JP2002214771A - Radiation sensitive positive resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chemical amplification type radiation sensitive resist composition giving an improved resist pattern shape independently of the wavelength of ionizing radiation for irradiation. SOLUTION: The radiation sensitive positive type resist composition contains a resin having a rate of dissolution in an alkali developing solution increased by the action of an acid, a compound which generates the acid when irradiated with ionizing radiation, a solvent and a compound having a bond which is cleaved by the acid to generate ionic compounds, at least one of which contains a compound nonreactive with a proton donative compound in the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Various electronic components such as semiconductor integrated circuits such as LSIs require ultra-fine processing, and resists are widely used in such processing techniques. In particular, in order to achieve high-density integration with high-density electronic components, ultra-fine resist patterns are required.

On the other hand, apart from the chemically amplified resist,
A method for improving various properties by adding a photobase generator to a photosensitive composition has been reported. The photobase generator refers to a compound that generates a base when a bond is cleaved by irradiation with ionizing radiation such as light. For example, a method of improving the resolution and standing wave by adding a photobase generator (Japanese Patent Laid-Open No.
83079) and a method of improving the resist pattern shape and resolution by adding a basic compound that decomposes upon irradiation with ionizing radiation such as light (Japanese Patent Application Laid-Open No.
-266100), a method of increasing the sensitivity by using an acyloxyimino group-containing compound (Japanese Patent No. 2687578), and the like.

However, in the method utilizing the irradiation of actinic rays or radiation, the efficiency of base generation is low, and the effect of improvement is not sufficiently obtained in any case. That is, in the case of the photobase generator, when the intrinsic absorption deviates from the exposure wavelength, the generation efficiency of the base decreases. That is, KrF
(248 nm), there is sufficient absorption, and even if the effect is obtained, the same effect cannot be obtained if the absorption coefficient is low with ArF (193 nm).

In the above prior art, no consideration is given to the generation efficiency of the base, and in order to obtain a sufficient effect, it is necessary to match the absorption of the photobase generator to the exposure wavelength. Even if the absorption is not appropriate, in order to obtain a sufficient effect, it is necessary to add a large amount, and as a result, problems such as a significant decrease in sensitivity occur.

[0006]

An object of the present invention is to provide a chemically amplified radiation-sensitive positive resist composition having an improved resist pattern shape without depending on the wavelength of ionizing radiation to be irradiated. is there.

[0007]

According to the present invention, a radiation-sensitive resist composition having the following constitution is provided, and the above object of the present invention is achieved. (1) (A1) a resin whose dissolution rate in an alkali developer is increased by the action of an acid, (B) a compound which generates an acid by irradiation with ionizing radiation, (C) a solvent, and (D) a bond is cleaved by an acid. A radiation-sensitive positive resist composition comprising: a compound which generates an ionic compound by heating, and at least one of the ionic compounds contains a compound which does not react with the proton-donating compound in the composition. (2) The component (D) has the following general formulas (1) and (2)
The radiation-sensitive positive resist composition according to the above (1), which is at least one compound selected from the group consisting of compounds represented by the formula:

[0008]

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In the general formula (1): A ₁ and A ₂ each independently represent an electron donating group. Z is a carbon atom, -SO
Represents _2- or -C (= O)-. E represents a 3- to 7-membered ring structure containing an adjacent carbon atom, oxygen atom and Z, and this ring structure may have a substituent and a condensed ring. In the general formula (2): G represents two adjacent carbon atoms and X
And an electron-donating ring structure in which at least one other ring having a substituent is condensed with a 3- to 8-membered ring structure. X represents a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. Z and E have the same meanings as Z and E in the general formula (1). (3) The radiation-sensitive positive resist composition according to the above (1) or (2), further comprising (E) a nitrogen-containing basic compound. (4) The radiation-sensitive positive resist composition according to any one of the above (1) to (3), further comprising (F) a surfactant.

According to the findings of the present inventors, a chemically amplified resist that forms a pattern by generating an acid upon irradiation and decomposing a polymer using the acid as a catalyst to increase the solubility of the polymer after exposure to light is generated. Bonds are cleaved by the acid to generate an ionic compound, and by adding a compound that does not react with the proton-donating compound in the composition, the shape of the resist pattern is significantly affected without being affected by the exposure wavelength. To be improved. As described above, a compound that is cleaved by light and converted into an ionic compound (polarity is converted) to exhibit a function is effective in a resist. Its effectiveness may come from the ions generated themselves or from additional reactants from the ions generated. In the present invention, the effect (converted high polarity) brought about by the generated ions themselves is used. In that case, since the converted ionic compound functions effectively, it is desired that the ionic structure be stable so that the ionic compound is not deactivated. In the present invention, since the generated ionic compound does not react with the proton donating compound, the ionic compound is not deactivated and the ionic structure is stable.

The reason is that the exposure wavelength is no longer affected if the mechanism is a mechanism that is converted into a functional substance by the action of an acid as in the component (D) in the present invention. For example, a compound that was effective with a KrF excimer laser is also effective with an ArF or F ₂ excimer laser, an electron beam, or an i-line. The fact that the conversion efficiency by acid is higher than the conversion efficiency by light also contributes to the advantage of the mechanism by acid. Still further, compounds that are simultaneously converted by light and acid are considered more effective. For these reasons, the compound of the above-mentioned component (D) of the present invention utilizing an acid can obtain the same effect as a conventional photobase generator more efficiently without being affected by the exposure wavelength.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, components used in the present invention will be described in detail. In the present invention, the resin (A
1) A positive resist composition using a resin whose dissolution rate in an alkali developing solution is increased by the action of an acid.

[1] (D) The compound (D) component in which the bond is cleaved by an acid to generate an ionic compound, and at least one of the ionic compounds does not react with the proton donating compound in the composition, It is essential that the ionic compound generated as described above does not react with the proton donating compound in the composition. In the present invention, as the “ionic compound”, a compound exhibiting an inhibition function with respect to the alkali solubility of the resist is preferable. Specifically, such as having a conjugated structure and stabilizing the cation,
Examples thereof include a benzyl cation, an aryl cation, an allyl cation, and a zwitter ion having a structure having a positive charge and a negative charge during conjugation. The proton-donating compound in the composition includes, for example, a compound having a carboxyl group such as a residual alcoholic solvent or an unprotected acidic group in a polymer, for example, a phenolic hydroxyl group such as polyhydroxystyrene or a polyacrylate or polymethacrylate. . Further, that the ionic compound generated as described above does not react with the proton donating compound in the composition means that the ionic compound does not react with the acidic group in the proton donating compound, and specifically, Is that the ionic compound does not form a new covalent bond such as forming an ester bond with groups such as -OH and -COOH in the proton donating compound, and the ionic compound does not lose ionicity. . When a proton is received from the proton-donating compound and a new salt is formed with the proton-donating compound, the ion is maintained, and therefore, it is not considered to have reacted.

When the generated ionic compound reacts with the proton-donating compound in the composition, rapid fading in the near ultraviolet and visible light regions is often observed in the above composition. Therefore, the fact that the generated ionic compound does not react with the proton-donating compound in the composition can be confirmed by the fact that any one of the transmittance and the absorbance of the composition does not fluctuate. Confirmed by absorbance measurement. That is, if the absorption maximum in the near ultraviolet light or visible light region is dramatically shifted to the shorter wavelength side and its ε is within the error range, and is reduced to 0.7 times or less, the proton donation in the composition is Is determined to have reacted with the sex compound. When all the ionic compounds in the generated ionic compound react with the proton-donating compound in the composition, the effect of the present invention cannot be obtained. This is because, when reacted with a proton donating compound, the ionicity of the ionic compound is deactivated.

The component (D) has a pKa of 9.5.
Hereinafter, a compound in which a bond is cleaved by an acid of 4.5 or less to generate an ionic compound is particularly preferable. pKa is 9.
As the acid of 5 to 4.5, for example, phenol (pKa:
9.9) stronger acids such as acetic acid (pKa: 4.8). As an acid having a pKa of 4.5 or less, succinic acid (pKa: 4.2), benzoic acid (pKa: 4.2), trifluoroacetic acid (pKa: 0.2), benzenesulfonic acid (pKa: -2. 6), sulfuric acid (pKa: about -3), perfluoroalkylsulfonic acid (pKa: -12 or less)
Is exemplified. However, if these pKa values are different,
For example, if you use another calculation formula such as Taft's calculation method,
The relative values of these numbers apply analogously. Hereinafter, the bond of the component (D) in the present invention is cleaved by the action of an acid,
An example in which an ionic compound is generated will be described by taking the following compound as an example.

[0016]

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As the component (D) which is preferable from the structural point of view, compounds represented by the above general formulas (1) and (2) can be mentioned. These compounds can be used alone or in combination of two or more.

A ₁ and A _{2 in} the general formula (1) each independently represent an electron donating group. A ₁ in the general formula (I)
And the electron donating group represented by A ₂ are those having an oxidation potential “E ^OX ” of +
1.80 V (vs. SCE) or higher group, preferably +1.
It means a group of 70 V (vs. SCE) or more. Specific examples include a substituted or unsubstituted aryl group having 5 to 22 carbon atoms and a substituted or unsubstituted alicyclic group having 3 to 12 carbon atoms.

Preferred substituted or unsubstituted aryl group skeletons include phenyl, biphenyl, fluorene,
Thiophene, furan, naphthalene (+1.60 V), phenanthrene (+1.58 V), anthracene (+1.60 V).
16V), pyrene (+ 1.20V), perylene (+0.
85V), indene (+ 1.23V), xanthene, thioxanthene, phenothiazine (+ 0.59V), phenoxazine, carbazole, and azulene. Of these aryl skeletons, phenyl, biphenyl, fluorene, thiophene, and furan preferably have a substituent. Preferred substituted or unsubstituted alicyclic skeletons include adamantane, norbornene, norbornadiene, (+1.54 V), quadricyclane (+0.9
1V). Examples of the substituent include an alkoxy group having 1 to 20 carbon atoms in the alkyl chain, a monoalkylamino group, a dialkylamino group, and an amino group.

The oxidation potential (E ^OX ) is +1.80 V (vs.
SCE) or more electron-donating groups include phenyl, biphenyl, fluorene, thiophene, and furan in which at least one of the above substituents is substituted, and naphthalene, phenanthrene, anthracene, pyrene, perylene, and indene which may be substituted with the above substituents. , Xanthene, thioxanthene, phenothiazine, phenoxazine, sorbazole, azulene, adamantane, norbornene, norbornadiene,
Quadricyclans are exemplified.

When the aryl skeleton is a phenyl group, a monoalkoxyphenyl group having 1 to 20 carbon atoms in the alkyl chain;
Dialkoxyphenyl group, trialkoxyphenyl group,
Monoalkylaminophenyl, dialkylaminophenyl, and bisdialkylaminophenyl groups are preferably used.

Specific examples of the above-mentioned monoalkoxyphenyl group, dialkoxyphenyl group and trialkoxyphenyl group include a methoxyphenyl group (+1.76 V), a dimethoxyphenyl group (+1.45 V), and a trimethoxyphenyl group (+1.49 V). ), Ethoxyphenyl, diethoxyphenyl, triethoxyphenyl, isopropoxyphenyl, diisopropoxyphenyl, triisopropoxyphenyl, n-butoxyphenyl, din
-Butoxyphenyl group, tri-n-butoxyphenyl group,
tert-butoxyphenyl group, di-tert-butoxyphenyl group, tri-tert-butoxyphenyl group, se
c-butoxyphenyl group, disec-butoxyphenyl group, trisec-butoxyphenyl group, cyclopropoxyphenyl group, cyclobutoxyphenyl group, cyclopentyloxyphenyl group, cyclohexyloxyphenyl group, nC ₁₀ H ₂₁ -oxyphenyl group , n-C ₁₂ H ₂₅ -
An oxyphenyl group, an nC ₁₆ H ₃₃ -oxyphenyl group,
n-C ₁₈ H ₃₇ - oxyphenyl group, tetrahydrofuranyl oxyphenyl group include di oxa oxy phenyl group.

Specific examples of the above monoalkylaminophenyl group, dialkylaminophenyl group, and bisdialkylaminophenyl group include a methylaminophenyl group, a dimethylaminophenyl group (+0.78 V), and a bisdimethylaminophenyl group (+0. 16V), ethylaminophenyl group, diethylaminophenyl group (+0.73 V), bisdiethylaminophenyl group, n-propylaminophenyl group, di-n-propylaminophenyl group, bis (di-n
-Propylamino) phenyl group, n-butylaminophenyl group, di-n-butylaminophenyl group, bis (di-n-butylaminophenyl group)
(Butylamino) phenyl group, tert-butylaminophenyl group, tert-amylaminophenyl group, cyclopentylaminophenyl group, dicyclopentylaminophenyl group, dihexylaminophenyl group, cyclohexylaminophenyl group, dicyclohexylaminophenyl group, heptylaminophenyl group , octyl aminophenyl group, a nonyl aminophenyl group, di-n-C ₁₀ H ₂₁ - aminophenyl group, di-n-C ₁₂ H ₂₅ - aminophenyl group, di-n-C ₁₆ H ₃₃ - aminophenyl group, di n- C ₁₈ H ₃₇ - aminophenyl group, trityl aminophenyl group, benzyloxycarbonylamino phenyl group, monophenyl aminophenyl group (+ 0.79 V), diphenylamino phenyl group (0 + 0.98 V) is.

The oxidation potential (E ^OX ) is +1.70 V (vs.
SCE) or more of the electron donating site is an alkyl group having at least two alkoxy groups having 1 to 20 carbon atoms, and
Phenyl, biphenyl, fluorene, thiophene, furan having at least one monoalkylaminophenyl group, dialkylaminophenyl and amino group substituted, and naphthalene, phenanthrene, anthracene, pyrene, perylene, indene which may be substituted by the above substituents ,
Xanthene, thioxanthene, phenothiazine, phenoxazine, carbazole, azulene, adamantane, norbornene, norbornadiene and quadricyclane are exemplified. Specific substituents are the same as described above.

Further, A ₁ and A ₂ have an oxidation potential (E ^OX ) of at least one of them of +1.80 V (vs. S.
CE) It may have the following substituents within a range satisfying the above. That is, an aromatic amine substituent, a heterocyclic amine substituent, an amide group, an imide group, an ester group, a halogen group, a halogen-substituted alkyl group, a halogen-substituted aryl group, a hydroxyl group, a carboxyl group, a thiol group, a cyano group,
Examples thereof include a nitro group, a formyl group, a sulfonyl group, a sulfonamide group, an acyl group, an aroyl group, an alkyl group having 1 to 20 carbon atoms, a heterocyclic group, an aryl group, an alkenyl group, and an aralkyl group.

Specific examples of the aromatic amine and heterocyclic amine substituents (substituted on a carbon atom or a nitrogen atom) include aniline derivatives (for example, aniline, N-methylaniline, N-ethylaniline, N, N'-dimethylaniline, N, N'-diethylaniline, N-propylaniline, 2-methylaniline, 3-methylaniline,
-Methylaniline, 2,6-dinitroaniline, etc.), diphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (for example, pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-
Dimethylpyrrole, 2,4-dimethylpyrrole, 2,5
-Dimethylpyrrole, etc.), oxazole derivatives (eg, oxazole, isoxazole, etc.), thiazole derivatives (eg, thiazole, isothiazole, etc.), imidazole derivatives (eg, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), Pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg, pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (eg, pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine Derivatives (eg pyridine, methylpyridine, ethylpyridine,
Propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-
Methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2
-Pyridone, 4-pyrrolidinopyridine, 1-methyl-4
-Phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.),
Pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazolone derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, guanidine derivatives, quinoline derivatives (for example, quinoline, 3- Quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives,
Quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives,
Phenazine derivatives, phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like are exemplified.

As the amide group, a carbamoyl group, N-
Examples thereof include a methylcarbamoyl group, an N, N-dimethylcarbamoyl group, an acetamido group, an N-methylacetamido group, a propionamide group, a benzamide group, a methacrylamide group, a decanylamide group, a laurylamide group, a partimylamide group, and a stearylamide group. . Examples of the imide group include a phthalimide group, a succinimide group, and a maleimide group.

As the ester group, a carbamate group, a methyl ester group, an ethyl ester group, a propyl ester group, an isopropyl ester group, an n-butyl ester group,
sec-butyl ester group, tert-butyl ester group, pentyl ester group, isopentyl ester group, t
Examples thereof include an ert-amyl ester group, a hexyl ester group, a heptyl ester group, an octyl ester group, a cyclopentyl ester group, a cyclohexyl ester group, a cycloheptyl ester group, a norbornyl ester group, and an adamantyl ester group.

Examples of the halogen-substituted alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group,
Examples thereof include a 1,1,1-trichloroethyl group and a nonafluorobutyl group. As the halogen-substituted aryl group,
Fluorobenzene group, chlorobenzene group, 1,2,3
Examples thereof include a 4,5-pentafluorobenzene group. Examples of the alkyloxy group and the alkenyloxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, an n-butoxy group, a sec-butoxy group,
t-butoxy group, pentyloxy group, isopentyloxy group, tert-amyloxy group, hexyloxy group,
Examples include a heptyloxy group, an octyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a norbornyloxy group, an adamantyloxy group, an acryloxy group, and a methacryloxy group.

Examples of the heterocyclic group include thiophene, furan, tetrahydrofuran, morpholine, pyran, tetrahydropyran, dioxane, thiocarbazole, xanthene group and thioxanthene group. As the alkyl group, those having 1 to 20 carbon atoms are preferable, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, Isopentyl group, tert-amyl group, hexyl group, heptyl group, octel group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, adamantyl group, decanyl group , Lauryl group, partimyl group, stearyl group and the like.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms. Specifically, a phenyl group, a naphthyl group,
Biphenyl group, phenanthrenyl group, anthranyl group,
Alkoxyphenyl groups such as fluorenyl group, pyrene group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group A 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, an ethylphenyl group,
Alkylphenyl groups such as 4-tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group, alkylnaphthyl groups such as methylnaphthyl group and ethylnaphthyl group, alkoxynaphthyl groups such as methoxynaphthyl group and ethoxynaphthyl group, and dimethyl Examples thereof include a dialkylnaphthyl group such as a naphthyl group and a diethylnaphthyl group, and a dialkoxynaphthyl group such as a dimethoxynaphthyl group and a diethoxynaphthyl group.

The alkenyl group preferably has 2 to 10 carbon atoms, and specific examples include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group and a cyclohexenyl group. The aralkyl group is preferably one having 7 to 15 carbon atoms, specifically, a benzyl group,
Examples thereof include a phenylethyl group and a phenethyl group.

Z is a carbon atom, —SO ₂ —, or —C
(= O)-. E represents a 3- to 7-membered ring structure containing an adjacent carbon atom, oxygen atom, and Z;
Another ring may be condensed or may have a substituent. Among them, 5- and 6-membered ring structures are preferred. E may include an oxygen atom, a nitrogen atom, and a sulfur atom. Examples of the 3- to 7-membered ring structure of E include α-lactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, propane sultone, butane sultone, dioxane, tetrahydrofuran, tetrahydropyran and the like. Can be Another ring that may be condensed into a 3- to 6-membered ring structure can be selected from the group consisting of a substituted or unsubstituted aromatic group and an alicyclic group. As the aromatic ring of the aromatic group, an oxygen atom, a sulfur atom, or a nitrogen atom may be contained in the ring. Specific examples of the aromatic ring include a benzene ring, a furan ring, a pyrrole ring, a pyrazole ring, and an imidazole. Ring, oxazole ring, thiazole ring,
Thiophene ring, oxadiazole ring, triazole ring,
Examples include a pyridine ring, a pyrazine ring, a pyridazine ring, and a pyrimidine ring. As the alicyclic structure of the alicyclic group, an oxygen atom, a sulfur atom, and a nitrogen atom may be contained in the ring, and specific examples of the alicyclic structure include a cyclopentane ring,
Cyclohexane ring, cycloheptane ring, cyclooctane ring, pyrrolidine ring, dioxolane ring, pyrazoline ring, pyrazolidine ring, pyran ring, piperidine ring, dioxane ring, morpholine ring, piperazine ring, norbornene ring.

G has a 3- to 8-membered ring structure, preferably a 5- or 6-membered ring structure containing two adjacent carbon atoms and X, and has at least one other ring having a substituent thereon. Represents a condensed electron-donating ring structure. In G, a 3- to 8-membered ring structure containing two adjacent carbon atoms and X includes cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, oxirane, oxetane, oxolane, dioxolane, oxane, Dioxane, tetrahydrothiofuran,
Tetrahydrothiopyran, pyrrolidine, pyrazolidine,
Piperidine, piperazine, morpholine, tetrahydropyran, γ-butyrolactone and the like.

The ring fused to the 3- to 8-membered ring structure is the same as another ring which may be fused to the 3- to 7-membered ring structure relating to E. A substituent which may be present on the ring of E, the fused ring of E, the fused ring of G, or A ₁ , A ₂
As a further substituent which may be contained,
20 alkyl groups, aryl groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aralkyl groups having 7 to 15 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, 2 to 20 carbon atoms
And further include a primary aliphatic amino group, a secondary aliphatic amino group, a mixed amine substituent, an aromatic amine substituent, a heterocyclic amine substituent, and an amide. Group, imide group, halogen atom, halogen-substituted alkyl group, halogen-substituted aryl group, alkenyloxy group, alkyl ester group, heterocyclic group, hydroxyl group, carboxyl group, thiol group, cyano group, nitro group, formyl group, sulfonyl group, It may have a substituent such as a sulfonamide group, an alkoxy group, an acyl group and an acyloxy group. Furthermore, primary aliphatic amino groups, secondary aliphatic amino groups, hybrid amines substituents, aromatic amines substituents,
Heterocyclic amine substituents, amide group, imide group, halogen atom, halogen-substituted alkyl group, halogen-substituted aryl group, alkenyloxy group, alkyl ester group, heterocyclic group, hydroxyl group, carboxyl group, thiol group, cyano group, nitro Represents a group, a formyl group, a sulfonyl group, a sulfonamide group, an alkoxy group, an acyl group, or an acyloxy group.

Here, the alkyl group preferably has 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. , Pentyl, isopentyl, tert-amyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, adamantyl Group, decanyl group, lauryl group, partimyl group, stearyl group and the like.

The aryl group preferably has 6 to 20 carbon atoms, and specifically includes a phenyl group, a naphthyl group, a biphenyl group, a phenanthrenyl group, an anthranyl group, a fluorenyl group, a pyrene group, and a p-methoxyphenyl group. , M
-Methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group,
alkoxyphenyl groups such as m-tert-butoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-t
alk-naphthyl groups such as tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group; alkylnaphthyl groups such as methylnaphthyl group and ethylnaphthyl group; methoxynaphthyl group and ethoxynaphthyl group; and dimethylnaphthyl group. And a dialkylnaphthyl group such as a diethylnaphthyl group, and a dialkoxynaphthyl group such as a dimethoxynaphthyl group and a diethoxynaphthyl group. The alkenyl group preferably has 2 to 10 carbon atoms, and specific examples include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. The aralkyl group preferably has 7 to 15 carbon atoms, and specific examples include a benzyl group, a phenylethyl group, and a phenethyl group.

Primary aliphatic amine substituents include amino, methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, sec-butylamino and the like. , T
tert-butylamino group, pentylamino group, tert
-Amylamino group, cyclopentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group, cetylamino group, methylenediamino group, ethylenediamino group, tetraethylenepentaamino group Etc. are exemplified.

Secondary aliphatic amine substituents include dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino, diisobutylamino, di-sec- Butylamino group, dipentylamino group, dicyclopentylamino group, dicyclohexylamino group, diheptylamino group,
Examples thereof include a dioctylamino group, a dinonylamino group, a didecylamino group, a didodecylamino group, and a dicetylamino group.

Specific examples of the aromatic amine and heterocyclic amine substituents (substituted on a carbon atom or a nitrogen atom) include aniline derivatives (for example, aniline, N-methylaniline, N-ethylaniline, N, N'-dimethylaniline, N, N'-diethylaniline, N-propylaniline, 2-methylaniline, 3-methylaniline,
-Methylaniline, 2,6-dinitroaniline, etc.), diphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (for example, pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-
Dimethylpyrrole, 2,4-dimethylpyrrole, 2,5
-Dimethylpyrrole, etc.), oxazole derivatives (eg, oxazole, isoxazole, etc.), thiazole derivatives (eg, thiazole, isothiazole, etc.), imidazole derivatives (eg, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), Pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg, pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (eg, pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine Derivatives (eg pyridine, methylpyridine, ethylpyridine,
Propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-
Methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2
-Pyridine, 4-pyrrolidinopyridine, 1-methyl-4
-Phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.),
Pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazolone derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, guanidine derivatives, quinoline derivatives (for example, quinoline, 3- Quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives,
Quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives,
Phenazine derivatives, phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like are exemplified.

As the amide group, a carbamoyl group, N-
Examples thereof include a methylcarbamoyl group, an N, N-dimethylcarbamoyl group, an acetamido group, an N-methylacetamido group, a propionamide group, a benzamide group, a methacrylamide group, a decanylamide group, a laurylamide group, a partimylamide group, and a stearylamide group. . Examples of the imide group include a phthalimide group, a succinimide group, and a maleimide group.

As the ester group, a carbamate group, a methyl ester group, an ethyl ester group, a propyl ester group, an isopropyl ester group, an n-butyl ester group,
sec-butyl ester group, tert-butyl ester group, pentyl ester group, isopentyl ester group, t
Examples thereof include an ert-amyl ester group, a hexyl ester group, a heptyl ester group, an octyl ester group, a cyclopentyl ester group, a cyclohexyl ester group, a cycloheptyl ester group, a norbornyl ester group, and an adamantyl ester group.

Examples of the halogen-substituted alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group,
Examples thereof include a 1,1,1-trichloroethyl group and a nonafluorobutyl group.

Examples of the halogen-substituted aryl group include a fluorobenzene group, a chlorobenzene group, 1,2,3,4,5
-Pentafluorobenzene group and the like.

Examples of the alkyloxy group and the alkenyloxy group include a methoxy group, an ethoxy group, a propyloxy group,
Isopropyloxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, tert-amyloxy group, hexyloxy group, heptyloxy group, octyloxy group,
Examples thereof include a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a norbornyloxy group, an adamantyloxy group, an acryloxy group, and a methacryloxy group. As the heterocyclic group, thiophene,
Examples thereof include furan, tetrahydrofuran, morpholine, pyran, tetrahydropyran, dioxane, thiocarbazole, xanthene group, and thioxanthene group.

In the general formula (1), A ₁ and A ₂ represent groups of each ring of naphthalene, phenanthrene, anthracene, pyrene, xanthene, thioxanthene, phenothiazine and phenoxazine, a methoxyphenyl group, a dimethoxyphenyl group, Methoxyphenyl group, ethoxyphenyl group, diethoxyphenyl group, triethoxyphenyl group, n-butoxyphenyl group, di-n-butoxyphenyl group, tri-n-butoxyphenyl group, tert-butoxyphenyl group, ditert-butoxyphenyl group , Tritert-butoxyphenyl group, methylaminophenyl group, dimethylaminophenyl group, bisdimethylaminophenyl group, ethylaminophenyl group, diethylaminophenyl group, bisdiethylaminophenyl group, di-n-butylaminophenyl Group, a bis (di-n-butylamino) phenyl group, a dicyclopentylaminophenyl group, and a dihexylaminophenyl group. As Z, -C (=
O) -, - SO ₂ - is preferred. E is preferably a 4- to 6-membered ring. In the general formula (2), G is preferably a xanthene, thioxanthene, or fluorene skeleton.
The Z, -C (= O) - , - SO 2 - is preferred.
E is preferably a 4- to 6-membered ring.

Specific examples of the compound represented by the general formula (1) are shown below.

[0048]

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[0049]

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Specific examples of the compound represented by the general formula (2) are described below.

[0051]

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[0052]

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The amount of the component (D) added to the composition is as follows:
Usually 0.0% based on the total solid content of the resist composition.
The content is 1 to 20% by weight, preferably 0.05 to 10% by weight, and more preferably 0.07 to 5% by weight.

[2] The resin as the component (A1) used in the present invention is a resin whose dissolution rate in an alkali developing solution is increased by the action of an acid (also referred to as “acid-decomposable resin”).
If so, known ones can be used. Preferred (A1)
The acid-decomposable resin has an alicyclic structure in the main chain or side chain of the resin. Particularly preferred acid-decomposable resin (A1) is an alkali developer by the action of an acid containing a repeating structural unit represented by the following general formula (I ′) and a repeating structural unit represented by the following general formula (II ′) And a resin having an increased dissolution rate with respect to water.

[0055]

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[0056]

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In the general formula (I ′), R _{11 to} R ₁₄ each independently represent a hydrogen atom or an alkyl group which may have a substituent. a is 0 or 1; In the general formula (II ′), R ₁ is
Represents a hydrogen atom or a methyl group. A represents a single bond, an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, or a combination of two or more groups selected from the group consisting of an ester group. W,
It represents at least one of partial structures containing alicyclic hydrocarbons represented by the following general formulas (pI) to (pVI).

[0058]

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In the formula, R ₁₅ is a methyl group, an ethyl group, n-
Represents a propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. R _{16 to} R ₂₀ each independently represent a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{16 to} R ₁₈ , or Either R ₁₉ or R ₂₀ represents an alicyclic hydrocarbon group. R ₂₁
To R ₂₅ are each independently a hydrogen atom, a group having 1 to 4 carbon atoms,
It represents a linear or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R _{21 to} R ₂₅ represents an alicyclic hydrocarbon group. Further, any of R ₂₃ and R ₂₅ represents a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms. R ₂₆ to R ₂₉ each independently of 1 to 4 carbon atoms, represents a linear or branched alkyl group or alicyclic hydrocarbon group, provided that at least one of R ₂₆ to R ₂₉ are fat Represents a cyclic hydrocarbon group.

In the general formula (I ′) showing the repeating structural unit of the acid-decomposable resin, R _{11 to} R ₁₄ represent a hydrogen atom or an alkyl group which may have a substituent, as described above. The alkyl group of R _{11 to} R ₁₄ has 1 to 12 carbon atoms.
Are preferred, more preferably those having 1 to 10 carbon atoms, specifically methyl, ethyl, propyl,
Isopropyl group, n-butyl group, isobutyl group, sec
-Butyl group, t-butyl group, pentyl group, hexyl group,
Preferable examples include a heptyl group, an octyl group, a nonyl group and a decyl group. Examples of the substituent of the alkyl group include a hydroxy group, an alkoxy group and an alkoxyalkoxy group. The preferred carbon number of these alkoxy groups and alkoxyalkoxy groups is 4 or less. In the general formula (I ′), a is 0 or 1.

In the general formula (II ′) representing a repeating structural unit of the acid-decomposable resin, R ₁ represents a hydrogen atom or a methyl group.
In the general formula (II ′), the alkylene group for A includes:
Examples include groups represented by the following formulas. -[C (Rf) (Rg)] r- In the above formula, Rf and Rg represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, and they may be the same or different. . As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r is an integer of 1 to 10. General formula (II ')
In the above, the cycloalkylene group for A has 3 carbon atoms.
And a cyclopentylene group, a cyclohexylene group, a cyclooctylene group and the like.

W in the general formula (II ′) is represented by the general formula (p
It represents at least one of the partial structures containing alicyclic hydrocarbons represented by I) to (pVI). General formula (pI)
In (pVI), the alkyl group for R _{16 to} R ₂₉ may be substituted or unsubstituted.
Represents a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-
Examples thereof include a butyl group, an isobutyl group, a sec-butyl group and a t-butyl group. Further, as a further substituent of the alkyl group, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, Examples include a carboxy group, an alkoxycarbonyl group, and a nitro group.

The alicyclic hydrocarbon group for R _{15 to} R _{29 or} the alicyclic hydrocarbon group formed by Z and a carbon atom may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The number of carbon atoms is preferably from 6 to 30, particularly preferably from 7 to 25. These alicyclic hydrocarbon groups may have a substituent. Below, the structural example of an alicyclic part among alicyclic hydrocarbon groups is shown.

[0064]

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[0065]

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[0066]

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

Examples of the substituent of these alicyclic hydrocarbon groups include an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, and more preferably a methyl group, an ethyl group, a propyl group, and a substituent selected from the group consisting of an isopropyl group. Represent. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

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

[0070]

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

[0072]

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[0073]

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[0074]

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The (A1) acid-decomposable resin used in the present invention may further contain a repeating unit represented by the following general formula (III ′).

[0076]

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In the general formula (III ′),_TwoIs -O-
Or -N (R_Three)-. Where R _ThreeIs a hydrogen atom, water
Acid group or -O-SO_Two-R_FourRepresents R_FourIs an alkyl
Group, haloalkyl group, cycloalkyl group or camphor residue
Represent.

The alkyl group for R ₄ 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. , More preferably a methyl group,
Ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group.

Examples of the haloalkyl group for R ₄ include a trifluoromethyl group, a nanofluorobutyl group, a pentadecafluorooctyl group, and a trichloromethyl group. Examples of the cycloalkyl group for R ₄ include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

Hereinafter, specific examples of the monomer corresponding to the repeating structural unit represented by the general formula (III ′) are shown, but the invention is not limited thereto.

[0081]

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[0082]

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The acid-decomposable resin as the component (A1) is, in addition to the above-mentioned repeating structural units, dry etching resistance, standard developing solution suitability, substrate adhesion, resist profile, and general necessary properties of a resist. Various repeating structural units can be contained for the purpose of adjusting resolution, heat resistance, sensitivity and the like.

Examples of such a repeating structural unit include, but are not limited to, repeating structural units corresponding to the following monomers. Thereby, the performance required for the acid-decomposable resin, in particular, (1) solubility in a coating solvent, (2) film-forming property (glass transition point),
Fine adjustment of (3) alkali developability, (4) film loss (hydrophobicity, selection of alkali-soluble group), (5) adhesion of unexposed portion to substrate, (6) dry etching resistance, etc. becomes possible. .

As such a monomer, for example, an addition-polymerizable unsaturated bond selected from acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like can be used. And the like.

Specifically, the following monomers can be mentioned. Acrylic esters (preferably alkyl acrylate having an alkyl group having 1 to 10 carbon atoms): methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylic Acid-t-octyl, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate,
Trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate,
Methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate and the like.

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

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

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

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

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

Vinyl esters: vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl 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: dimethyl itaconate, diethyl itaconate, dibutyl itaconate and the like. Dialkyl esters or monoalkyl esters of fumaric acid; dibutyl fumarate;

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

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

In the acid-decomposable resin, the molar ratio of each repeating structural unit depends on the dry etching resistance of the resist, the suitability for a standard developing solution, the substrate adhesion, the resist profile, and the resolving power, heat resistance, which is a general required performance of the resist. It is set as appropriate to adjust properties, sensitivity, and the like. Further, the content of the repeating structural unit represented by the general formula (I ′) in the acid-decomposable resin is preferably from 25 to 70 mol%, more preferably from 28 to 65 mol%, even more preferably in all the repeating structural units. Is 30 to 60 mol%. In the present invention, the content of the repeating structural unit represented by the general formula (II ′) in the acid-decomposable resin is 5 to 3 in all the repeating structural units.
0 mol% is preferred, and more preferably 15 to 25 mol%.
And more preferably 15 to 20 mol%.

The content of the repeating structural unit represented by the general formula (III ′) in the acid-decomposable resin is preferably from 20 to 80 mol%, more preferably from 25 to 7 mol%, based on all the repeating structural units.
It is 0 mol%, and more preferably 30 to 60 mol%.

The content of the repeating structural unit based on the monomer of the additional copolymer component in the resin can be appropriately set according to the desired resist properties. It is preferably at most 99 mol%, more preferably at most 90 mol%, even more preferably at most 80 mol%, based on the total number of moles of the repeating structural units represented by (I ') and (II').

The molecular weight of the acid-decomposable resin as described above is weight average (Mw: polystyrene conversion value by GPC method).
In the range of preferably 1,000 to 1,000,000, more preferably 1,500 to 500,000, still more preferably 2,000 to 200,000, and still more preferably 2,500 to 100,000 Yes, the bigger,
While the heat resistance and the like are improved, the developability and the like are lowered, and the balance is adjusted to a preferable range by these balances. The acid-decomposable resin used in the present invention can be synthesized according to a conventional method (for example, radical polymerization).

In the positive photoresist composition of the present invention, the compounding amount of the acid-decomposable resin (A1) in the whole resist composition is preferably 40 to 99.99% by weight based on the total solid content. Preferably 50 to 99.97% by weight
It is.

Preferred specific examples of combinations of the repeating structural units of the acid-decomposable resin (A1) are shown below.

[0102]

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[0103]

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[0104]

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[3] The compound (photoacid generator) which generates an acid upon irradiation with ionizing radiation as the component (B) will be described. As the photoacid generator used in the present invention, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or a microresist is used. Known light (ultraviolet light of 400 to 200 nm, far ultraviolet light, particularly preferably g-line, h-line, i-line, K
rF excimer laser light), ArF excimer laser light, an electron beam, an X-ray, a molecular beam or a compound capable of generating an acid by an ion beam, and a mixture thereof can be appropriately selected and used.

Other photoacid generators used in the present invention include, for example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts and the like.
Organic halogen compound, organic metal / organic halide, o
A photoacid generator having a nitrobenzyl-type protecting group; a compound represented by photolysis such as iminosulfonate that generates sulfonic acid; a disulfone compound; a diazoketosulfone; and a diazodisulfone compound.
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 photoacid generators, an example of the photoacid generator that can be effectively used is a photoacid generator in which the anion has a fluorine atom. For example, the cation portion is composed of iodonium or sulfonium, and the anion portion is R ^F
SO ₃ ^- (wherein, the R ^F is, a fluorine-substituted alkyl group having 1 to 10 carbon atoms) photoacid generator is selected from the sulfonic acid salt is composed of an anion represented by is used . The fluorine-substituted alkyl group represented by R ^F may be linear, branched, or cyclic. Preferred R ^F is represented by CF ₃ (CF ₂ ) y, wherein y is 0.
A fluorine-substituted linear alkyl group, which is an integer of from 9 to 9;
The cation part of the photoacid generator is preferably represented by the following general formulas (I) to (III).

[0109]

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In the above general formulas (I) to (III), R ₁
To R ₃₇ are the same or different and each represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, a halogen atom or -S
—R represents a ₃₈ group. R ₃₈ represents a linear, branched or cyclic alkyl group or aryl group. R _{1 to} R ₁₅ , R ₁₆ to
Two or more of R ₂₇ , R _{28 to} R ₃₇ are bonded to form a ring containing one or more selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom; Is also good.

In the general formulas (I) to (III), R _{1 to} R
The linear or branched alkyl group of ₃₈ may have a substituent and may have a carbon number such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. 1-4 are mentioned. Examples of the cyclic alkyl group include those having 3 to 8 carbon atoms which may have a substituent, such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group. Examples of the linear or branched alkoxy group for R _{1 to} R ₃₇ include a methoxy group, an ethoxy group,
Those having 1 to 4 carbon atoms such as a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a t-butoxy group are exemplified. Examples of the cyclic alkoxy group include a cyclopentyloxy group, for example, a cyclopentyloxy group and a cyclohexyloxy group. Examples of the halogen atom for R _{1 to} R ₃₇ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the aryl group for R ₃₈ include those having 6 to 14 carbon atoms which may have a substituent such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group. Preferably, these substituents have 1 carbon atom.
~ 4 alkoxy groups, halogen atoms (fluorine atom, chlorine atom, iodine atom), aryl groups having 6 to 10 carbon atoms,
Examples thereof include an alkenyl group having 2 to 6 carbon atoms, a cyano group, a hydroxy group, a carboxy group, an alkoxycarbonyl group, and a nitro group.

Further, R _{1 to} R ₁₅ , R _{16 to} R ₂₇ , R _{28 to} R
Of _37, two or more of formed by combining a single bond, carbon, oxygen, one selected sulfur, and nitrogen or 2
Examples of the ring containing more than one kind include a furan ring, a dihydrofuran ring, a pyran ring, a trihydropyran ring, a thiophene ring, a pyrrole ring, and the like. Specific examples (A1-1) to (A) of the photoacid generator that can be used in the present invention.
1-64) is shown below.

[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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Further, the following photoacid generators can also be preferably used. (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)
_{Shows 3} . 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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[0125]

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

[0127]

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Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. R ²⁰³ , R ²⁰⁴ ,
R ²⁰⁵ each independently represents a substituted or unsubstituted alkyl group or aryl group. Z ⁻ represents a counter anion, for example, BF ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , Si
_{^{F 6 2-, ClO 4 -,}} CF 3 SO 3 - perfluoroalkane sulfonate anion such as, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid Examples of the dye include an anion and a sulfonic acid group-containing dye, but are not limited thereto.

Further, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded via a single bond or a substituent. Specific examples include the following compounds, but are not limited thereto.

[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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The onium salts represented by the general formulas (PAG3) and (PAG4) are known and described, for example, in US Pat.
It can be synthesized by the methods described in 2,807,648 and 4,247,473, JP-A-53-101,331 and the like.

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

[0140]

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In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group. Specific examples include the following compounds, but are not limited thereto.

[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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

[0148]

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

[0150]

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The amount of these photoacid generators to be added is generally in the range of 0.001 to 40% by weight, preferably 0.01 to 20% by weight, more preferably 0.01 to 20% by weight, based on the solids in the composition. Is used in the range of 0.1 to 5% by weight. When the addition amount of the photoacid generator is less than 0.001% by weight, the sensitivity is lowered. When the addition amount is more than 40% by weight, the light absorption of the resist becomes too high, and the profile deteriorates,
The process (especially baking) margin is unfavorably reduced.

[6] The solvent (C) will be described. Examples of the solvent contained in the radiation-sensitive positive resist composition of the present invention as component (C) include, for example, ethylene glycol monoethyl ether acetate, cyclohexanone,
Heptanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, β-methoxyisobutyrate,
Ethyl butyrate, propyl butyrate, methyl isobutyl ketone,
Ethyl acetate, isoamyl acetate, ethyl lactate, toluene,
Xylene, cyclohexyl acetate, diacetone alcohol, N-methylpyrrolidone, N, N-dimethylformamide, γ-butyrolactone, N, N-dimethylacetamide, propylene carbonate, ethylene carbonate and the like. These solvents are used alone or in combination. The choice of the solvent is important because it affects the solubility in the radiation-sensitive positive resist composition of the present invention, coatability on a substrate, storage stability and the like. It is preferable that the amount of water contained in the solvent be small because it affects various resist properties.

Further, as the solvent (C), at least one selected from the following solvent A group and at least one selected from the following solvent B group, or at least one selected from the following solvent B group and the following solvent A mixed solvent containing at least one selected from the group C is preferable, and this makes it possible to obtain a radiation-sensitive positive resist composition which is excellent in reducing particles increase when a resist solution is stored. it can. Group A: propylene glycol monoalkyl ether carboxylate Group B: propylene glycol monoalkyl ether, alkyl lactate and alkoxyalkyl propionate, Group C: γ-butyrolactone, ethylene carbonate and propylene carbonate The range of the content is generally 0.5 to 99.9% by weight, the range of the content of the group B solvent is generally 0.1 to 95.0% by weight, and the content of the group C solvent. Is generally 0.1 to 60.0% by weight.

In addition, at least one kind selected from the solvent A group and at least one kind selected from the solvent B group
A mixed solvent containing a seed and at least one selected from the above-mentioned solvent C group is also preferable. In this mixed solvent, the range of the content of the solvent of Group A is generally 0.5 to 98.0% by weight, and the range of the content of the solvent of Group B is generally 0.1 to 9% by weight.
The range of the content of 95.0% by weight and the group C solvent is generally 0.1 to 50.0% by weight.

A mixed solvent containing at least one kind of alkyl lactate and at least one kind of ester solvent and alkoxyalkyl propionate is also preferable. Examples of the ester solvent include ethyl butyrate, propyl butyrate, ethyl acetate, and isoamyl acetate.
In this mixed solvent, the content range of the alkyl lactate is generally 0.5 to 99.9% by weight, the content range of the ester solvent is generally 0.1 to 95.0% by weight, The content range of the alkyl propionate is generally 0.1 to 99.9% by weight. These mixed solvents are
As long as each of the specified solvents is within the above-mentioned addition amount range, other solvents may be contained.

In the radiation-sensitive positive resist composition of the present invention, the radiation-sensitive positive resist composition having the above-mentioned components has a viscosity of 6.0 m at 25 ° C.
Pa · sec or less, preferably 0.9 to 5.0 mPa ·
sec, more preferably 1.5 to 4.5 mPa · sec.
It is good to be in the range of. If the viscosity exceeds 6.0 mPa · sec, the resolution performance deteriorates, which is not preferable. 25 ° C
Can be measured with an E-type viscometer or the like, for example, after keeping in a precision high-temperature bath at 25 ° C. for 30 minutes.

The viscosity can be adjusted mainly by the use ratio of the solvent (C) to the component (A). Usually, 4 parts by weight of the solvent (C) is added to 100 parts by weight of the component (A).
It is used in an amount of from 00 to 5,000 parts by weight, preferably from 700 to 2,000 parts by weight. As a specific method of adjusting the viscosity, for example, first, the component (A) 100
Using 400 parts by weight of the solvent (C) with respect to parts by weight, the solid content is dissolved, and the component (B) is added and dissolved therein. Other additives can be added as needed. The viscosity of the obtained composition is measured. If the viscosity is higher than desired, the composition is sequentially diluted with the same solvent in which the solid content is dissolved as described above, and the viscosity is measured. The viscosity of the composition depends on the type of the repeating unit of the component (A), the copolymerization ratio, the molecular weight and the degree of dispersion,
Also, it greatly changes depending on the combination with other additive components.
For this reason, it is extremely difficult to predict in advance the optimum amount of solvent used and the amount of change in viscosity due to dilution, so the above specific method is effective.

[7] The resist composition of the present invention preferably contains, as the component (E), a nitrogen-containing basic compound having no acidic group. This has the effect of improving PED stability (resist performance does not change with time from exposure to subsequent heating). The preferred organic basic compound having no acidic group that can be used in the present invention is a compound that is more basic than phenol.
The acidic groups that the organic basic compound does not have include phenolic hydroxyl groups, sulfonic acid groups, and phosphoric acid groups. In particular, a nitrogen-containing basic compound having no acidic group is preferable, and examples thereof include compounds having the following structures.

[0159]

Embedded image

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl having 1 to 6 carbon atoms. 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.

[0161]

Embedded image

(Wherein, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R
²⁵⁶ independently 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 examples of the nitrogen-containing basic compound include guanidine, 1,1-dimethylguanidine,
1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine,
-Dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-
Amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-amino Ethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) Pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-
3-methyl-1-p-tolylpyrazole, pyrazine, 2
-(Aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-
Aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4.3.0] nona
5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2]
Octane, 2,4,5-triphenylimidazole, N
-Methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethylthiourea (CHMET
U) and other tertiary morpholine derivatives, JP-A-11-5257
Hindered amines described in Japanese Patent Publication No. 5 (for example, those described in the publication [0005]) are exemplified, but not limited thereto.

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

Among them, 1,5-diazabicyclo [4.
3.0] non-5-ene, 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 basic compounds having no acidic group are used alone or in combination of two or more.
The amount used is generally 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the solid content of the entire radiation-sensitive positive resist composition. If the amount is less than 0.001% by weight, the effect of the addition of the basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed portion tends to deteriorate.

[8] The resist composition of the present invention comprises a component (F) a fluorine-based surfactant, a silicon-based surfactant, a surfactant containing both a fluorine atom and a silicon atom, and a nonionic surfactant. It is preferable to contain one or two or more of the agents. This is effective in reducing the particle initial value when the resist component is dissolved in the solvent.

As these surfactants, for example, those described in
No. 62-36663, JP-A-61-226746, JP-A-61-226745,
JP-A-62-170950, JP-A-63-34540, JP-A-7-23016
No. 5, JP-A-8-62834, JP-A-9-54432, JP-A-9-598
No. 8, U.S. Pat.No. 5,405,720, No. 5360692, No. 5529881,
No. 5296330, No. 5436098, No. 5576143, No. 5294511
And No. 5,824,451, and the like, and the following commercially available surfactants can be used as they are. As a commercially available surfactant, for example, F-top EF301, EF303, (manufactured by Shin-Akita Chemical Co., Ltd.), Florad FC43
0, 431 (manufactured by Sumitomo 3M Limited), Mega Fuck F171, F1
73, F176, F189, R08 (Dai Nippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troysol S-366 (Troy Chemical Co., Ltd.) )) Or a silicon-based surfactant. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant.

The amount of the fluorine-based and / or silicon-based surfactant is usually 0.001% by weight to 2% by weight, preferably 0.1% by weight, based on the solid content in the composition of the present invention.
It is from 01% by weight to 1% by weight. These surfactants may be added alone or in some combination. Examples of the surfactant that can be used in addition to the above include, specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether. , Polyoxyethylene alkyl allyl ethers such as polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan Monooleate, sorbitan trioleate,
Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate,
Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate can be exemplified. The amount of these other surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, more preferably 0.01 to 1% by weight, per 100 parts by weight of the solids in the composition of the present invention. It is.

[0170]

[9] Other components The resist composition of the present invention further contains an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, and a compound that promotes solubility in a developing solution, if necessary. Can be done.

The solution composition of the present invention is applied on a substrate, and the solvent is removed by subsequent drying to form a resist coating film. The thickness of this coating film is 0.02 to 1.2 μm.
m is preferable, and more preferably 0.05 to 0.35 μm
It is. In the present invention, the formed resist coating film has a wavelength of 40 to 70% / 200 with respect to light having a wavelength of 193 nm.
It is preferable to have a transmittance of μm, especially 45 to 65% / 200 μm. When the resist coating film has the transmittance in the above range, it is possible to obtain a rectangular profile in which only a standing wave is not generated, and a preferable result is obtained.

As a method of adjusting the transmittance, for example, the transmittance of the composition for light having a wavelength of 193 nm can be adjusted by the type, copolymerization ratio, and molecular weight of each repeating unit in the resin (A1). . Further, component (B) having absorption at the wavelength, acid-decomposable dissolution inhibiting compound, dye, plasticizer, surfactant, photosensitizer, organic base compound,
And by appropriately adjusting the amount of a compound that promotes the solubility of the exposed portion in a developer.

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

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

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

[0176]

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.

[(A1) Synthesis example of acid-decomposable resin] (1) Norbornene, tert-butyl acrylate, and maleic anhydride were charged into a reaction vessel at a molar ratio of 40/20/40, and dissolved in methyl ethyl ketone. Min 60%
Was prepared. This was heated at 60 ° C. under a nitrogen stream. 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 10 hours, the reaction mixture was diluted twice with methyl ethyl ketone, and then poured into a large amount of tert-butyl methyl ether to precipitate a white powder. The precipitated powder was taken out by filtration and dried to obtain the target resin (1). When molecular weight analysis of the obtained resin (1) by GPC was attempted, it was 15300 (weight average) in terms of polystyrene. In addition, from the NMR spectrum, the resin (1)
Has a molar ratio of norbornene / t-butyl acrylate / maleic anhydride of the present invention of 38/17/45.
Met. Resins (2) to (14) were synthesized in the same manner as in Synthesis Example (1). Table 1 shows the resin composition ratio and the weight average molecular weight (Mw).

[0178]

[Table 1]

Examples 1 to 18 and Comparative Examples 1 to 8 [Preparation of Radiation-Sensitive Positive Resist Composition] Acid Decomposable Resin 1.37 g Photoacid Generator 30 mg Basic Compound 1.5 mg (D) Compound 3 30 mg of 0 mg surfactant was blended and dissolved in 6.0 g of the solvent shown in Table 2. The obtained solution was filtered through a 0.1 μm microfilter to prepare radiation-sensitive positive resist compositions of Examples 1 to 18 having the compositions shown in Table 2. In addition, as shown in Table 2, as Comparative Examples 1 to 8, a radiation-sensitive positive resist composition was prepared in the same manner as in Examples 1 to 18, except that a compound not corresponding to the component (D) was used. Prepared.

[0180]

[Table 2]

The compounds (D) and (B) photoacid generators used are indicated by the numbers of the specific examples described above. The nitrogen-containing basic compounds are as follows. 1: 1,8-diazabicyclo [4.3.0] nona-5
-Ene 2: 2,6-diisopropylaniline 3: 4-dimethylaminopyridine 4: 2,4,5-triphenylimidazole 5: triethylamine 6: 1,5-diazabicyclo [4.3.0] nona-5
-Ene 7: 1,5-diazabicyclo [2.2.2] octane 8: hexamethylenetetramine 9: CHMETU 10: bis (1,2,2,6,6-pentamethyl-4)
-Piperidyl) sebagate 11: piperazine 12: phenylguanidine

The surfactants are as follows. W1: Megafac F176 (manufactured by Dainippon Ink and Chemicals, Inc.) (fluorine) W2: Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.) (fluorine and silicone) W3: Polysiloxane polymer KP-341 (Manufactured by Shin-Etsu Chemical Co., Ltd.) W4: polyoxyethylene triphenyl ether W5: Troysol S-366 (Troy Chemical Co., Ltd.)
Made)

The solvents are as follows. S1: propylene glycol monomethyl ether acetate S2: propylene glycol monomethyl ether propionate S3: ethyl lactate S4: butyl acetate S5: 2-heptanone S6: propylene glycol monomethyl ether S7: ethoxytyl propionate S8: γ-butyrolactone S9 : Ethylene carbonate S10: propylene carbonate S11: cyclohexanone

(Evaluation Test) The resist solution prepared above was applied to a DUV30 (1600) manufactured by Brewer using a spin coater.
After coating on the substrate coated with Å) at a film thickness of 3500 Å or less, it was dried at 140 ° C. for 90 seconds to obtain a resist film.

The wafer thus obtained was subjected to an excimer laser (KrF (wavelength: 248 nm), ArF
(Wavelength: 193 nm), F ₂ (wavelength: 153 nm)) and electron beam (EB). Thereafter, the mixture was heated in a clean room at 125 ° C. for 90 seconds, and then heated with a tetramethylammonium hydroxide developer (2.38% by weight).
The pattern was developed for 2 seconds and rinsed with distilled water. The resist pattern of the silicon wafer thus obtained was observed with a scanning electron microscope. Further, the resist was evaluated as follows. Table 3 shows the evaluation results.

[PED stability]: A resist composition solution was applied and baked to form a resist film having a thickness of 0.15 μm.
(For example, ArF excimer laser: 14 mJ / cm ² or EB: 10 μC / c)
m ² ), and the wafer subjected to the irradiation step was left in a clean room for 2 hours. Subsequently, development was carried out following baking after radiation irradiation, and the deviation of the 0.15 μm line and space pattern from the designed dimensions was measured. | Design dimension-Actual dimension | / Design dimension × 100 (%) It was judged that the smaller the value, the better.

[Number of particles and number of particles increased after storage over time]: Immediately after preparation of the radiation-sensitive positive resist composition solution (coating solution) prepared as described above (initial value of particles), and at 4 ° C. The particles in the liquid after standing for one week (the number of particles after aging) were counted by a particle counter manufactured by Rion. Along with the initial particle value, (number of particles after aging)
-The particle increase calculated by (initial value of particles) was evaluated.

[0188]

[Table 3]

As shown in Table 3, the radiation-sensitive positive resist composition of the present invention has an improved resist pattern shape irrespective of the wavelength of the ionizing radiation to be irradiated.

[0190]

As described above, the chemically amplified radiation-sensitive resist composition of the present invention has an improved resist pattern shape irrespective of the wavelength of ionizing radiation to be irradiated.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/45 C08K 5/45 5/46 5/46 C08L 101/14 C08L 101/14 G03F 7/039 601 G03F 7/039 601 H01L 21/027 H01L 21/30 502R (72) Inventor Shoichiro Anami 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Inside Fujisha Shin Film Co., Ltd. (72) Inventor Tsukasa Yamanaka, Yoshida-cho, Haibara-gun, Shizuoka Prefecture 4000 No. Kawajiri F-term in Fuji Shashin Film Co., Ltd. EV307 EV317 EW176 FD319 GP03 HA05

Claims (4)

[Claims] (1) a resin whose dissolution rate in an alkali developing solution is increased by the action of an acid, (B) a compound which generates an acid upon irradiation with ionizing radiation, (C) a solvent, and (D) a bond formed by an acid. A radiation-sensitive positive resist composition, which is cleaved to generate an ionic compound, wherein at least one of the ionic compounds contains a compound that does not react with the proton-donating compound in the composition. 2. The composition according to claim 1, wherein the component (D) is at least one selected from the group consisting of compounds represented by the following general formulas (1) and (2).
The radiation-sensitive positive resist composition according to claim 1, wherein the composition is a seed. Embedded image In the general formula (1): A ₁ and A ₂ each independently represent an electron donating group. Z is a carbon atom, —SO ₂ —, or —C
(= O)-. E represents a 3- to 7-membered ring structure containing an adjacent carbon atom, oxygen atom and Z, and this ring structure may have a substituent and a condensed ring. In the general formula (2): G represents two adjacent carbon atoms and X
And an electron-donating ring structure in which at least one other ring having a substituent is condensed with a 3- to 8-membered ring structure. X represents a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. Z and E have the same meanings as Z and E in the general formula (1). 3. The radiation-sensitive positive resist composition according to claim 1, further comprising (E) a nitrogen-containing basic compound. 4. The radiation-sensitive positive resist composition according to claim 1, further comprising (F) a surfactant.