JPH11125907A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain positive type and negative type radiation sensitive resin compsns. excellent in resolution and pattern shape and not causing a nano-edge roughenese or film surface roughening. SOLUTION: The positive type radiation sensitive resin compsn. contains an acid-dissociable group-contg. resin or an alkali-soluble resin and an alkali solubility controlling agent and a radiation sensitive acid generating agent comprising a compd. when generates a carboxylic acid having >=150 deg.C b.p. when irradiated and a compd. which generates an acid other than the carboxylic acid when being irradiated. The negative type radiation sensitive resin compsn. contains an alkali-soluble resin, a crosslinking agent and the above radiation sensitive acid generating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a radiation-sensitive resin composition, and more particularly to a combination of a compound capable of generating a carboxylic acid upon irradiation with a compound capable of generating another acid upon irradiation. The present invention relates to a positive and negative radiation-sensitive resin composition containing a radiation-sensitive acid generator, and useful as a resist suitable for fine processing using various radiations.

[0002]

2. Description of the Related Art In the field of microfabrication represented by the manufacture of integrated circuit elements, design rules in lithography have been rapidly miniaturized in order to obtain a higher degree of integration of integrated circuits. The development of a lithography process capable of stably performing high-precision fine processing with a line width of 0.5 μm or less has been strongly promoted. For this reason, resists used for microfabrication are required to be able to accurately form a resist pattern having a line width of 0.5 μm or less. However, conventional visible light (wavelength 800 to 400 nm) and near ultraviolet (wavelength) 400 ~
In the method using (300 nm), it is extremely difficult to form such a fine pattern with high accuracy. Therefore, a lithography process using radiation of a short wavelength (wavelength of 300 nm or less) that can achieve a wider depth of focus and is effective for miniaturization of design rules has been proposed. A lithography process using such short-wavelength radiation includes, for example, a bright line spectrum (wavelength 2) of a mercury lamp.
54 nm), KrF excimer laser (wavelength 248 n)
m), a method using a charged particle beam such as an X-ray such as far ultraviolet rays represented by an ArF excimer laser (wavelength 193 nm), synchrotron radiation or an electron beam, or the like. As a high-resolution resist corresponding to these short-wavelength radiations, a “chemically amplified resist” has been proposed, and improvements in the chemically amplified resist are being actively pursued. The chemically amplified resist is irradiated with radiation to a radiation-sensitive acid generator contained therein (hereinafter, referred to as “radiation-sensitive acid generator”).
This is called "exposure". ) To generate an acid, and a catalytic reaction of the acid causes a chemical reaction (for example, change in polarity, cleavage of chemical bond, cross-linking reaction, etc.) in the resist film, and the solubility in the developing solution changes in the exposed portion. A pattern is formed by utilizing the phenomenon. Conventionally, as such a chemically amplified resist, a resin in which an alkali-affinity group in an alkali-soluble resin is protected by a t-butyl ester group or a t-butoxycarbonyl group as a resin component (see Japanese Patent Publication No. 2-27660). ), A resin in which an alkali-affinity group in an alkali-soluble resin is protected by a silyl group (JP-B-3
JP-A-44290), a resin in which an alkali-affinity group in an alkali-soluble resin is protected by a ketal group.
Chemical amplification such as a resist using a resin in which an alkali-affinity group in an alkali-soluble resin is protected by an acetal group (see JP-A-2-161436 and JP-A-5-249682). There have been many reports on mold resists. However, these chemically amplified resists have their own problems, and it has been pointed out that various difficulties are involved particularly in practical application to fine processing with a design size of 0.25 μm or less. When performing microfabrication in the vicinity of 20 μm with a film thickness of 0.5 μm or less, irregularities on the surface and side surfaces of the resist film after pattern formation become large, which hinders microfabrication according to design dimensions. The issue of "roughness" or "film surface roughness" has begun to be pointed out. On the other hand, in the positive-type and negative-type radiation-sensitive resin compositions, line width control is performed by using a combination of a radiation-sensitive acid generator and a compound that can be decomposed into a neutral compound by exposure as a photosensitive compound. (See Japanese Patent Application Laid-Open No. 9-43837). However, although this composition is excellent in resolution, heat resistance and etching resistance, it is not particularly satisfactory in terms of "nano edge roughness" or "film surface roughness". Therefore, there is a strong demand for the development of a chemically amplified resist that is excellent in resolution, pattern shape, and the like, and that can solve the problem of “nano edge roughness” or “film surface roughness”.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to effectively respond to various kinds of radiation such as far ultraviolet rays, X-rays and charged particle beams, to have excellent resolution and pattern shape, and to particularly provide "nano edge roughness" or "nano edge roughness". To provide a radiation-sensitive resin composition useful as a positive-type and negative-type chemically amplified resist capable of stably forming a high-accuracy fine resist pattern without causing "film surface roughness". It is in.

[0004]

According to the present invention, the above object is firstly achieved by (A) (a) an alkali-insoluble or alkali-insoluble resin protected by an acid-dissociable group, wherein A resin which becomes alkali-soluble when the dissociable group is dissociated, or (b) an alkali-soluble resin and an alkali solubility controller, and (B) a radiation-sensitive acid generator comprising two or more compounds, At least one of the compounds constituting the component (B) consists of “a compound that generates a carboxylic acid having a boiling point of 150 ° C. or higher at normal pressure by irradiation with radiation”, and at least one of the compounds constituting the component (B). Achieved by a positive-type radiation-sensitive resin composition (hereinafter, referred to as a "first invention"), characterized in that one type comprises a "compound that generates an acid other than a carboxylic acid upon irradiation with radiation". It is.

According to the present invention, the above-mentioned problem is secondly solved.
The component (B), comprising (C) an alkali-soluble resin, (D) a compound capable of crosslinking the alkali-soluble resin in the presence of an acid, and (B) a radiation-sensitive acid generator comprising two or more compounds. At least one of the compounds constituting the above (B) comprises a compound that generates a carboxylic acid having a boiling point of 150 ° C. or higher at normal pressure by irradiation with radiation, and
A negative-type radiation-sensitive resin composition (hereinafter, referred to as a "first invention") wherein at least one of the compounds constituting the component is composed of "a compound which generates an acid other than a carboxylic acid upon irradiation with radiation". )).

Hereinafter, the present invention will be described in detail. Acid-Dissociable Group-Containing Resin An alkali-insoluble or alkali-soluble resin protected by an acid-dissociable group used in the first invention (component (A) (a)), wherein the acid-dissociable group is dissociated. Sometimes an alkali-soluble resin (hereinafter referred to as “acid-dissociable group-containing resin”
That. ) Is one or more acid dissociable groups capable of dissociating a hydrogen atom of an acidic functional group in a resin containing at least one acidic functional group such as a phenolic hydroxyl group and a carboxyl group in the presence of an acid. Is an alkali-insoluble or alkali-insoluble resin per se. The term “alkali-insoluble or poorly alkali-soluble” used herein refers to an alkali developing agent used when forming a resist pattern from a resist film formed using a radiation-sensitive resin composition containing an acid-dissociable group-containing resin. Under the conditions, when a film using only an acid-dissociable group-containing resin is developed in place of the resist film, 50% or more of the initial film thickness of the film remains after development. Examples of the acid dissociable group in the acid dissociable group-containing resin include, for example, a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a silyl group, a germyl group, an alkoxycarbonyl group, an acyl group,
And cyclic acid dissociable groups. Examples of the substituted methyl group include methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, methoxyethoxymethyl group, benzyloxymethyl group, benzylthiomethyl group, phenacyl group, bromophenacyl group, methoxyphenacyl Group, methylthiophenacyl group,
α-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxybenzyl group, methylthiobenzyl group, ethoxybenzyl group, ethylthiobenzyl group, piperonyl Group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-
Propoxycarbonylmethyl group, isopropoxycarbonylmethyl group, n-butoxycarbonylmethyl group, t-
Butoxycarbonylmethyl group and the like.
Examples of the 1-substituted ethyl group include a 1-methoxyethyl group, a 1-methylthioethyl group, a 1,1-dimethoxyethyl group, a 1-ethoxyethyl group, a 1-ethylthioethyl group, and a 1,1- Diethoxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-
Diphenoxyethyl group, 1-benzyloxyethyl group,
1-benzylthioethyl group, 1-cyclopropylethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1-n-propoxycarbonylethyl group , 1-isopropoxycarbonylethyl group, 1-n
-Butoxycarbonylethyl group, 1-t-butoxycarbonylethyl group and the like. The above 1
-As a branched alkyl group, for example, an isopropyl group,
Examples thereof include a sec-butyl group, a t-butyl group, a 1,1-dimethylpropyl group, a 1-methylbutyl group, and a 1,1-dimethylbutyl group. Examples of the silyl group include a trimethylsilyl group, an ethyldimethylsilyl group, a methyldiethylsilyl group, a triethylsilyl group, an isopropyldimethylsilyl group, a methyldiisopropylsilyl group, a triisopropylsilyl group, a t-butyldimethylsilyl group, -T-butylsilyl group, tri-t-butylsilyl group, phenyldimethylsilyl group,
Examples thereof include a methyldiphenylsilyl group and a triphenylsilyl group. Further, as the germyl group,
For example, trimethylgermyl, ethyldimethylgermyl, methyldiethylgermyl, triethylgermyl, isopropyldimethylgermyl, methyldiisopropylgermyl, triisopropylgermyl, t-
Examples thereof include a butyldimethylgermyl group, a methyldi-t-butylgermyl group, a tri-t-butylgermyl group, a phenyldimethylgermyl group, a methyldiphenylgermyl group, and a triphenylgermyl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, and a t-butoxycarbonyl group. Examples of the acyl group include an acetyl group,
Propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauryloyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, succinyl group, glutaryl group, adipoyl group, piperoyl group , Suberoyl group, azelaoil group, sebacoil group, acryloyl group, propioyl group, methacryloyl group,
Crotonoyl, oleoyl, maleoyl, fumaroyl, mesaconoyl, camphoroyl, benzoyl, phthaloyl, isophthaloyl, terephthaloyl, naphthoyl, toluoyl, hydroatropoyl, atropoyl, cinnamoyl, floyl Group, thenoyl group, nicotinoyl group, isonicotinoyl group, p-
Examples thereof include a toluenesulfonyl group and a mesyl group. Further, as the cyclic acid dissociable group, for example, cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, 4-methoxycyclohexyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiopyranyl group, tetrahydro Thiofuranyl group, 3-bromotetrahydropyranyl group, 4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, 3-tetrahydrothiophene-
Examples thereof include a 1,1-dioxide group.

Among these acid dissociable groups, t-butyl, benzyl, 1-methoxyethyl, 1-ethoxyethyl, trimethylsilyl, t-butoxycarbonylmethyl, tetrahydropyranyl, tetrahydrofuranyl , A tetrahydrothiopyranyl group, a tetrahydrothiofuranyl group and the like.

The rate of introduction of acid-dissociable groups into the resin having acid-dissociable groups (the ratio of the number of acid-dissociable groups to the total number of acidic functional groups and acid-dissociable groups in the resin having acid-dissociable groups) is Although it cannot be specified unconditionally depending on the kind of the acid-dissociable group or the alkali-soluble resin into which the group is introduced, preferably 10 to 10
0%, more preferably 15 to 100%. Also,
The weight molecular weight in terms of polystyrene (hereinafter, referred to as “Mw”) of the acid-dissociable group-containing resin measured by gel permeation chromatography is preferably 1,000 to 1.
50,000, more preferably 3,000 to 100,
000. The acid-dissociable group-containing resin can be produced, for example, by introducing one or more acid-dissociable groups into a previously produced alkali-soluble resin, and one or more monomers having an acid-dissociable group. Can be produced by (co) polymerization, (co) polycondensation of at least one polycondensation component having an acid-dissociable group, or the like. Examples of the acid-dissociable group-containing resin in the first invention include resins in which a part of hydrogen atoms of hydroxyl groups in poly (hydroxystyrene) is substituted with the acid-dissociable group, hydroxystyrene and / or hydroxy-
A resin in which a part or all of the hydrogen atom of the hydroxyl group and / or the hydrogen atom of the carboxyl group in the copolymer of α-methylstyrene and (meth) acrylic acid is substituted with the acid dissociable group is preferable. The acid-dissociable group-containing resin also has the property of controlling the alkali solubility of the alkali-soluble resin, and dissociates in the presence of an acid to reduce or eliminate the effect of controlling the alkali solubility of the alkali-soluble resin. Or has an action of promoting the alkali solubility of the alkali-soluble resin, and comprises the component (A) of the first invention.
It falls under the category of the alkali solubility control agent in (b).

In the first invention, a particularly preferred acid-dissociable group-containing resin is, for example, a random copolymer or a block copolymer represented by the following formula (1) or (2).

[0010]

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[In the formula (1), R ¹ and R ² may be the same or different from each other, and a plurality of R ¹ and R ² may be the same or different from each other, and represent a hydrogen atom, a methyl group or An ethyl group; R ³ represents a hydrogen atom or a t-butoxycarbonyloxy group; a, b, and c each represent the number of repeating units; a and b are integers of 1 or more; c is an integer of 0 or more; is there. ]

[0012]

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[In the formula (2), R ⁴ and R ⁵ independently represent a hydrogen atom or a methyl group, and R ⁶ represents a hydrogen atom, a t-butoxy group or —OC (R ⁷ ) ₂ —OC (R ⁸ ) ₃ (however, R ⁷ and R ⁸ may be the same or different from each other, and a plurality of R ⁷ and R ⁸ may be the same or different from each other, and represent a hydrogen atom, a methyl group or an ethyl group .)
And d, e and f indicate the number of each repeating unit, and d
And e are integers of 1 or more, and f is an integer of 0 or more. In the first invention, the acid-dissociable group-containing resins can be used alone or in combination of two or more.

Alkali-soluble resin The alkali-soluble resin used in the first invention (component (A) (b)) and the second invention (component (C)) has a functional group having an affinity for an alkali developing solution, for example, It is a resin having at least one acidic functional group such as a phenolic hydroxyl group and a carboxyl group and soluble in an alkaline developer. As such an alkali-soluble resin, for example, the following formula (3)
Examples thereof include addition polymerization resins having one or more kinds of repeating units represented by formulas (1) to (5), and polycondensation resins having one or more kinds of repeating units represented by the following formula (6).

[0015]

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[In the formula (3), R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents —OH, —COOH, —R ¹¹ COOH,
-OR ¹¹ COOH or -OCOR ¹¹ COOH where R ¹¹ is-(CH) g-
And g is an integer of 1 to 4. Indicates｝. ]

[0017]

Embedded image [In the formula (4), R ¹² represents a hydrogen atom or a methyl group. ]

[0018]

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[0019]

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[In the formula (6), R ¹³ , R ¹⁴ , R ¹⁵ ,
R ¹⁶ and R ¹⁷ may be the same or different from each other, and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When the alkali-soluble resin is an addition polymerization resin, it may be composed of only the repeating units represented by the formulas (3) to (5), provided that the produced resin is soluble in the alkali developer. In addition, another repeating unit may be further provided. Such other repeating units include, for example,
Styrene, α-methylstyrene, maleic anhydride, (meth) acrylonitrile, crotonitrile, maleinitrile, fumaronitrile, mesaconitrile, citraconitrile, itaconitrile, (meth) acrylamide, crotonamide, maleamide, fumamide,
Mesaconamide, citraconamide, itaconamide,
Examples thereof include units in which a polymerizable double bond portion of a monomer having a polymerizable double bond such as vinylaniline, vinylpyridine, vinyl-ε-caprolactam, vinylpyrrolidone, or vinylimidazole has been cleaved. The addition polymerization-based resin may include, for example, one or more monomers corresponding to the repeating units represented by Formulas (3) to (5), together with a monomer corresponding to the other repeating unit, if necessary. It can be produced by (co) polymerization. In these (co) polymerizations, a polymerization initiator or a polymerization catalyst such as a radical polymerization initiator, an anion polymerization catalyst, a coordination anion polymerization catalyst, or a cationic polymerization catalyst is appropriately added depending on the type of the monomer, the reaction medium, and the like. Bulk polymerization, solution polymerization, precipitation polymerization, emulsion polymerization,
It can be carried out by an appropriate polymerization method such as suspension polymerization or bulk-suspension polymerization. When the alkali-soluble resin is a polycondensation resin, it may be composed of only the repeating unit represented by the formula (6), but other resins may be used as long as the produced resin is soluble in the alkali developer. May be further provided. Such a polycondensation resin is obtained by combining one or more phenols corresponding to the repeating unit represented by the formula (6) with one or more aldehydes, and optionally forming a polymer capable of forming another repeating unit. It can be produced by (co) polycondensation in an aqueous medium or a mixed medium of water and a hydrophilic solvent in the presence of an acidic catalyst together with the condensation component. Examples of the phenols include o-cresol, p-cresol, 2,3-xylenol,
4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol and the like, and the aldehydes Examples thereof include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde and the like. Although the content of the repeating units represented by the formulas (3) to (6) in the alkali-soluble resin cannot be unconditionally defined depending on the type of the other repeating unit optionally contained, it is preferably 10 to 100 mol%. And more preferably 20 to 100 mol%. The Mw of the alkali-soluble resin varies depending on the desired properties of the radiation-sensitive resin composition, but is preferably from 1,000 to 150,0.
00, more preferably 3,000 to 100,000. When the alkali-soluble resin has a repeating unit containing a carbon-carbon unsaturated bond represented by the formula (3) or (6), it can be used as a hydrogenated product. The hydrogenation rate in this case is usually 70% or less, preferably 50% or less, more preferably 50% or less of the carbon-carbon unsaturated bonds contained in the repeating units represented by the formulas (3) and (6). 40% or less. If the hydrogenation ratio exceeds 70%, the development characteristics of the alkali-soluble resin with an alkali developer may be reduced. As the alkali-soluble resin in the first invention and the second invention, in particular, poly (hydroxystyrene), a copolymer of hydroxystyrene and hydroxy-α-methylstyrene, a copolymer of hydroxystyrene and styrene, etc. are mainly used. Is preferred. In the first invention and the second invention, the alkali-soluble resins can be used alone or in combination of two or more.

Alkali Solubility Control Agent Next, the alkali solubility control agent used in the first invention (component (A) (b)) includes, for example, an acidic functional group such as a phenolic hydroxyl group and a carboxyl group. And a compound into which one or more substituents that can be dissociated in the presence of (hereinafter, referred to as “acid-dissociable substituents”) are introduced. Examples of such an acid dissociable substituent include the substituted methyl group, 1-
Examples thereof include groups similar to acid dissociable groups such as a substituted ethyl group, a silyl group, a 1-branched alkyl group, a germyl group, an alkoxycarbonyl group, an acyl group, and a cyclic acid dissociable group.
The alkali solubility controlling agent may be a low molecular weight compound or a high molecular weight compound. Specific examples of the low molecular weight compound include compounds represented by the following formulas (7) to (11).

[0022]

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[In the formula (7), R ¹⁸ is a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a silyl group, a germyl group, an alkoxycarbonyl group, an acyl group or a cyclic acid dissociable group. Represents an acid dissociable group, a plurality of R ¹⁸ may be the same or different from each other, and R ¹⁹ represents an alkyl group having 1 to 4 carbon atoms, a phenyl group or a 1-naphthyl group, and a plurality of R ¹⁹ represent P may be the same or different, p is an integer of 1 or more, q is an integer of 0 or more, p
+ Q ≦ 6. ]

[0024]

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[In the formula (8), R ¹⁸ and R ¹⁹ have the same meanings as in the formula (7), and A is a single bond, -S-, -O-, -CO-,
-COO-, -SO-, -SO _2- , -C (R ²⁰ ) (R ²¹ )-(however, R ²⁰ and R ²¹ may be the same or different, and a hydrogen atom,
It represents an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 11 carbon atoms, a phenyl group or a naphthyl group. ) Or

[0026]

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(Where R ¹⁹ is the same as above and x is 0)
-4. ), P, q, r and s are each an integer of 0 or more, and p + q ≦ 5, r + s ≦ 5, p +
r ≧ 1. ]

[0028]

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[In the formula (9), R ¹⁸ and R ¹⁹ have the same meaning as in the formula (7), and R ²² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and p, q, r , S,
t and u are each an integer of 0 or more, and p + q ≦ 5, r
+ S ≦ 5, t + u ≦ 5, and p + r + t ≧ 1. ]

[0030]

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[In the formula (10), R ¹⁸ and R ¹⁹ have the same meaning as in the formula (7), A has the same meaning as in the formula (8), and R
²² has the same meaning as in the formula (9), and a plurality of R ²² may be mutually the same or different, and p, q, r, s, t, u, v
And w are each an integer of 0 or more, and p + q ≦ 5, r +
s ≦ 5, t + u ≦ 5, v + w ≦ 5, p + r + t + v ≧ 1
It is. ]

[0032]

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[In the formula (11), R ¹⁸ and R ¹⁹ have the same meaning as in the formula (7), and R ²² has the same meaning as in the formula (9);
A plurality of R ²² may be the same or different from each other;
p, q, r, s, t, u, v, and w are each an integer of 0 or more, and p + q ≦ 5, r + s ≦ 5, t + u ≦ 5, v +
w ≦ 4 and p + r + t + v ≧ 1. In addition, as the polymer alkali solubility controller, for example, the above-mentioned acid-dissociable group-containing resin can be used. In the first invention, the alkali solubility controlling agent is a low molecular weight compound or a high molecular weight compound (that is, a resin containing an acid dissociable group).
Each of them can be used alone or in combination of two or more, and a low molecular compound and a high molecular compound can be used in combination.

Crosslinking Agent The crosslinking agent used in the second invention (component (D)) is
A compound capable of crosslinking an alkali-soluble resin in the presence of an acid, for example, an acid generated by exposure. Examples of such a cross-linking agent include compounds having one or more substituents having a cross-linking reactivity with an alkali-soluble resin (hereinafter, referred to as “cross-linking substituents”). Examples of the crosslinkable substituent in the crosslinking agent include groups represented by the following formulas (12) to (16).

[0035]

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[0036] In [Equation (12), k is 1 or 2, Q ^1, when the k = 1, single bond, -O-, -S-, -COO
-Or -NH-, or when k = 2, represents a trivalent nitrogen atom, Q ² represents -O- or -S-, and i represents 0 to
An integer of 3 and j is an integer of 1 to 3 and i + j = 1 to 4. ]

[0037]

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[In the formula (13), Q ³ represents -O-, -COO-
Or -CO-, R ²³ and R ²⁴ may be the same or different from each other, and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ²⁵ is an alkyl group having 1 to 5 carbon atoms, 6
Represents an aryl group having from 12 to 12 or an aralkyl group having from 7 to 14 carbon atoms, and y is an integer of 1 or more. ]

[0039]

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[In the formula (14), R ²⁶ , R ²⁷ and
R ²⁸ may be the same or different, and represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[0041]

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[In the formula (15), R ²³ and R ²⁴ have the same meaning as in the formula (13), and R ²⁹ and R ³⁰ may be the same or different from each other, and represent an alkylol group having 1 to 5 carbon atoms. And y is an integer of 1 or more. ]

[0043]

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[In the formula (16), R ²³ and R ²⁴ have the same meaning as in the formula (13), and R ³¹ has any one of an oxygen atom, a sulfur atom and a nitrogen atom, and has 3 to 8 members. It represents a divalent organic group forming a ring, and y is an integer of 1 or more. Specific examples of such a crosslinkable substituent include a glycidyl ether group, glycidyl ester group, glycidylamino group, methoxymethyl group, ethoxymethyl group, benzyloxymethyl group, dimethylaminomethyl group, diethylaminomethyl group, dimethylol Examples include an aminomethyl group, a diethylolaminomethyl group, a morpholinomethyl group, an acetoxymethyl group, a benzoyloxymethyl group, a formyl group, an acetyl group, a vinyl group, and an isopropenyl group. Examples of the compound having a crosslinkable substituent include a bisphenol A-based epoxy compound, a bisphenol F-based epoxy compound, a bisphenol S-based epoxy compound, a novolak resin-based epoxy compound, a resol resin-based epoxy compound, and a poly (hydroxystyrene) -based epoxy compound. Compound, methylol group-containing melamine compound, methylol group-containing benzoguanamine compound, methylol group-containing urea compound, methylol group-containing phenol compound, alkoxyalkyl group-containing melamine compound, alkoxyalkyl group-containing benzoguanamine compound, alkoxyalkyl group-containing urea compound, alkoxyalkyl group -Containing phenolic compound, carboxymethyl-containing melamine resin, carboxymethyl-containing benzoguanamine resin, carboxymethyl-containing urea resin Carboxymethyl group-containing phenol resin, carboxymethyl group-containing melamine compounds,
Examples thereof include carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compounds, and carboxymethyl group-containing phenol compounds. Among these compounds having a crosslinkable substituent, a methylol group-containing phenol compound, a methoxymethyl group-containing melamine compound, a methoxymethyl group-containing phenol compound, a methoxymethyl group-containing glycoluril compound, a methoxymethyl group-containing urea compound, and an acetoxymethyl group Phenol-containing compounds are preferred, and melamine compounds containing methoxymethyl groups (eg, hexamethoxymethylmelamine), glycoluril compounds containing methoxymethyl groups, urea compounds containing methoxymethyl groups, and the like are more preferred. The methoxymethyl group-containing melamine compound is CYME
L300, CYMEL301, CYMEL303, CY
Product names such as MEL305 (Mitsui Cyanamid)
The methoxymethyl group-containing glycoluril compound is CYM
With product names such as EL1174 (Mitsui Cyanamid)
The methoxymethyl group-containing urea compound is MX290
(Manufactured by Sanwa Chemical Co., Ltd.). As the cross-linking agent, a compound in which the cross-linkable substituent is introduced into an acidic functional group in an alkali-soluble resin to impart properties as a cross-linking agent can also be suitably used. In such a case, the introduction rate of the crosslinkable functional group cannot be unconditionally defined by the type of the crosslinkable functional group or the alkali-soluble resin into which the group is introduced, but is usually relative to all the acidic functional groups in the alkali-soluble resin. , 5 to 60 mol%, preferably 10 to 50 mol%, more preferably 15 to 40 mol%. In this case, if the introduction ratio of the crosslinkable functional group is less than 5 mol%, the residual film ratio tends to decrease, and the pattern tends to meander or swell, and if it exceeds 60 mol%, the developability deteriorates. Tend to. As the crosslinking agent in the second invention, a methoxymethyl group-containing compound such as dimethoxymethylurea or tetramethoxymethylglycoluril is particularly preferred. In the second invention, the crosslinking agents can be used alone or as a mixture of two or more.

(B) Radiation-Sensitive Acid Generator First Invention (Component (B)) and Second Invention (Component (B))
The radiation-sensitive acid generator used in the above comprises at least two compounds, at least one of which is a "compound capable of generating a carboxylic acid having a boiling point of 150 ° C. or more at normal pressure by exposure" , "Acid generator (B
1) ". ) And at least one compound comprises a "compound capable of generating an acid other than a carboxylic acid upon exposure" (hereinafter referred to as "acid generator (B2)"). In the present invention, by using a combination of the acid generator (B1) and the acid generator (B2) as the radiation-sensitive acid generator, "nano edge roughness" or "film surface roughness" is remarkably suppressed. be able to.

In the acid generator (B1), examples of the carboxylic acid having a boiling point of 150 ° C. or more at normal pressure generated by exposure include a saturated aliphatic carboxylic acid, an unsaturated aliphatic carboxylic acid and a halogen atom-containing aliphatic carboxylic acid. Acid, hydroxyl group-containing aliphatic carboxylic acid, alkoxyl group-containing aliphatic carboxylic acid, keto group-containing aliphatic carboxylic acid, aldehyde group-containing aliphatic carboxylic acid, alicyclic skeleton-containing aliphatic carboxylic acid, aromatic ring-containing conjugated carboxylic acid (Ie, a carboxylic acid in which the C ＝ O group of the carboxyl group has a conjugate relationship with a double bond in the aromatic ring), an aromatic ring-containing non-conjugated carboxylic acid, and the like. In the first invention and the second invention, such an acid generator (B1) that generates a carboxylic acid having a boiling point of 150 ° C. or more at normal pressure is combined with an acid generator (B2) that generates another acid. By using
A resist pattern having a particularly excellent pattern shape can be formed.

Preferred acid generators (B1) include, for example, (a) onium salt compounds of carboxylic acids represented by the following formulas (17) to (30) (hereinafter referred to as "acid generator (B1-
a) ". ), (B) a carboxyimide compound produced by a dehydration condensation reaction between a carboxylic acid represented by the following formulas (17) to (30) and a compound having a hydroxyimide skeleton (hereinafter referred to as “acid generator (B1- b) ")).

[0048]

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[In the formula (17), R ³² has 1 to 1 carbon atoms.
20 linear, branched or cyclic alkyl groups, C1-20 linear, branched or cyclic alkenyl groups, C1-20 linear, branched or cyclic alkynyl groups; A linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms, a group in which at least a part of the hydrogen atoms of the alkyl group is substituted with a halogen atom and / or a hydroxyl group, and at least one hydrogen atom of the alkenyl group Represents a group in which the moiety is substituted with a halogen atom and / or a hydroxyl group, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. ]

[0050]

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[In the formula (18), h is an integer of 2 to 6. ]

[0052]

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[0053]

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[In equations (19) and (20),
R ³³ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, a linear, branched or cyclic alkenylene group having 1 to 20 carbon atoms, and at least a part of hydrogen atoms of the alkylene group is been substituted with halogen atoms and / or hydroxyl, represents at least part of which is substituted with a halogen atom group or alkoxide alkylene group having 2 to 20 carbon atoms, the hydrogen atoms of the alkenylene group, R ³³ there are a plurality of May be the same or different from each other. ]

[0055]

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[0056]

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[In equations (21) and (22),
R ³² has the same meaning as in formula (17), R ³³ has the same meaning as in formula (19), and a plurality of R ³³ may be mutually the same or different. ]

[0058]

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[0059]

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[In equations (23) and (24),
R ³² has the same meaning as in formula (17), a plurality of R ³² may be mutually the same or different, R ³³ has the same meaning as in formula (19), R ³⁴ represents a hydroxyl group or a halogen atom, The R ³⁴ present may be the same or different from each other, m and n are integers from 0 to 3, and m + n ≦ 5. ]

[0061]

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[In the formula (25), R ³² is the formula (17)
And a plurality of R ³² may be mutually the same or different, R ³³ has the same meaning as in formula (19), R ³⁴ has the same meaning as in formula (23), and a plurality of R ³⁴ M, n, m ′ and n ′ may be the same or different from each other;
Where m + n ≦ 5 and m ′ + n ′ ≦ 5. ]

[0063]

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[In the formula (26), R ³² is the formula (17)
And m is an integer of 0 to 3. ]

[0065]

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[In the formula (27), R ³² is the formula (17)
And a plurality of R ³² may be mutually the same or different, R ³³ has the same meaning as in formula (19), R ³⁴ has the same meaning as in formula (23), and a plurality of R ³⁴ M, n, m ′ and n ′ may be the same or different from each other;
M + n ≦ 4, m ′ + n ′ ≦ 3, and z is 0
Or 1. ]

[0067]

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[0068]

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[In equations (28) and (29),
R ³² has the same meaning as in formula (17), a plurality of R ³² may be mutually the same or different, R ³³ has the same meaning as in formula (19), and R ³⁴ has the same meaning as in formula (23). And a plurality of R ³⁴ may be the same or different, and m, n, m ′ and n ′ are integers of 0 to 3, and m + n ≦ 5, m ′ + n ′ ≦
4, and z is 0 or 1. ]

[0070]

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[In the formula (30), R ³² is the formula (17)
And a plurality of R ³² may be mutually the same or different, R ³³ has the same meaning as in formula (19), R ³⁴ has the same meaning as in formula (23), and a plurality of R ³⁴ M and n may be the same or different, and m and n are an integer of 0 to 3;
+ N ≦ 4, and z is 0 or 1. As particularly preferred acid generators (B1-a), for example,
Iodonium salts such as bis (t-butylphenyl) iodonium salt and diphenyliodonium salt of a carboxylic acid represented by the above formulas (17) to (30);
Examples thereof include sulfonium salts such as a triphenylsulfonium salt of a carboxylic acid represented by (30) and 4-t-butylphenyl / diphenylsulfonium salt.
Specific examples of such iodonium salts and sulfonium salts include compounds represented by the following formulas (31) to (36).

[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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Particularly preferred acid generators (B1-b)
Are, for example, carboxylic acids represented by the above formulas (17) to (30), N-hydroxysuccinimide, N-
Hydroxyphthalimide, N-hydroxydiphenylmaleimide, N-hydroxybicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-hydroxy-7-oxabicyclo [2.2.1] hept -5
-Ene-2,3-dicarboximide, N-hydroxybicyclo [2.2.1] heptane-5,6-oxy-
Dehydration condensation products with 2,3-dicarboximide, N-hydroxynaphthylimide and the like can be mentioned. As a specific example of such a dehydration condensation product, the following formula (3)
7) to compounds represented by formula (40).

[0079]

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[0080]

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[0081]

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[0082]

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These acid generators (B1) can be used alone or in combination of two or more.

Next, as the acid generator (B2), a compound that generates sulfonic acid and / or sulfinic acid upon exposure to light is preferable. Examples of such a compound include the following compounds. Onium Salt Compound Examples of the onium salt compound include an iodonium salt, a sulfonium salt, a phosphonium salt, a diazonium salt, an ammonium salt, and a pyridinium salt. Specific examples of the onium salt compound include bis (4-t-butylphenyl) iodonium perfluorobutane sulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, and bis (4-t-butylphenyl) iodonium pyrene sulfonate , Screw (4-
t-butylphenyl) iodonium dodecylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate, bis (4-t-butylphenyl) iodoniumbenzenesulfonate, bis (4-t-butylphenyl) iodonium- 10-camphorsulfonate, bis (4-t-butylphenyl)
Iodonium octanesulfonate, bis (4-t-butylphenyl) iodonium-2-trifluoromethylbenzenesulfonate, diphenyliodonium perfluorobutanesulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium pyrene sulfonate, diphenyliodonium dodecylbenzenesulfonate, diphenyliodonium- p
-Toluenesulfonate, diphenyliodonium benzenesulfonate, diphenyliodonium-10-camphorsulfonate, diphenyliodonium octanesulfonate, diphenyliodonium-2-trifluoromethylbenzenesulfonate, triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenyl Sulfonium pyrene sulfonate, triphenylsulfonium dodecylbenzenesulfonate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, triphenylsulfonium-10-camphorsulfonate, octanesulfonate, triphenylsulfonium-2-
Trifluoromethylbenzenesulfonate, 4-t-butylphenyl / diphenylsulfonium perfluorobutanesulfonate, 4-t-butylphenyl / diphenylsulfonium trifluoromethanesulfonate, 4-
t-butoxyphenyl / diphenylsulfonium pyrene sulfonate, 4-t-butoxyphenyl / diphenylsulfonium dodecylbenzenesulfonate, 4-t-
Butoxyphenyl diphenylsulfonium-p-toluenesulfonate, 4-t-butoxyphenyl diphenylsulfonium benzenesulfonate, 4-t-butoxyphenyl diphenylsulfonium-10-camphorsulfonate, 4-t-butoxyphenyl diphenylsulfonium octanesulfonate, etc. Can be mentioned.

Sulfone compound Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof. Specific examples of the sulfone compound include phenacylphenylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, 4-trisphenacylsulfone, and the like. Sulfonic acid ester compound Examples of the sulfonic acid ester compound include alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, and haloarylsulfonic acid esters. Specific examples of the sulfonic acid ester compound include benzoin tosylate, pyrogallol tristrifluoromethanesulfonate, pyrogallol methanesulfonic acid triester, nitrobenzyl-
9,10-diethoxyanthracene-2-sulfonate, α-methylol benzoin tosylate, α-methylol benzoin octane sulfonate, α-methylol benzoindodecyl sulfonate and the like can be mentioned.

Sulfonimide Compounds The sulfonimide compounds include, for example, those represented by the following formula (4)
The compound represented by 1) can be mentioned.

[0087]

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(In the formula (41), X represents a divalent group such as an alkylene group, an arylene group, or an alkoxylene group, and R ³⁵ represents an alkyl group, an aryl group, a halogen-substituted alkyl group, a halogen-substituted aryl group, or the like. Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N-
(Trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (perfluoro Butylsulfonyloxy) succinimide, N- (perfluorobutylsulfonyloxy) phthalimide, N- (perfluorobutylsulfonyloxy) diphenylmaleimide, N- (perfluorobutylsulfonyloxy) bicyclo [2.2.1] hept-5- Ene-2,3-dicarboximide, N- (perfluorobutylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide, N- (perfluorobutylsulfonyloxy) bicyclo [2.2.1]
Heptane-5,6-oxy-2,3-dicarboximide, N- (perfluorobutylsulfonyloxy) naphthylimide, N- (camphorsulfonyloxy) succinimide, N- (camphorsulfonyloxy) phthalimide, N- (camphor) Sulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy)
Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-
5,6-oxy-2,3-dicarboximide, N-
(Camphorsulfonyloxy) naphthylimide, N-
(4-methylphenylsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) phthalimide, N- (4-methylphenylsulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2 .1] Hept-5
-Ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( 4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) naphthylimide, N- (2-tri Fluoromethylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] Hept-5-ene-
2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2 -Trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-
5,6-oxy-2,3-dicarboximide, N-
(2-trifluoromethylphenylsulfonyloxy)
Naphthylimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) phthalimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide,
N- (4-Fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2. 2.1] Hept-5
-Ene-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.
1] Heptane-5,6-oxy-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) naphthylimide and the like.

Diazomethane compound The diazomethane compound includes, for example, a compound represented by the following formula (42)
Can be mentioned.

[0090]

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[In the formula (42), R ³⁶ and R ³⁷ may be the same or different and each represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group and a halogen-substituted aryl group. Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, Examples thereof include 1-cyclohexylsulfonyl-1- (1,1-dimethylethylsulfonyl) diazomethane and bis (1,1-dimethylethylsulfonyl) diazomethane. Particularly preferred acid generators (B2) include, for example, bis (4-t-butylphenyl) iodonium perfluorobutanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t- Butylphenyl) iodonium-p-toluenesulfonate, bis (4-t-butylphenyl) iodonium-1
0-camphorsulfonate, triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfonium-10-camphorsulfonate, 4
-T-butoxyphenyl diphenylsulfonium-p
-Toluenesulfonate, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximide, bis (cyclohexylsulfonyl) diazomethane and the like can be mentioned. These acid generators (B2) can be used alone or in combination of two or more. In the first invention and the second invention, the use ratio (B1 / B2) (weight ratio) of the acid generator (B1) and the acid generator (B2) is
Usually, it is 0.01 to 5, preferably 0.02 to 2,
The total amount of the acid generator (B1) and the acid generator (B2) used is usually 0.5 to 20 parts by weight, preferably 1 to 100 parts by weight of the resin component in the radiation-sensitive resin composition. ~
15 parts by weight. In this case, if the usage ratio (B1 / B2) (weight ratio) of the acid generator (B1) and the acid generator (B2) is less than 0.01, the resist may have “nano edge roughness” or “film surface roughness”. On the other hand, when the value exceeds 5, the sensitivity as a resist decreases, and pattern formation may be difficult. If the total amount of the acid generator (B1) and the acid generator (B2) used is less than 0.5 parts by weight, it is difficult to sufficiently generate a chemical change due to the catalytic action of the acid generated by exposure. On the other hand, if the content exceeds 20 parts by weight, application unevenness may occur during application of the radiation-sensitive resin composition, and scum may occur during development.

Acid Diffusion Control Agent In the first and second inventions, the diffusion phenomenon of the acid generated from the radiation-sensitive acid generator (B) in the resist film by the exposure is controlled to further control the unexposed area. An acid diffusion controller having an action of suppressing an undesirable chemical reaction or the like can be blended. By using such an acid diffusion controlling agent, it is possible to further suppress the occurrence of eaves particularly in the upper layer portion of the pattern, to further improve the pattern shape, and to further improve the dimensional fidelity to the design dimensions. As the acid diffusion controller, a nitrogen compound whose basicity is not changed by exposure or heat treatment in a resist pattern forming step is preferable. Specific examples of such nitrogen compounds include:
Ammonia, trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n
-Pentylamine, tri-n-hexylamine, tri-n-
Heptylamine, tri-n-octylamine, aniline,
N-methylaniline, N, N-dimethylaniline, 2-
Methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, 1-naphthylamine, 2-
Naphthylamine, diphenylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, pyrrolidone, piperidine, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, thiabendazole, pyridine, 2-methylpyridine, 4-ethylpyridine , 2-phenylpyridine, 4-phenylpyridine, 1-methyl-
4-phenylpyridine, 2- (1-ethylpropyl) pyridine, 2-benzylpyridine, nicotinamide, dibenzoylthiamine, ribofuramine tetrabutyrate, 4,4′-
Diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone,
4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2-
(4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4
-Hydroxyphenyl) propane, 1,4-bis [1-
(4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-
[Methylethyl] benzene. Among these acid diffusion controllers, particularly, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, N, N-dimethylaniline, benzimidazole,
4-phenylpyridine, 4,4'-diaminodiphenyl ether, nicotinamide and the like are preferred. The acid diffusion controllers can be used alone or in combination of two or more. The amount of the acid diffusion controller varies depending on the type thereof, the combination with the acid generator (B1) and / or the acid generator (B2), etc., but 100% by weight of the total resin components in the radiation-sensitive resin composition. The amount is usually 10 parts by weight or less, preferably 5 parts by weight or less per part. In this case, if the amount of the acid diffusion controller exceeds 10 parts by weight, the sensitivity as a resist and the developability of the exposed portion tend to decrease.

Surfactant In the first invention and the second invention, a surfactant having an effect of improving the coating property, striation, developability and the like of the radiation-sensitive resin composition can be blended.
As such a surfactant, any of anionic, cationic, nonionic and amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyethylene glycol, and the like, and KP (manufactured by Shin-Etsu Chemical Co., Ltd.) under the following trade names. , Polyflow (manufactured by Kyoeisha Yushi Kagaku Kogyo), F-Top (manufactured by Tochem Products), Megafac (manufactured by Dainippon Ink and Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass) Can be mentioned.
These surfactants can be used alone or in combination of two or more. The amount of the surfactant is per 100 parts by weight of all resin components in the radiation-sensitive resin composition,
As an active ingredient of the surfactant, it is usually not more than 2 parts by weight. In the first and second aspects of the present invention, the sensitizer absorbs radiation energy and transmits the energy to the radiation-sensitive acid generator (B), thereby increasing the amount of acid generated. As shown, a sensitizer having an effect of improving the apparent sensitivity of the radiation-sensitive resin composition can be blended. Preferred sensitizers include, for example, acetophenones, benzophenones, naphthalenes, biacetyl,
Eosine, rose bengal, pyrenes, anthracenes, phenothiazines and the like can be mentioned. These sensitizers can be used alone or in combination of two or more. The compounding amount of the sensitizer is usually 50 parts by weight or less, preferably 30 parts by weight or less based on 100 parts by weight of all the resin components in the radiation-sensitive resin composition. In addition, by blending a dye or a pigment, the latent image in the exposed area can be visualized, and the effect of halation at the time of exposure can be reduced.By blending an adhesion aid, the adhesion to the substrate can be improved. it can. Further, as other additives, an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improver, and the like, specifically, 4-hydroxy-4′-methylchalcone and the like can be blended.

The positive-working radiation-sensitive resin composition of the first invention and the negative-working radiation-sensitive resin composition of the second invention are mixed with a solvent at the time of use so that the solid content concentration becomes, for example, 5 to 50% by weight. After dissolution, the composition is prepared as a composition solution by filtering through, for example, a filter having a pore size of about 0.2 μm. Examples of the solvent include ethers, esters, ether esters, ketones, ketone esters, amides, amide esters, lactams, lactones, (halogenated) hydrocarbons, and the like. More specifically, ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, acetates, hydroxyacetates, lactates, ethylene glycol monoalkylethers Acetates, propylene glycol monoalkyl ether acetates, alkoxyacetates, (non) cyclic ketones, acetoacetates, pyruvates, propionates, N, N Dialkyl formamides, N, N- dialkyl acetamides, N-
Examples include alkylpyrrolidones, γ-lactones, (halogenated) aliphatic hydrocarbons, (halogenated) aromatic hydrocarbons, and the like. Specific examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether,
Diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, isopropenyl acetate,
Isopropenyl propionate, toluene, xylene,
Methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutyric acid Methyl, 3-
Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, propyl acetate, butyl acetate, methyl acetoacetate, Ethyl acetoacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide And the like. Among these solvents, 2-hydroxypropionic esters, 3-alkoxypropionic esters, propylene glycol monoalkyl ether acetates and the like are preferred. The solvent may be used alone or
A mixture of more than one species can be used. Further, the solvent, if necessary, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, One or more high-boiling solvents such as benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate can also be added.

Formation of Resist Pattern When a resist pattern was formed from the positive radiation-sensitive resin composition of the first invention and the negative radiation-sensitive resin composition of the second invention, the resist pattern was prepared as described above. A resist film is formed by applying the composition solution onto a substrate such as a silicon wafer or a wafer coated with aluminum by means of spin coating, casting coating, roll coating, or the like, and then subjecting to a heat treatment ( Thereafter, the resist film is exposed through a predetermined mask pattern. The radiation that can be used at that time is the emission spectrum of a mercury lamp (wavelength 254 n
m), KrF excimer laser (wavelength 248 nm), A
Far ultraviolet rays such as rF excimer laser (wavelength 193 nm) are preferable, but charged particles such as X-rays and electron beams such as synchrotron radiation are used depending on the type of the acid generator (B1) and / or the acid generator (B2). Lines and the like can also be used. Exposure conditions such as radiation dose are appropriately selected according to the composition of the radiation-sensitive resin composition, the type of additive, and the like. After the exposure, a heat treatment (hereinafter, referred to as “PEB”) is preferably performed in order to improve the apparent sensitivity of the resist. The heating conditions vary depending on the composition of the radiation-sensitive resin composition, types of additives, and the like.
The temperature is 0 to 200 ° C, preferably 50 to 150 ° C. Thereafter, a predetermined resist pattern is formed by developing with an alkali developing solution. Examples of the alkali developer include alkali metal hydroxide, aqueous ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo [5.4]. .0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5.
One or more alkaline compounds such as nonene,
An alkaline aqueous solution dissolved to a concentration of 10 to 10% by weight, preferably 2 to 5% by weight is used, and a particularly preferred alkaline developing solution is an aqueous solution of tetraalkylammonium hydroxides. In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the developer composed of the alkaline aqueous solution. When a developer composed of an alkaline aqueous solution is used, washing is generally performed after development.

[0096]

Embodiments of the present invention will be described below more specifically with reference to examples. However, the present invention is not limited to these embodiments. Here, “parts” are based on weight. The measurement of Mw and Mw / Mn and the evaluation of each resist in Examples and Comparative Examples were performed as follows. After changing the exposure amount on the resist film formed on the resolution silicone wafer and performing exposure, immediately perform PEB, then develop with alkali, wash with water, and dry to form a resist pattern. The exposure amount for forming the line-and-space pattern (1L1S) to have a line width of 1: 1 is defined as the optimum exposure amount, and the minimum dimension (μm) of the resist pattern resolved when exposed at this optimum exposure amount is , Resolution. Pattern Size The lower side dimension La and the upper side dimension Lb of a square cross section of a line and space pattern (1L1S) having a line width of 0.26 μm formed on a silicon wafer are measured using a scanning electron microscope. 0.85 ≦ Lb / La ≦ 1 and having no “gouge” near the base of the pattern or “eave” in the upper layer portion, the pattern shape is regarded as “good”, and at least one of these conditions is satisfied. Those that did not satisfy one were determined to have a "poor" pattern shape. For the line-and-space pattern (1L1S) having a designed line width of 0.26 μm, the cross-sectional dimension of the line pattern was measured by a scanning electron microscope, and as shown in FIG.
Among the cross-sectional dimensions of the line pattern, the minimum dimension is Lin,
The maximum dimension was defined as Lout, and (Lout−Lin) was defined as ΔL. FIG.
Are more exaggerated than they actually are. ΔL is less than 0.01 μm: good ΔL is 0.01 μm or more: bad

Each component used in each Example and Comparative Example was
It is as follows. [I] Positive radiation-sensitive resin composition Acid-dissociable group-containing resin A-1: a resin (Mw) in which 32 mol% of hydrogen atoms of phenolic hydroxyl groups of poly (hydroxystyrene) are substituted with 1-ethoxyethyl groups. A-2: A resin in which 20 mol% of hydrogen atoms of phenolic hydroxyl groups of poly (hydroxystyrene) are substituted with t-butoxycarbonylmethyl group (Mw = 25,000) A-3: Poly (hydroxystyrene) Resin (Mw = 16,000) in which 25 mol% of hydrogen atoms of phenolic hydroxyl group of hydroxystyrene) are substituted with 1-ethoxyethyl group and 8 mol% of the hydrogen atom are substituted with t-butoxycarbonyl group. A-4: p-hydroxy-α-methylstyrene and t-
Copolymer with butyl acrylate (copolymer molar ratio = 5:
A-5: Copolymer of p-hydroxystyrene, t-butyl acrylate and styrene (copolymer molar ratio = 6: 5, Mw = 12,000)
2: 2, Mw = 13,000) Alkali-soluble resin A-6: poly (p-hydroxystyrene) (Mw =
7,500) Alkali solubility controlling agent α-1: bis (t-butoxycarbonylated) bisphenol A

Acid generator (B1) B1-1: Formula (31) B1-2: Formula (32) B1-3: Formula (33) B1-4: Formula (34) B1-5: Formula (35) B1 -6: Formula (36) B1-7: Formula (37) B1-8: Formula (38) B1-9: Formula (39) B1-10: Formula (40) Acid Generator (B2) B2-1: Tri Phenylsulfonium trifluoromethanesulfonate B2-2: bis (4-t-butylphenyl) iodonium perfluorobutanesulfonate B2-3: bis (4-t-butylphenyl) iodonium-10-camphorsulfonate B2-4: N- (4 -Methylphenylsulfonyloxy) naphthylimide B2-5: N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide B2-6: bis (S B hexyl) diazomethane

Other Components As an acid diffusion controller, tri-n-hexylamine (β-1)
Alternatively, using benzimidazole (β-2) and using ethyl 2-hydroxypropionate (γ-1) and propylene glycol monomethyl ether acetate (γ-
2) Ethyl 3-ethoxypropionate (γ-3) was used.

[II] Negative radiation-sensitive resin composition Acid generator (B1) and acid generator (B2) [I] The same compounds as used in the positive radiation-sensitive resin composition were used. Alkali-soluble resin C-1: poly (p-hydroxystyrene) (Mw =
7,500) C-2: Copolymer of p-hydroxystyrene and styrene (copolymerization molar ratio = 7: 3, Mw = 7,000) Crosslinking agent D-1: Dimethoxymethylurea (trade name: MX29)
D-2: tetramethoxymethyloluril (trade name C)
YMEL 1174, manufactured by Mitsui Cyanamid) Other Components [I] The same components as the acid diffusion controller and solvent used in the positive-type radiation-sensitive resin composition were used.

[0101]

EXAMPLES Examples 1 to 18 and Comparative Examples 1 to 4 Each component shown in Table 1 (positive radiation-sensitive resin composition) or Table 2 (negative radiation-sensitive resin composition) is mixed to form a uniform solution. After that, the solution was filtered through a membrane filter having a pore size of 0.2 μm to prepare a composition solution. Thereafter, each composition solution was spin-coated on a silicon wafer.
(Positive radiation-sensitive resin composition) or PB, exposure and P under the conditions shown in Table 4 (negative radiation-sensitive resin composition)
EB was performed. In this spin coating, the number of revolutions was adjusted so that the film thickness after PB became 0.7 μm.
Then, after developing at 23 ° C. for 1 minute using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide,
After washing with pure water for 30 seconds and drying, a resist pattern was formed. Table 5 shows the evaluation results of the examples and comparative examples.
(Positive radiation-sensitive resin composition) and Table 6 (negative radiation-sensitive resin composition).

[0102]

[Table 1]

[0103]

[Table 2]

[0104]

[Table 3]

[0105]

[Table 4]

[0106]

[Table 5]

[0107]

[Table 6]

[0108]

The positive radiation-sensitive resin composition and the negative radiation-sensitive resin composition of the present invention are excellent in resolution and pattern shape and, in particular, cause "nano edge roughness" or "film surface roughness". There is no. In addition, the radiation-sensitive resin composition of the present invention has a
It can effectively respond to various radiations such as radiation and charged particle radiation. Therefore, the positive-type radiation-sensitive resin composition and the negative-type radiation-sensitive resin composition of the present invention are extremely suitably used as a chemically amplified positive type resist for manufacturing semiconductor devices, which is expected to be further miniaturized in the future. can do.

[Brief description of the drawings]

FIG. 1 is a side sectional view of a resist pattern illustrating a method for evaluating film surface roughness.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shinichiro Iwanaga 2-11-11 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd.

Claims (2)

[Claims] (A) (A) an alkali-insoluble or alkali-soluble resin protected by an acid-dissociable group, which is alkali-soluble when the acid-dissociable group is dissociated, or ) An alkali-soluble resin and an alkali-solubility controlling agent, and (B) a radiation-sensitive acid generator composed of two or more compounds, and at least one of the compounds constituting the component (B) is "irradiation with radiation". And at least one of the compounds constituting the component (B) generates an acid other than a carboxylic acid by irradiation with radiation. A positive-type radiation-sensitive resin composition comprising a compound. 2. It comprises (C) an alkali-soluble resin, (D) a compound capable of crosslinking the alkali-soluble resin in the presence of an acid, and (B) a radiation-sensitive acid generator comprising two or more compounds. At least one of the compounds constituting the component (B) has a boiling point at normal pressure of 1 upon irradiation.
A compound that generates a carboxylic acid at 50 ° C. or higher ”
A negative radiation-sensitive resin composition, wherein at least one of the compounds constituting the component (B) comprises a "compound which generates an acid other than a carboxylic acid upon irradiation with radiation".