represented by formula (PAG6). Embedded image In the formula (Ia): R ₁ and R ₂ are each independently a hydrogen atom,
Cyano group, hydroxyl group, -COOH, -COOR _5, -CO
—NH—R ₆ , —CO—NH—SO ₂ —R ₆ , an optionally substituted alkyl group, alkoxy group or cyclic hydrocarbon group, or the following —Y group. X represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or -NHSO ₂ NH-
Represents Here, R ₅ may have a substituent,
Represents an alkyl group, a cyclic hydrocarbon group or the following -Y group. R
₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. A represents a single bond or a divalent linking group. —Y group; (In the —Y group, R _{21 to} R ₃₀ each independently represent a hydrogen atom or an alkyl group which may have a substituent. A and b represent 1 or 2.) In the formula (Ib) : Z ₂ is, -O- or -N (R ₃₎ - represents a. Here, R ₃ represents a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OSO ₂ —R ₄ . R ₄ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue. In the formula (II), 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 two bonded carbon atoms (C
-C) and represents an atomic group for forming an alicyclic structure which may have a substituent. Embedded image In the general formula (CI), X represents an oxygen atom, a sulfur atom, -N
(R ₅₃ ) — or a single bond. R ₅₁ , R ₅₂ and R
₅₃ independently represents a hydrogen atom or an alkyl group which may have a substituent, and R ′ represents —COOR ′, a group constituting an acid-decomposable group. R represents a bridged hydrocarbon, a saturated cyclic hydrocarbon or an n1 valent residue containing a naphthalene ring. n1 represents an integer of 1 to 4, and q1 represents an integer of 0 to 10. In the general formula (CII), R ₆₀ represents an alkyl group which may have a substituent or a halogen atom;
₆₁ represents a group constituting an acid-decomposable group at -OR ₆₁ , m
1 shows the integer of 0-4. p1 represents an integer of 1 to 4. Embedded image R ²⁰⁶ represents a linear, branched, or cyclic alkyl group which may have a substituent, an aralkyl group which may be substituted, a substituted or unsubstituted aryl group, or a camphor group. A ² is a linear or branched alkylene group which may have a substituent, a monocyclic or polycyclic alkylene group which may have a substituent and may contain a hetero atom, Straight-chain, branched alkenylene group which may be substituted,
A monocyclic or polycyclic alkenylene group which may contain a hetero atom, an arylene group which may be substituted, and an aralkylene group which may be substituted; 2. The positive photoresist composition for deep ultraviolet exposure according to claim 1, further comprising a sulfonium salt as an acid generator. 3. The positive photoresist composition for deep ultraviolet exposure according to claim 2, wherein the sulfonium salt is a compound represented by the general formula (SI). Embedded image In the general formula (SI), Rs _{4 to} Rs ₆ each independently represent an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, a nitro group, a halogen atom, a hydroxyl group, or a carboxyl group. Represent. 1: 1-5 m: 0-5 n: 0-5. When l + m + n = 1, Rs ₄ represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, or an acyloxy group. Xs ⁻ : R—SO ₃ ⁻ , R: represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group.